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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1521-1772
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
CONTENTS
Abstract
The aim of this study is the treatment of liquid effluents from a petroleum industry (NAFTAL /Algeria) by an electrochemical
treatment process (electrocoagulation). The electrocoagulation has proved to be useful for the treatment of wastewater, but in order
to enhance its ecological characteristic we found it would be essential to carry out our experiments with ecological energy derived
from a photovoltaic solar module, which would contribute to sustainability objectives. The electrocoagulation process in a
continuous mode using anodes (aluminum and iron) and a graphite cathode was studied. Changes in the Chemical Oxygen Demand
were analyzed which stated the efficiency of the method. The current density, the duration of treatment, the pH and the amount of
electrolyte added in order to optimize these operating parameters lead to a better reduction of the pollution load. After 1h of
electrolysis, optimum conditions were: current density of 100 A/m2, with initial pH 7.4 and a flow rate of 3.94.10-3 L/s. More than
94% of COD were removed with an aluminum anode.
Key words: COD removal, electrocoagulation, electrode, petroleum oil, photovoltaic energy
Received: January, 2014; Revised final: July, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: mdtaleb_fr@yahoo.fr; Phone: +213 21 24 79 19; Fax: +213 21 24 79 19
Ighilahriz et al./Environmental Engineering and Management Journal 17 (2018), 7, 1521-1529
wastewater in the oil industry should be developed. In effects of the main operating variables on the
recent years, there has been a growing interest for the efficiency of the EC process, like the anode materials,
use of electrochemical methods for the treatment of the operating time and the current density in order to
industrial wastewater especially electrocoagulation determine the optimal conditions for it to remove
(EC). This process is well known in wastewater pollutants. The sludge formed was characterized. The
treatments (Martinez-Huitle and Brillas, 2009; second purpose of the study was to explore a new
Mohammed et al., 2009). In fact, it has been solution for treating oily wastewater with a renewable
successfully used for the treatment of drinking water energy through a photovoltaic solar power which is a
(Pop et al., 2017; Vik et al., 1984) and wastewaters new form of non-polluting, abundant and renewable
generated from aquaculture (Lin and Chen, 1997), energy. Photovoltaic modules last long and involve
industries (Ramirez, 1981), textile industry (Lin and low maintenance costs (Valero et al., 2008); they can
Peng, 1996; Pajootan et al., 2016), tannery industry produce a high direct current when exposed to the
(Benhadji et al., 2011), restaurants (Chen et al., 2000), sunlight and connected in series and/or in parallel.
landfill leachate, municipal sewage (Biwyk et al., Based on the above facts, the photovoltaic energy can
1980) and urban wastewater (Pouet and Grasmick, be used directly in electrocoagulation to treat
1995). This process was used to remove phenol (Awad wastewater, and this is becoming a popular trend in the
and Abuzaid, 2000) and surfactants (Ciorba et al., environmental protection field. The use of the
2000) and even the oil industry (El-Naas et al., 2009; photovoltaic solar power, an eco-friendly energy can
Hariz et al., 2013) used it to cut oil–water emulsions produce a high direct current when exposed to
(Bensadok et al., 2008), oil suspension used for sunlight. The photovoltaic module can be installed
machining and drilling operations (Pansares et al., near a remote or absent power region (Navarro-Solis
2008) and for oil drilling mud treatment (Ighilahriz et et al., 2010; Valero et al., 2008; Zhang et al., 2013).
al., 2013). Electrocoagulation (EC) is an effective
method wherein the flocculating agent is produced by 2. Material and methods
the electro-oxidation of a single-use anode made of
iron or aluminum mostly. This process turns a suitable 2.1. Water samples
pH into an insoluble metal hydroxide that can remove
pollutants. In this process, the treatment is done An effluent was selected from NAFTAL
without the addition of chemical flocculants or (Algeria) oil industry which contains kerosene/ water
coagulants, thereby reducing the amount of sludge that emulsions taken downstream of the local sewage
should be removed. treatment plant at the industrial site. The sample
This technique is easy and requires simple containers were preserved in a refrigerator at 4°C
equipment and a small amount of sludge (Mollah et before use. At the beginning of the study, the main
al., 2004; Yehya et al., 2015) is produced. Its characteristics of the collected samples were analyzed
technology’s efficiency and reliability were stated and and the water temperature was increased to the room
it provides an environmentally compatible method to temperature before each electrocoagulation test. Table
reduce a wide variety of pollutants (Ciorba et al., 1 shows the characteristics of the effluent used during
2000). the process.
During the electrocoagulation process, the
electrochemical reactions of electrodes in aluminum Table 1. The main characteristics of oily wastewater
are summarized as follows:
Permissible levels
At the anode Eq. (1): Parameters Values
[Decree, 2006]
3+ COD (mg O2/L) 292 100
𝐴𝐴𝐴𝐴(𝑠𝑠) → 𝐴𝐴𝐴𝐴(𝑎𝑎𝑎𝑎) + 3𝑒𝑒 − (1) BOD5 (mg O2/L) 30 25
pH 7.50 5.5-8.5
At the cathode: Conductivity
0.36 -
The reaction occurring at the cathode is dependent on (mS/cm)
pH. Indeed, under neutral or basic conditions Turbidity (NTU) 2.32 -
hydrogen is produced through Eq. (2), whereas under
acidic conditions, Eq. (3) better describes the 2.2. The electrocoagulation unit
hydrogen evolution:
It is composed of two compartments. The first
− −
2𝐻𝐻2 𝑂𝑂(𝑙𝑙) + 2𝑒𝑒 → 𝐻𝐻2(𝑔𝑔) + 2𝑂𝑂𝐻𝐻(𝑎𝑎𝑎𝑎) (2) consists of a 10-L cylindrical tank. The second
compartment is provided with a cathode of graphite
+
2𝐻𝐻(𝑎𝑎𝑎𝑎) + 2𝑒𝑒 − → 𝐻𝐻2(𝑔𝑔) (3) and anodes of cylindrical shapes made of aluminum
(with a 0.8-cm internal diameter, a 12.1-cm height
with an active area of 30.39 cm2) and iron (with 0.3-
In this study, EC using aluminum and iron
cm internal diameter, a 12.1-cm height with an active
electrodes in continuous mode was studied in the
area of 11.39 cm2). The electrodes were placed at the
treatment of an oily wastewater generated from a
middle bottom of the reactor, parallel to each other in
petroleum industry at Dar el Beida (Algiers, Algeria).
the cell at a fixed distance of 1 cm. The EC cell was
The first purpose of this study was to observe the
fed continuously by a peristaltic pump (Iwaki Magnet
1522
Efficiency of an electrocoagulation treatment of water contaminated by hydrocarbons in a continuous mode
Pump; 16-19 L/min) with the effluents from a initial pH, the duration of the EC, the nature of the
wastewater tank. The reactor operates as a closed electrode material and the current density. In order to
reactor with full recirculation, the total solution does extend the process performance, the effects of those
not exceed 2-L, and electrodes were connected to a DC parameters were studied and the results are stated
power supply (HEP-613; 0-2 A; 40-V). The cell was below. The solution was prepared with 1 L of pure
powered by a photovoltaic system. The battery had an effluent and 1 L of distilled water which led us to add
internal resistance of 17 mΩ, a 4.8 A maximum electrolyte support to raise the solution conductivity,
charging current and a minimum safe end discharge to decrease the voltage between electrodes due to the
voltage of 1.60 V/cell. The SOLAR23 solar module decreased resistance of polluted water and to reduce
line was especially designed for PV off grid systems energy consumption.
and covered modules in the range from 5 to 100 Wp.
Samples were taken at various time interval. The 3.1. Effect of current density and electrolysis duration
experimental equipment is schematically shown in on EC process
Fig. 1.
The operation lasted 2 h; samples were taken The current density is considered as a key
from the reactor every 15 min and were analyzed. parameter in EC (Khemis et al., 2006; Xu and Zhu,
Their pH, conductivity and COD were determined. 2004) especially for the reduction kinetics of COD. It
The pH measurement was carried out with a HANNA is knowledged that current density determines the
Digital Display model SED pH meter using 12500 V. production rate of coagulant as well as the adjustment
The conductivity measurements were made by using a of bubble production, and hence it affects the growth
HANNA.COD conductivity meter. COD was of flocs (Chen et al., 2004; Mollah et al., 2004). In
measured using a thermo ECO reactor refluxing by order to assess the effect of the applied current density,
titration method following the NFT 90-101 standard. a set of experiments was planned at an initial pH 7.4
Boiling under reflux in the presence of mercury sulfate (since it was the natural pH of the solution) and
(II), a test sample, in the presence of a known amount varying applied current density (50-125 A/m2) for a
of potassium dichromate and a silver catalyst, strongly concentration of supporting salt NaCl of 0.5 g/L.
acidified with sulfuric acid for a period of time during The COD reduction kinetics goes fast during
which a portion of dichromate was reduced by the the first 15–30 min of EC and is almost stabilized
oxidizable matter present in the solution. The thereafter. One can say that when the current density
dichromate excess was titrated with a standard increases, the processing time decreases thanks to the
solution of iron sulfate (II) and ammonium. strong electrodes dissolution. In fact, when current
Calculation of COD was done from the amount of the density increases the production rate of hydrogen
reduced dichromate. BOD5 analysis was carried out by bubbles increases and their size decreases. This
a Schrank Aqua Lytic Thermostat following the NF highlights an effective elimination of the pollutant by
T90-103 standard. The sample was incubated for 5 flotation (Ben Hariz et al., 2013). Moreover, the
days at 20 °C. The microorganisms consumed the increase of current density entails the increase in the
dissolved oxygen and the carbon dioxide released was amount of coagulant as a consequence of greater
trapped by sodium hydroxide. The amount of sludge removal rate. At a lower current density, the anode
generated after the EC treatment under optimal dissolution does not provide a destabilization of
conditions using aluminum electrodes was particles because of the low anode dissolution rate.
characterized using a FT-IR spectrometer (Perkin- However, some COD removal is noticeable
Elmer N°200139). which can be explained by an indirect oxidation of the
oil suspension provided by oxidizing species such as
3. Results and discussion ClO- allowing the indirect electrochemical treatment
of the wastewater (Adhoum et al., 2004). The most
The EC process is quite complex and is significant reduction rate (92 %) occurred at a current
affected by several operating parameters such as the density of 100 A/m2 for 1 h.
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Ighilahriz et al./Environmental Engineering and Management Journal 17 (2018), 7, 1521-1529
The fact that for higher current densities the final pH, the treated solution was adjusted between pH
COD removal decreases can be explained by an 4 and pH 10 with 0.1 M sodium hydroxide or 0.1 M
overdose of coagulant, which can carry an excessive hydrochloric acid. The current density was set at
adsorption of cations and reversing the charge of the 100A/m2 and likewise the NaCl concentration was
particles. The particles could then be stabilized again fixed at 0.5 g/L. Fig. 3 shows that COD removal
(Amirtharajah and O'Melia, 1990). Fig. 2 (a) proves increased from 34 % for pH 4 to 92 % for pH 7.4.
that duration has effects on experimental change Former studies already revealed that EC gave best
results in COD reduction for different current results when the initial pH varied from pH 3 to neutral
densities. pH 7 forming a majority of aluminum complexes
From Fig. 2 (b) one can infer that the decrease which played an active part during the removal of
in conductivity, being related to the current density pollutant through EC (Alaton et al., 2009).
during this spell of time, is due to the precipitation of With a pH 8 solution the removal efficiency
salts produced during the EC reaction with aluminum decreased because of the amphoteric character of the
electrodes. For the case of the experiments made at aluminum hydroxide Al(OH)3 whose solubility
150 A/m2 the conductivity is lower. The reason of this increases when the solution becomes either more
finding may be that the increment of current density acidic or alkaline (Bensadok et al., 2008; Koparal and
causes an excessive presence of ions produced during Ogutveren, 2002; Mollah et al., 2004). Moreover, a
EC leading to lower conductivity measured after high pH entails the formation of Al(OH)4−, which is
decantation. The forthcoming experiments were all soluble and useless for the removal of oil emulsion
run at the current density of 100 A/m2. (Koren and Syversen, 1995). Therefore, a further
increase of the influential pH does not help the COD
3.2. Effect of initial pH on EC process removal.
During the electrolysis the solution pH changes
It is established that the initial pH is a as shown in Fig. 4 and thus, the final pH was 6.3, 7.2,
significant factor affecting the electrocoagulation 7.3, 8.3 for the initial pH of 4, 5, 6, 7.4 respectively,
process (Asselin et al., 2008; Yildiz et al., 2008). In which was due to the OH- ions produced in the solution
order to study its effect on the COD removal and the by the water electrolysis.
Fig.2. Effect of current density on: (a) COD and (b) conductivity vs. time.
pH=7.4, CNaCl=0.5g/L, Q=5.79.10-3 L/s (Aluminum anode)
Fig.3. Effect of initial pH on COD, j= 100 A/m2, t=1h, CNaCl=0.5g/L, Q=5.79.10-3L/s (Aluminum anode)
1524
Efficiency of an electrocoagulation treatment of water contaminated by hydrocarbons in a continuous mode
We can observe that for a medium alkaline pH gradually increased from 3.94.10-3 to 16.3.10-3 L/s at
of 8, the final pH was not that different (pH = 8.5). For 100 A/m2; pH = 7.4 and CNaCl = 0.5 g/L.
a basic pH of 10, the final pH decreased to 9.3 by the
production of H+. On one hand, metal hydroxides
Al(OH)3 are formed and on the other hand, the
oxidation of water to oxygen can help to reduce the pH
of the water to be treated (Chen et al., 2004).
In order to study the effect of NaCl on the COD The composition of the electrode material is a
removal (Fig. 5), various concentrations were key element in the electrochemical treatment; the
analyzed (from 0.25 to 1.0 g/L). choice of the adequate electrode material is important
to reach better removal efficiency.
3.4. Flow rate effect on EC process Aluminum and iron are commonly used
because they are cheap. Thus, experiments were
In order to investigate the effect of time on the conducted for both aluminum and iron anodes under
COD removal efficiency, the flow rate at start (Q) was the same operational conditions.
1525
Ighilahriz et al./Environmental Engineering and Management Journal 17 (2018), 7, 1521-1529
𝑈𝑈𝑈𝑈𝑈𝑈
Fig. 7 shows the effect of current density on 𝐸𝐸𝐶𝐶 = × 103 (7)
𝑉𝑉×𝛥𝛥𝛥𝛥𝛥𝛥𝛥𝛥
COD removal. We found out that the rate of COD
reduction at a current density of 100 A/m2 was greater
where U is cell voltage (V), I is the applied electrical
with aluminum electrode whereas it was almost the
current (A), t is the reaction time (h), V is the reactor
same at a current density of 50 A/m2. With a density
volume (L) and ΔCOD is the subtraction of COD (mg
of 125 A/m2, removal was more effective with iron
O2/L) before and after the electrolysis (COD removed
anodes. The trends for COD removal in Fig. 7 by
during electrochemical treatment).
different anode materials (aluminum and iron) did not
have the same trends at different current densities this
can be explained by the generation of various shapes
and multiples species of Aluminum such as
monomeric species including, Al(OH)2+ , Al(OH)+2 ,
Al(OH)- 4 and Al2(OH)4+2 and the polymeric species
such as Al2(OH)+5 , Al6(OH)3+15 , Al13(OH)5+34 ,
Al7(OH)4+17 , Al8(OH)204+ , Al13O4(OH)7+24 (Mollah et
al., 2001).
𝐶𝐶ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢
Fig.7. Rate abatement as function of current density using 𝐶𝐶𝐶𝐶𝐶𝐶 = × 103 (8)
𝑉𝑉×∆𝐶𝐶𝐶𝐶𝐶𝐶
pH = 7.4, t=1h, CNaCl=0.5 g/L, Q= 3.94.10-3 L/s
for aluminum and iron electrodes The electrode consumption (kg/kg COD) was
calculated according to Eq. (9):
Both followed the same trends and the scatter
diagram shows that the optimum pH obtained with the 𝐼𝐼×𝑡𝑡×𝑀𝑀
aluminum electrodes (7.4) is not the same as with iron 𝐸𝐸𝐸𝐸𝐸𝐸 = × 103 (9)
𝑛𝑛×𝐹𝐹×∆𝐶𝐶𝐶𝐶𝐶𝐶×𝑉𝑉
(6.0). This can be explained by the fact that aluminum
hydroxide has a greater compatibility with the where: M is the molar mass (kg ̸mol), n is the valence
pollutant compared to iron hydroxide. number (= 3) and F is the Faraday constant (96485
Fig. 8 compares the COD reduction according C.mol−1).
to pH with both electrodes and shows the worse results As seen in Fig. 9, a band appeared at 3434
obtained with iron electrodes under the same operating corresponding to O-H stretching (Jewel et al., 2007),
conditions as the experiments with aluminum - namely whereas the peak towards 1643 cm–1 is due to the
pHi equal to 7.4, Q =3.94.10-3 L/s, j = 100 A/m2 and presence of bending hydroxyl (Drouiche et al., 2009).
[NaCl] = 0.5 g/L. Indeed, a reduction of 95% was The operating cost was calculated from the following
achieved with aluminum electrodes against 69% with expression Eq. (10) (Khandegar and Saroha, 2013):
iron.
𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 𝑎𝑎𝑎𝑎𝑐𝑐 + 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 + 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 (10)
3.6. Electrical energy consumption
where: a is the electrical energy price (0.022 US$ per
kWh), b corresponds to the chemical consumption
One of the most important factors to be taken
price (12.60 US$ per kg of added NaCl) and c is the
into account for the selection of a water treatment
electrode material consumption (3.8 US$ per kg of
process is the cost. Electrodes, chemicals and the
aluminum). Working at 100 A/m 2 during 1 h of
energy used during EC add up to the process operating
electrolysis, Q= 3.94.10-3 L/s and CNaCl = 0.5 g/L and
costs (Ayhan Şengil and Özacar, 2006; Gebologlu,
pH 7.4, the operating cost of EC was 0.0761US$ per
2010; Kobya et al., 2003, Khandegar and Saroha,
kg of COD, with Algeria price electricity. These costs
2013). The electrical energy required for the removal
are in agreement with those given in the literature
of COD using aluminum electrodes was calculated in
(Saeedi and Khalvati-Fahlyani, 2011).
terms of kWh/kg COD using Eq. (7):
1526
Efficiency of an electrocoagulation treatment of water contaminated by hydrocarbons in a continuous mode
3.7. Characterization of sludge obtained with the EC effluent with aluminum and stainless-steel electrodes,
Journal of Hazardous Materials, 164, 1586-1594.
The sample obtained under the optimal Amirtharajah A., O’Mella C.R., (1990), Coagulation
conditions using aluminum electrodes was filtered to Processes: Destabilization, Mixing, and Flocculation,
In: Water Quality and Treatment: A Handbook of
get the sludge formed during the EC in order to be Community Water Supplies, Pontius F.W. (Eds.),
analyzed with the Fourier Transform Infrared AWWA, McGraw-Hill Inc., New York, 269-365.
Spectroscopy (FT-IR). The characteristic of Al–O-H Asselin M., Drogui P., Benmoussa H., Blais J.F., (2008),
bending is represented by the band at 872 cm−1 (Jewel Effectiveness of electrocoagulation process in
et al., 2007). These results account for a mechanism in removing organic compounds from slaughterhouse
which the pollutant was removed from wastewater in wastewater using monopolar and bipolar electrolytic
the EC process. In fact, the sludge contains aluminum cells, Chemosphere, 72, 1727-1733.
hydroxide in a major part which proves that the Al was Ayhan Şengil I., Özacar M., (2006), Treatment of dairy
turned into sludge. wastewaters by electrocoagulation using mild steel
electrodes, Journal of Hazardous Materials, 137, 1197-
1205.
4. Conclusions Awad Y.M., Abuzaid N.S., (2000), The influence of
residence time on the anodic oxidation of-phenol,
This study confirms that the electrocoagulation Separation and Purification Technology, 18, 227-236.
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Treatment of petroleum refinery sulfidic spent caustic
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residual (18 mg O2/L) was less than the permissible Bensadok K., Benammar S., Lapicque F., Nezzal G., (2008),
level of 100 mg O2/L. The operational cost of EC was Electrocoagulation of cutting oil emulsions using
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1530
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1531-1544
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
The performance of cathode affects the overall performance of a microbial fuel cell (MFC), and cathode configuration affects the
fabrication cost of this bioelectrochemical system in a large way. Various modifications in cathode structures have been observed
in MFCs. Among them air-cathode MFCs are considered to be the most efficient and sustainable option due to elimination of
aeration, as required in aqueous cathodes which consumes energy and increases operating cost of MFCs. An air cathode usually
consists of (a) a conductive base material, (b) current collectors, (c) catalyst layer, (d) binder layer, and (e) diffusion layer. In this
article the recent advances made in fabrication of air-cathode MFC are reviewed. The advantages and disadvantages of different
materials used for preparation of an air-cathode are analyzed. On-field application of MFC is limited even after a decade of
extensive research. This article also presents the challenges incurred in scaling-up of an MFC for real field application. In addition,
this review will assist to realize the advantages and disadvantages of different materials used in construction of air-cathodes. This
knowledge will help in intelligent selection of materials for fabrication of air-cathode MFC in future and will further aid to achieve
a competitive technology for electricity harvesting while treating wastewater.
Key words: air-cathode, binder, catalyst, current collector, microbial fuel cell
Received: January, 2014; Revised final: July, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: E-mail: ghangrekar@civil.iitkgp.ac.in; Phone: +91-3222-283440; Fax: +91-
3222-282254
Chatterjee et al./Environmental Engineering and Management Journal 17 (2018), 7, 1531-1544
application of MFCs are high fabrication cost and low oxygen reduction reaction at aqueous cathode is
energy conversion efficiency (Li et al., 2010; Oliveira restricted due to limited availability of oxygen. The
et al., 2016; Zhang et al., 2010b). Rozendal et al., single-chambered air cathode offers several
(2008) estimated capital costs for fabrication of advantages over two-chambered systems such as: (a)
MFCs, based on materials currently being used in the the catholyte does not need to be aerated, oxygen in
laboratory. They showed that the price of electrode the air can directly react at the electrode, (b) recycling
materials and separator can account for the 57% of or chemical regeneration of the catholyte is not
total capital cost. Hence to reduce the capital cost, it is required, (c) higher volumetric power density is easily
necessary to design efficient electrodes and achievable due to smaller cell volume (Liu and Logan,
search/synthesize cheaper electrode and separator 2004), and (d) the overall volume and footprint of the
materials. The material selected for separator should MFCs will be less in air cathode configuration due to
be effective in proton transfer, should minimize elimination of a cathodic chamber.
substrate diffusion from anode to cathode and also In spite of these advantages offered by air-
oxygen diffusion from cathode to anode (Alvarez- cathode MFCs, there are certain disadvantages related
Gallego et al., 2012). The material selected for mostly to the materials used in construction. The
electrode should offer higher specific surface area, and major disadvantages associated with air-cathode
cathode material should have lower oxygen reduction MFCs are (a) fouling of the cathode surface exposed
overpotential (Sevda et al., 2013). to air, (b) diffusion of oxygen into anodic chamber, (c)
There are a number of review articles electrolyte loss due to evaporation (Wei et al., 2011),
describing various aspects of MFC. However, most of (d) necessity of a catalyst on cathode for enhancing
them are based on particular topics like non-platinum oxygen reduction reaction (Freguia et al., 2007), and
based catalyst (Ben Liew et al., 2014), nano-carbon as (e) requirement of a binder. This review attempts to
electrode material (Ghasemi et al., 2013a), graphene elaborate the advantages and disadvantages of
based electrodes (Wang et al., 2013), anode different materials used in construction of air-
architecture (Kumar et al., 2013), and overall cathodes. This knowledge will help in intelligent use
development of MFC (Bullen et al., 2006; Du et al., of materials for making different components of air
2007; Logan et al., 2006a; Oliveira et al., 2013a; cathode MFC in future.
Rabaey and Verstraete, 2005). Power output of a MFC
can be increased by improving performance of the 3. Components of air cathode
cathode (Liu and Logan, 2004). Researchers have thus
focused on the performance of cathode as the most The separator has anolyte on one side and it is
challenging aspect of MFC design (Zhang et al., exposed to air on the other side. An air cathode usually
2011b). A MFC configuration consisting of an anode consists of (a) a conductive base material, (b) current
and a cathode chamber separated by a proton exchange collector, (c) catalyst layer, (d) binder layer, and (e)
membrane (PEM) is difficult to implement on a large diffusion layer (Wei et al., 2011).
scale (Kim et al., 2009). Therefore, researchers are
focusing on simpler reactor design to overcome this 3.1. Conductive base materials
problem. For example, single chamber air cathode
MFCs have been studied, where the cathode does not The base material for the electrode provides a
require placement in water (Ahmed et al., 2012; conductive path to the external circuit. To function as
Cheng et al., 2006; Duteanu et al., 2010; Feng et al., a good electrode, a material should have the following
2011; Kim et al., 2009; Liu and Logan, 2004; Logan properties namely (a) good conductivity, (b) high
et al., 2006b). Elmekawy et al., (2013) reviewed the chemical stability, (c) high mechanical strength, and
different challenges and potential opportunities of (d) low cost (Sharma et al.). Carbon in paper or cloth
microfluidic microbial fuel cells and mentioned that form is the most widely used material in air cathodes
these micro-sized MFCs offered lower internal (Ahmed et al., 2012; Cheng et al., 2006; Martin et al.,
resistance. In this article, the recent advances in air 2011; Shi et al., 2012; Sun et al., 2009; Zhang et al.,
cathode MFCs are explored. To overcome the 2009b). Although carbon is not very conductive, its
difficulties in scaling up of MFCs, the challenges that stability and lack of reactivity makes it a suitable
need to be addressed for practical implementation are electrode material. However, carbon cloth is
also discussed. expensive (Zhang et al., 2010a) and longtime stability
of carbon paper is doubtful due to the brittleness of the
2. Single chamber MFC: Advantages and material.
disadvantages Electrodes made of metals and alloys such as
stainless steel (SS) can also be used. For example,
In an attempt to minimize the operating cost of Zhang et al. (2011b) constructed a cathode by
MFCs air breathing single chambered MFCs were impregnating carbon powder around a stainless steel
developed by researchers. The major reaction that mesh and obtained a power density of 1616 mW/m2.
takes place at the cathode is reduction of oxygen. The Simple or modified carbon powders are also being
solubility of oxygen (mole fraction basis) in water is increasingly used as electrode materials (Duteanu et
only 4.6*10-6 at 25 °C, while that in air it is 0.21 al., 2010). Zhuang et al., (2010) applied a nickel (Ni)
(Logan, 2008; Wei et al., 2011). Because of this, based paint and manganese dioxide (MnO2) catalyst to
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A brief review on recent advances in air-cathode microbial fuel cells
carbon cloth and obtained a volumetric power density 3.2. Current collectors
of 11 W/m3. This carbon cloth served as both a
membrane and the base material for the cathode. It Although carbon based electrodes are
showed a high proton diffusion rate, reduced the extensively used in MFCs, these materials have very
internal resistance and gave higher power output. Sun low electrical conductivity. This can contribute to
et al., (2009) obtained a power density of 878 mW/m3 increased ohmic losses in larger anodic volume
using a platinum catalyst on carbon paper as cathode. (Zhang et al., 2010b). Rozendal et al., (2008) reported
Martin et al., (2011) used a platinum (Pt) catalyst on that the electrical resistance of graphite is 1375 µΩ
carbon paper cathode and obtained a power density of cm, while that of the metal titanium is 42 µΩ cm.
90 W/m3. Inclusion of a metal current collector on the cathode
This suggests, in spite of same cathodic surface can ensure proper distribution of current and
material used, the power output obtained is different also reduces the ohmic losses (Zhang et al., 2010b).
due to several reasons like differences in the MFC Zhang et al., (2011b) used commercially available
configuration, catalyst loading, anolyte composition, stainless steel (SS) mesh with varying characteristics
mode of operation, temperature, pH etc. Performance as current collectors and found that MFC performance
of some air cathode MFCs using different materials varies as a function of the current collector. The
for cathodes are listed in Table 1 through Table 4. An performance of MFCs using different current
air cathode MFC (Fig. 1) is prepared by impregnating collectors is compared in Table 1. For example, Zuo
the conductive electrode material, with or without et al. (2008) pressed a SS mesh against the cathode and
catalyst, to enhance oxygen reduction reaction on the the internal resistance decreased from 47 Ω (without
exposed surface of membrane separator, provided current collector) to 29 Ω.
with an appropriate current collector.
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Chatterjee et al./Environmental Engineering and Management Journal 17 (2018), 7, 1531-1544
The maximum power produced increased by possibility of leaching of these metals into the
28% compared to the same system without the mesh. catholyte and thus creating toxicity for the microbial
Other metals like titanium (Duteanu et al., 2010) and population hence reducing the opportunity and
nickel (Zhang et al., 2009b) have also been used. Air advantage of biocathode formation in the MFC. A new
cathode MFCs employing more uniformly spread type of binder-free gas diffusion electrode made of
current collector like a sock net give more consistent cobalt oxide (Co3O4) micro-particles directly grown
and dependable results for future use, and it is reported on stainless steel mesh (SSM), by using an ammonia-
to produce power density of 3.2 times higher than the evaporation-induced method, demonstrated improved
MFC having similar configuration but provided with performance in terms of electrocatalytic activity,
SS wire as current collector (Chatterjee and selectivity, durability and economics toward ORR in
Ghangrekar, 2014). pH-neutral solution, in comparison with conventional
carbon supported platinum catalyst (Gong et al.,
3.3. Catalyst 2014).
Use of an air cathode eliminates the problem of 3.3.2. Activated carbon powder
low aqueous solubility of oxygen, by direct diffusion Carbon is generally considered an inert
of oxygen to the cathode. The oxygen reduction material; however, it has some superficial activity due
reaction (ORR) however has a high overpotential for to the presence of heteroatoms such as oxygen,
reduction to water (Freguia et al., 2007). To overcome hydrogen, sulphur, nitrogen, etc. The activity of
this problem catalysts are often used on cathode carbon can be increased by optimizing the proportion
surface. Use of catalyst on the cathode helps in: (a) of these atoms on the carbon surface. Activated carbon
increasing the affinity of the cathode to oxygen, and powder thus produced can be used in place of other
(b) decreasing the activation energy of ORR (Duteanu ORR catalysts (Duteanu et al., 2010; Harnisch et al.,
et al., 2010). A catalyst layer is applied on the surface 2009; Pant et al., 2013; Pant et al., 2010b; Zhang et al.,
of cathodes by spray paint gun or brush. The catalysts 2009a; Zhang et al., 2011a). These non-metal catalysts
generally used in air cathode MFC can be grouped into are more stable than the commonly used platinum (Shi
three types: noble metal catalyst, non-noble metal et al., 2012). An air cathode MFC using N-doped
catalyst and activated carbon powder. carbon powder prepared by nitric acid (HNO3)
refluxing after heat treatment and acid treatment was
3.3.1. Noble and non-noble metal catalysts prepared by Shi et al. (2012) and their performance
Platinum (Pt) is the most widely used cathode was compared to a MFC using Pt catalyst on cathode.
catalyst; however, it is very costly and moreover it has Threefold increase in power, comparable with
poor ORR kinetics in neutral pH and at lower platinum catalyzed cathode, is reported using treated
temperature (Duteanu et al., 2010). Some other carbon as compared to the untreated carbon. Besides
cheaper catalysts like Co-tetra-methyl nitric acid refluxing, N-doped carbon powder can also
phenylporphyrin (CoTMPP) (Zuo et al., 2008), iron be synthesized by chemical vapor deposition (Feng et
phthalocyanine (FePc) (Cheng et al., 2006; Sun et al., al., 2011) and sol-gel polymerization (Jin et al., 2011).
2009) and manganese dioxide (Zhang et al., 2009b; Dong et al., (2012) prepared an air cathode by rolling
Zhuang et al., 2010a) are also used. Zuo et al., (2007) activated carbon (AC) and polytetreafluoroethylene
showed that a tube cathode MFC with two CoTMPP (PTFE), combined in different ratios. Maximum
coated tubes produced slightly less power (8.8 W/m3) power density was obtained for AC to PTFE ratio of 6
than that obtained with a carbon paper cathode with Pt (802 mW/m2) and lowest power density was obtained
catalyst (9.9 W/m3) (Table 2). Zuo et al., (2008) for a ratio of 11 (584 mW/m2). Duteanu et al., (2010)
measured the performance of CoTMPP as catalyst and prepared an air cathode by coating a polymer
found that both power and Coulombic efficiency (CE) electrolyte membrane with acid treated carbon powder
of MFC increased proportionately with the catalyst and compared its performance in MFCs using
loading. Longer operation times were needed as the cathodes prepared by coating the same membrane with
catalyst loading was decreased, allowing more oxygen untreated carbon with and without Pt catalyst; and
to diffuse through the cathode into the electrolyte. This comparable performance in the MFC using acid
oxygen was used by bacteria for aerobic degradation treated carbon powder to the Pt/C cathode was
of the acetate substrate, lowering the electron recovery reported. At lower current densities the Pt/C cathode
and therefore decreasing the CE (Zuo et al., 2008). performed better, while the acid treated carbon
Ghasemi et al., (2013b) used copper powder cathode had a comparable performance with
pthalocyanin (CuPc) and Ni nanoparticles and Pt/C electrode at higher current densities.
observed CuPc to be performing almost similar to Pt Recently, a porous nitrogen-doped carbon
catalyst followed by Ni nanoparticles. Use of nanosheet was used as an alternative to Pt catalyst in a
nanoparticles in cathode as catalyst increases the MFC (Wen et al., 2014), which gave a higher power
effective surface area for ORR, thus improving its density than a Pt catalyst. A higher volumetric power
performance. However, use of such metals like copper obtained with polypyrrole (PPy) compared with
or nickel needs further investigation for long-term conventionally used Vulcan XC exhibits that PPy is a
stability to operate MFCs for a long time. There is a better conductive support to ORR (Khilari et al.,
1534
A brief review on recent advances in air-cathode microbial fuel cells
2014). Cost effective manganese dioxide material for the replacement of expensive Pt in
nanotube/graphene composites are reported to constructing large-scale MFC for wastewater
demonstrate high ORR activity and high power treatment and bioelectricity production (Khilari et al.,
generation ability, hence making it a potential cathode 2013a) (Table 2).
1535
Chatterjee et al./Environmental Engineering and Management Journal 17 (2018), 7, 1531-1544
118.2
CuPc/C
mW/m2
120.8
Pt
mW/m2
1159.34 Wen et
PNCN
Carbon Carbon Not mW/m2 al. (2014)
Not mentioned SS net PTFE
powder brush mentioned 858.49
Pt
mW/m2
21.2
Pt
Carbon 4 layer mW/m3 Gong et
SS mesh Not mentioned SS net Nafion
cloth Teflon 17.8 al. (2014)
Co3O4
mW/m3
6.11
MnCo2O4/PPy
mW/m3
Carbon Carbon Not Not Not 4.22 Khilari et
Nafion MnCo2O4/C
cloth cloth mentioned mentioned mentioned mW/m3 al. (2014)
1.77
C
mW/m3
1536
A brief review on recent advances in air-cathode microbial fuel cells
Performances of MFCs using different binders performance decreased by 40%, unlike MFCs with
are summarized in Table 3. Best performance (766 lower diffusion layer porosity whose performance
mW/m2) was observed using four diffusion layers on decreased by only 20%. Liu et al., (2011) prepared a
the cathode surface (Table 4). Zhang et al. (2011b) novel air cathode MFC using a hydrophobic double-
compared the long-term performance and stability of sided cloth as the base material for cathodes without
MFCs having cathodes with diffusion layers of any diffusion layer. This decreased the cost and
varying porosity. They observed that although initially simplified the manufacturing of cathodes. However,
the power production was greater in the MFC with long-term stability of this configuration needs to be
higher porosity of diffusion layer, after one year its evaluated.
Max. power
Cathode Anode Membrane Binder Diffusion layer Catalyst Prepared by
density
2 layers of 150 ± 22
plastic wrap mW/m2
Activated Carbon Pulp laminated Not 1 layer of Not 110 ± 14 Hays et al.,
carbon mesh glass fiber mentioned plastic wrap mentioned mW/m2 (2011)
140 ± 6.4
PDMS
mW/m2
1592 ± 19
1 PDMS layer
mW/m2
1610 ±
SS mesh 2 PDMS layer
56mW/m2
Graphite Not 1010 Zhang et al.,
Not mentioned 3 PDMS layer Pt
fiber brush mentioned mW/m2 (2010b)
1553 ± 19
1 PDMS layer
Carbon mW/m2
cloth 1635 ± 62
3 PDMS layer
mW/m2
4 PTFE layer 766 mW/m2
633 ± 7
Carbon Carbon 8 PTFE layer Cheng et al.,
Carbon cloth Nafion Pt mW/m2
powder cloth (2006)
538 ± 6
No layer
mW/m2
70 % porous 734 ± 18
Activated Graphite Not layer of PTFE Not mW/m2 Zhang et al.,
Not mentioned
carbon fiber brush mentioned 30 % porous mentioned 789 ± 68 (2011b)
layer of PTFE mW/m2
Double 0.7 ± 0.02
No layer Pt-C
sided cloth Carbon Not mW/m2 Liu et al.,
Not mentioned
Carbon cloth mentioned 0.66 ± 0.01 (2011)
4 PTFE layers Pt-C
cloth mW/m2
Carbon Carbon Micro-fiber Not Polyolefine Tugtas et
Pt 750 mW/m2
cloth cloth cleaning cloth mentioned membrane al., (2011)
1537
Chatterjee et al./Environmental Engineering and Management Journal 17 (2018), 7, 1531-1544
Tugtas et al., (2011) used cheaper spun- configuration for scaling up of MFC. Carbon cloth
bonded polyolefin sheet as a diffusion layer in place containing catalyst was hot pressed to an ion exchange
of PTFE and obtained a power density of 750 mW/m2 membrane to prepare the MCAs. To prepare the CCA
using a carbon cloth cathode. Successful application a nickel based conductive paint and a catalyst was
of such cheaper material will contribute in bringing sprayed on a carbon cloth. The CCAs were reported to
down the production cost of MFC and enhancing its perform better in terms of power generation and COD
economic viability for full-scale application. removal because of their higher proton transfer rate,
establishing CCA as a cost-effective option for scaling
4. Membrane Electrode Assembly (MEA) up of MFCs. Composite membranes consisting of
polyvinyl alcohol (PVA), silicotungstic acid (STA),
In a conventional MFC the anodic and cathodic and graphene oxide (GO) were prepared and evaluated
compartments are separated by a membrane and as proton-conducting membranes in air-cathode
respective electrodes are placed in these MFCs. These synthesized PVA−STA−GO
compartments. This increases the distance between membranes showed excellent kinetic properties, better
cathode and anode and simultaneously increases the durability, reduced oxygen crossover and higher
length of the path required to be traversed by a proton power density compared to the commercially
thus increasing the internal resistance of the system available Nafion 117 (Khilari et al., 2013b).
(Wei et al., 2011). Construction of MFCs where this Ajayi and Weigele (2012) prepared a low cost
distance can be minimized may therefore provide for membrane electrode assembly by coating a terracotta-
devices with higher performance. Reactor designs pot with graphite paint and obtained a maximum
with electrodes placed on either side of the membrane power density of 33.13 mW/m2 using a graphite felt
are known as membrane electrode assembly (MEA) anode. Efforts are being made over the past few years
MFCs (Hays et al., 2011; Zhang et al., 2011b). to prepare a sustainable low cost wastewater treatment
Implementation of MEA-MFCs have improved the system using baked earthenware as separators (Behera
overall reactor performance and reduced the capital et al., 2010a; Behera et al., 2010b; Jana et al., 2010).
cost considerably (Kim et al., 2009; Liu and Logan, This material is quite effective for proton transfer and
2004; Zhuang et al., 2010). has been used successfully as a low cost substitute to
MEAs are generally constructed by the costly proton exchange membranes like Nafion,
following two steps: (a) hot pressing the membrane Ultrex, etc. It provides for better wastewater treatment
with the elctrodes to obtain close contact between the and higher electricity generation than expensive
membrane and the electrodes (Prakash et al., 2010; proton exchange membrane materials (Jana et al.,
Zhuang et al., 2010), and (b) applying a conductive 2010). The cost of this earthenware membrane is 100
layer, with or without catalyst, to the surface of the fold less than that of Nafion.
separator by a spray paint gun (Zhuang et al., 2010).
Catalysts are usually applied on that side of the 5. Membrane fouling
cathode which is facing the membrane (Prakash et al.,
2010). Complete contact between the electrodes and Membrane fouling is a problem in almost all
the membrane is a strict requirement for MEA membrane processes, which needs an immediate
constructed by this method, which makes it difficult solution. The common fouling types are organic,
for implementation of larger volume MFCs in field colloidal, biofouling and scaling (Vermaas et al.,
due to limitations of substrate diffusion (Zhuang et al., 2012). Although performance of fouled membrane in
2010). Moreover, this method is only suitable for other membrane processes can be partially restored by
Nafion-electrode assemblies or materials that can appropriate cleaning method, it will cause operational
withstand high temperature and not for other cheaper difficulties in MFCs and also add to the overall cost of
alternatives where thermal degeneration might occur the system (Ang et al., 2006; Creber et al., 2010; Kang
(Kim et al., 2009). This increases the cost of the entire and Cao, 2012). The major factors that affect
setup as we try to scale up the MFCs. To avoid this membrane fouling are its physicochemical properties
problem Zuo et al., (2007) constructed a new type of like water affinity, surface roughness, and electrostatic
membrane electrode assembly by coating a membrane charge (Kang and Cao, 2012; Louie et al., 2006).
with graphite paint and furthur coating it with a Fouling of membrane or more specifically cathode
catalyst. Duteanu et al., (2010) also used the same fouling in single chamber MFCs reduces overall
procedure to prepare a membrane electrode assembly. power output by reducing the exposed cathode surface
Kim et al., (2009) applied a layer of hydrophilic area and by reducing oxygen diffusion to the active
hydrogel between the membrane and the cathode catalytic sites. Fouling of cathode also increases the
which improved the performance by increasing resistance of the system (Vermaas et al., 2012).
hydration and maintaining proper contact between the Fouling might also cause limitations in cation transfer
membrane and electrode. thereby leading to losses in cathodic potential (Rikame
Zhuang et al., (2010) compared the et al., 2012). Xu et al., (2012) observed a 32.3%
performance of different membrane-cathode decrease in power production in MFC due to fouling
assemblies (MCA) and cloth-cathode assemblies of the membrane. Therefore, solutions are sought to
(CCA) in MFCs, to find an optimum cathode inhibit fouling and also for removing fouling.
1538
A brief review on recent advances in air-cathode microbial fuel cells
Surface modifications by changing the water formation was inhibited up to 46.3% on polystyrene
affinity of the surface could be a possible option to surface. Vanillin was also found to be effective in
reduce fouling. Researchers have said that hydrophilic inhibition of biofouling in MFC as reported by
membranes containing hydroxyl, carboxyl or ethylene Chatterjee and Ghangrekar (2013). A mixture of PVA
oxide groups are better fouling resistant because most and Vanillin was used as binder in a single chamber
of the potential fouling compounds are hydrophobic in air-cathode MFC, which demonstrated only 8%
nature and a thin water layer on the membrane surface decrease in power production as compared to 56%
prevents hydrophobic foulants from getting attached decrease for the MFC using only PVA, after five
to the membrane surface (Kang and Cao, 2012; Liu et weeks of operation. Titanium dioxide (TiO2) being a
al., 2012; Rana and Matsuura, 2010; Vermaas et al., well-known photocatalytic agent and having a
2012). However, for hydrophilic foulants membrane hydrophilic behavior, use of nano TiO2 particles as
hydrophilicity will even increase fouling further anti-fouling agent is reported in literature (Akuzov et
(Kwon et al., 2005). Chen et al., (2012) prepared an al., 2013). Other inorganic materials like silicon
air-cathode microbial fuel cell using hydrophilic dioxide (SiO2), Zeolite, silver nanoparticles and even
polyvinyl alcohol (PVA) as binder and reported better mesoporous materials improves membrane resistance
coulombic efficiency (94%) and power density (1220 to fouling when coated on membrane surface (Kang
mW/m2) of the MFC compared to the one prepared and Cao, 2012). Oxidative processes are important for
using glass fiber separator because of better fouling the cross-linking of the adhesive proteins secreted by
mitigation properties of PVA. microorganisms to adhere to any surface and
Another antifouling mechanism is to decrease inhibition of the oxidative processes could result in
the surface roughness of the membrane because low cohesion strength of the protein adhesive films of
fouling particles are more likely to be attached to microorganisms. Several antioxidants like gallic acid,
rough surfaces than to smooth ones (Elimelech et al., ascorbic acid, tannic acid can reduce fouling by
1997; Sagle et al., 2009; Vermaas et al., 2012; inhibiting their attachment to the surface (Akuzov et
Vrijenhoek et al., 2001). The surface charge of the al., 2013), but the feasibility of using all these agents
membrane is also an important factor in controlling are yet to be tested on cathodes of MFC.
fouling, as electrostatic repulsion between the Today most researches on reducing membrane
membrane surface and the foulants will reduce fouling are based on introduction of a hydrophilic
membrane fouling (Vermaas et al., 2012). In an layer, the reduction of surface roughness,
experiment on electrodialysis Vermaas et al., (2012) improvement of charge property, and utilization of
observed remnants of diatoms, clay minerals and steric repulsion effect and use of biocides (Kang and
organic fouling at the anion exchange membrane and Cao, 2012). The easiest way to obtain all these
scaling of calcium phosphate at the cation exchange modifications of membrane surface is by surface
membrane. However, the membranes will show coating. The modifiers used might only be connected
distinct tendencies of fouling depending on the nature to the membrane surface by van der Waals force of
of the foulant. Once the electrical charge of the foulant attraction, hydrogen bonding or electrostatic
is known this phenomenon can be easily used to interaction, hence the antifouling properties of the
reduce fouling. On a neutral surface deposition of modified membrane may be gradually lost due to loss
foulants is less due to elimination of charge interaction or leaching of coating after long term use (Kang and
between the membrane and foulants. Also steric Cao, 2012). Certain chemical processes can also be
repulsion due to presence of some surface-bound long- used to attain surface modification like using
chain hydrophilic molecule (like polyethylene glycol hydrophilizing treatment by certain acids (Kulkarni et
etc.) prevents attachment of larger molecules of al., 1996), radical grafting (Belfer et al., 2004),
foulants (Mcpherson et al., 1998; Nie et al., 2004; chemical coupling (Van Wagner et al., 2011), plasma
Vermaas et al., 2012; Wang et al., 2002; Wang et al., polymerization (Zou et al., 2011), vapor deposition
2010). (Yang et al., 2011) etc. Winfield et al. (2013) used
Applying anionic or cationic surfactants at natural rubber as membrane and reported reduced
suitable concentrations on hydrophobic surfaces not fouling even after operation for one year.
only reduces bacterial attachment to the surface but Researchers have obtained contradictive
also removes previously attached bacteria on the results in terms of antifouling properties of
surface (Akuzov et al., 2013; Vermaas et al., 2012). hydrophilic and hydrophobic surfaces. While some
However, when tested on hydrophilic surfaces the claim hydrophilic surfaces are better fouling resistive,
non-ionic surfactants showed no inhibition, showing others claim the opposite. Foulants can be inorganic or
that the reduction of biofouling is not only due to the organic, while inorganic fouling is resisted by
toxicity of the surfactants but because of some hydrophilic surfaces and it enhances biofouling,
hydrophobic interaction between the membrane providing a suitable surface for biotic organisms to
surface and microbial cell. Vanillin (4-hydroxy-3- grow. The major research papers on fouling resistance
methoxybenzaldehyde), a well-known food flavoring are dealing with water treatment and not with
agent, could be used as a potential compound that wastewater treatment. The properties of foulants in
reduces the biofilm formation on reverse osmosis water and wastewater are different. While inorganic
(RO) membranes (Ponnusamy et al., 2010). It is materials have to be majorly dealt with while treating
reported that after adding Vanillin the biofilm drinking water, the major culprit in membrane based
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Chatterjee et al./Environmental Engineering and Management Journal 17 (2018), 7, 1531-1544
1540
A brief review on recent advances in air-cathode microbial fuel cells
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1544
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1545-1554
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Several studies have been conducted in various fields comparing Mamdani and Sugeno fuzzy inference systems (FISs). This study
contributes to the literature by comparing the performance of Mamdani and Sugeno hierarchical fuzzy systems (HFSs) in terms of
their technical performance within the context of environmental impact assessment (EIA), a multi-criteria decision analysis
(MCDA) method, with the aim of illuminating practical issues that need to be taken into account during application. The context
is a non-commercial, research-oriented EIA of a pipeline project in southern Iran. Mamdani and Sugeno HFSs were developed
with data collected for and expertise gained via a previous formal EIA of the same project. The two developed HFSs were of binary
structure, reducing complexity while also facilitating sensitivity analysis. A sensitivity analysis was carried out with the full range
of possible HFS input values. Excluding the final FISs, the FIS outputs did not differ significantly between the two examined HFSs.
However, the behavior of the Sugeno HFS was found to be more linear than that of its Mamdani counterpart with a higher degree
of sensitivity to input value changes. This study indicates that the Mamdami HFS is unreliable in some areas due to fluctuations in
the output surface, which necessitates smoothing before it can be applied.
Key words: environmental impact assessment, hierarchical fuzzy system, Mamdani inference system, Sugeno inference system
Received: February, 2014; Revised final: July, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: nirari6754@yahoo.com; Phone: +98-21- 66466682, +98-21- 66466733; Fax:
+98-21- 66480419
Givargis et al./Environmental Engineering and Management Journal 17 (2018), 7, 1545-1554
reasoning and fuzzy modeling. Subjective judgment is whereas aggregation means that the outputs of
an inextricable component of EIA because it entails independent fuzzy expert systems are accumulated as
social and cultural value judgments as well as necessary for computing the final output of the entire
scientific data. Traditional multi-criteria decision- system (Aly and Vrana, 2007).
making methods are insufficient for informing The purpose of the present work is to compare
decisions because they are not able to model the technical performance of Mamdani and Sugeno
qualitative human thinking processes. Conversely, HFSs in the realm of EIA from a multi-criteria
fuzzy logic has the capacity to deal with such criteria decision analysis perspective with the aim of
and problems. Fuzzy systems compute numerical highlighting some crucial aspects of utilizing the
outputs based on a “qualitative human thinking developed models. These HFS models have probable
process” that uses words to analyze complex systems applications in future studies of similar situations. The
(Chen et al., 2017; Liu et al., 2006). As a result, fuzzy present study is not a real EIA and does not analyze
expert systems can help stakeholders understand the and compare any actual alternatives, which would be
rationale behind the tangible values computed by an beyond the capacity of this paper. Rather, it scrutinizes
EIA (Aly and Vrana, 2007; Pislaru et al., 2010). the way both systems can behave in supporting
Likewise, these systems can provide a tool that environmental decisions.
stakeholders can use to incorporate their views and Two EIA case studies utilizing HFSs are
preferences into the assessment process and observe summarized herein. These studies laid the foundation
the numerical results of their reasoning. A fuzzy upon which the current study builds and to which this
expert system is a knowledge-based, quantitative work adds new features and provides new practical
expert system that functions using fuzzy sets, insights. This study utilizes a simplified structure
membership functions, if-then rules, and logical relative to the mentioned studies via developing binary
operators such as “AND”, “OR”, and “NOT” HFSs. In section 2, a brief discussion of some case
(Horsekotte, 2005; Shepard, 2005). Mamdani and studies comparing Mamdani and Sugeno inference
Sugeno models are the most commonly employed systems is presented, mainly from the engineering
fuzzy expert systems (Zaheeruddin and Jane, 2006). modeling perspective. These case studies provided the
The main feature of the Mamdani fuzzy inference impetus for the present study to investigate a different
system (FIS) is the fact that both the antecedents and facet of such comparisons to illuminate some practical
consequents of its rules are fuzzy. Building this type aspects of the systems.
of model requires four steps: fuzzification,
implication, aggregation, and defuzzification 2. Case studies
(Mathworks Inc., 2006).
The Sugeno system (a.k.a. TSK based on its Some case studies of EIA schemes have made
originators Takagi, Sugeno and Kang) is similar to the use of HFSs as decision support tools. As a case in
Mamdani system in the fuzzification step and its use point, Siqueira Campos Boclin and Mello, (2006)
of fuzzy operators. However, it is distinguished by the developed an EIA fuzzy decision support system for a
feature of having output membership functions that highway project in Brazil. They examined four
are not fuzzy. The Sugeno system can employ a linear alternative development scenarios, including the “pre-
(first-order) output membership function or a constant existing situation” and “no action”. They created a
(zero-order) membership function (Mathworks Inc., decision tree which integrates the outputs of fuzzy
2006; Zaheeruddin and Jane, 2006), and its final sub-systems to compute the total environmental
output is computed through the weighted average situation. All of the subsystems were of the Mamdani
method with the outputs of fired rules (Mathworks type and all of the variables in the model were
Inc., 2006). standardized to the universe of discourse [0, 1]. The
In standard fuzzy systems, the number of rules membership functions pertaining to the linguistic
and parameters increases exponentially in relation to terms “good”, “bad”, and “critical” were S-shaped.
the number of input variables. This so-called curse of The defuzzification method was the center of gravity,
dimensionality damages the transparency of systems which generated output values within an interval
since humans are unable to understand and justify smaller than in their study [0, 1]; put differently, the
“hundreds or thousands of fuzzy rules and parameters” final outputs were in the range [0.158, 0.842].
(Wang et al., 2006). This problem has been addressed Therefore, the authors added a final normalization step
by hierarchical fuzzy systems (HFSs), which preclude to each subsystem, as well as to the final output, to
a large number of expert rules, prevent the expansion rescale the outputs at each step to the interval [0, 1]. In
of knowledge into a colossal system, and support the this example, the final outputs were converted by
organization of inter-input variable relationships into subtracting the lower endpoint of the interval (0.158)
a logical structure. Hierarchical systems accomplish and dividing the result by the length of the interval.
this restraint by combining or aggregating several Likewise, Liu et al., (2009) developed a fuzzy
smaller fuzzy expert systems into the computation of decision support system for an EIA of a Taiwanese
the final result. high-speed rail project. They divided the project line
In this context, combination means that the into three segments and analyzed three different
outputs of logically-related fuzzy expert systems are scenarios for each of the segments. They created a
integrated into a single output using logical rules, hierarchy of Mamdani fuzzy expert systems to assess
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Application of landscape metrics for assessment of land use/ land cover (LULC) changes in Varjin protected area, Iran
the impact on environmental criteria and subcriteria. only when using the Sugeno FIS.
Their model was developed using the Matlab Fuzzy
Logic Toolbox. The computed output of each fuzzy 3. Material and methods
expert system was the significance of the associated
environmental impact. The universe of discourse 3.1. Background
relating to all output variables was the interval [0, This study is a research-oriented, non-
100]. Triangular fuzzy membership functions were commercial EIA based on the data and expertise
used for the output variables, with linguistic utilized in a formal EIA study of the South Pars gas
interpretations ranging from “very insignificant” to pipeline project, Phases 15 and 16. The project area
“very significant”. The defuzzification method was extends from landfall in the vicinity of the coastal
the center of gravity. The authors reported that the real village of Assaluyeh to the zone of the platforms of
output range was narrower than the interval [0, 100]. South Pars Deck 15 (Phase 15) and South Pars Deck
As with the Boclin and Mello (2006) study, Lui et al., 16 (Phase 16), approximately 100 km off the southern
(2009) rescaled all intermediate and final outputs so Iranian coast in the Persian Gulf. The landfall area
that their lower and upper bounds corresponded to 0.0 defined in the program stretches from Kilometer Point
and 100, respectively. (KP) 0.0 to KP 4.7. From KP 4.04 to KP 15.46, the
It should be mentioned that each higher-ranked desired pipelines pass through Nayband national
system of the hierarchy consisted of two to five sub- Marine Park (Pouyandegan Mohit Zist, 2011).
systems in both of these models. Studies comparing Nayband National Marine Park is one of the most
Mamdani and Sugeno FISs have been carried out in valuable habitats of the Persian Gulf, sheltering coral
fields other than EIA. For example, Jassbi et al., reefs and marine tortoises.
(2006) compared the performance of Mamdani and A prior formal EIA of this project was carried
Sugeno FISs in detecting generic system faults of the out with a Leopold Matrix (Canter, 1996) with the aim
ENVISAT satellite gyroscope. Both FISs were of assessing the environmental impact associated with
developed to trigger an alarm. The authors observed “action” and “no action” alternatives. The area
that, of the two, the Sugeno FIS was much faster, targeted by the EIA was a 5-km–wide pathway (2.5
requiring 14 times less processing time. The Sugeno km on either side of the pipeline) running through the
FIS was more robust than its Mamdani counterpart coastal regions and sea bed (Pouyandegan Mohit Zist,
when interpreting noisy data; however, it was also 2011).
more sensitive to very high noise levels. On this basis,
the authors concluded that the Sugeno FIS behaved 3.2. Hierarchical fuzzy systems
more realistically than did the Mamdani FIS.
Ultimately, they reported that transitions between In this study, we have developed two HFSs
states were smoother in the Sugeno FIS and that the using the same data and expertise that were involved
Sugeno FIS was more sensitive to imprecision where in creating the formal EIA. Our HFSs have been
the input fuzzy sets overlapped. Guney and Sarikaya developed with the cooperation of PMZ Company’s
(2009) compared Mamdani and Sugeno FISs for experts through brainstorming sessions, using their
resonant frequency calculation of rectangular professional knowledge and the data that were
microstrip antennas. The designed parameters of both collected for the formal EIA. The conceptual models
FISs were adjusted using various training algorithms. (Fig. 1 and Fig. 2), fuzzy membership functions (Fig.
The absolute errors between the measured resonant 3), and all the rule bases (Table 1), are the resultant
frequencies and the frequencies calculated by the FISs outputs of such sessions. The present study does not
were small. However, the best performance was entail public participation or stakeholder views and
achieved by the Sugeno FIS trained by the least lies outside the scope of a formal EIA scheme.
squares algorithm. Özger (2009) compared Mamdani We compare the results obtained with a
and Sugeno FISs developed to predict stream flow of Mamdani FIS-based HFS and a Sugeno FIS-based
the Euphrates River in Turkey. Both FISs were trained HFS with identical structures. The input variables are
on the basis of experimental data. The parameters of all environmental factors scrutinized in the original
the Mamdani FIS were adjusted using a genetic EIA. The HFSs are binary systems in which every
algorithm, while the Sugeno FIS was trained using upper rank FIS consists of two sub-systems, thereby
artificial neural networks (ANNs). reducing the complexity of the hierarchy and
In this case, the Mamdani FIS outperformed its facilitating sensitivity analysis.
Sugeno counterpart in terms of accuracy. However,
the performances of both FISs were surpassed by that 3.2.1. Mamdani HFS
of a conventional model. Kaur and Kaur (2012) The Mamdani HFS (developed with the Matlab
compared Mamdani and Sugeno FISs for the operation R2006b Fuzzy Logic Toolbox) involves the same
of an air conditioning system. In both systems, the membership functions for each fuzzy sub-system. All
input variables were temperature and humidity, and input and output variables are rated in the overlapping
the single output variable was compressor speed. fuzzy categories “Poor”, “Mediocre”, and “Good”,
Despite the fact that both systems operated similarly, reflecting the performance quality of the project for
the air conditioning system worked at full capacity that environmental criterion.
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Givargis et al./Environmental Engineering and Management Journal 17 (2018), 7, 1545-1554
Fig. 1. The conceptual model associated with the Biophysical Index (FL – Fuzzy logic)
Table 1. Fuzzy rules used to calculate the Sea-Bed, Biophysical and Total indices
If Then
Rule no.
Input1a is And Input 2b is Sea-Bed is Biophysical is Total is
1 Poor Poor Poor Poor Poor
2 Poor Mediocre Poor Poor Poor
3 Poor Good Mediocre Mediocre Poor
4 Mediocre Poor Mediocre Poor Poor
5 Mediocre Mediocre Mediocre Mediocre Mediocre
6 Mediocre Good Mediocre Good Good
7 Good Poor Mediocre Mediocre Poor
8 Good Mediocre Good Good Mediocre
9 Good Good Good Good Good
a: Sea-Bed Sediment for the Sea-Bed Index, Physical for the Biophysical Index, and Biophysical for the Total Index; b: Sea-Bed Morphology for
the Sea-Bed Index, Biological for the Biophysical Index, and Socio-Economic and Cultural for the Total Index.
The Mamdani and Sugeno HFSs compute manner to compute the total performance of the
project performance indices relating to the project in the order shown in Fig. 1 and 2, respectively.
environmental components within the interval [0, 1]. The conceptual models through which the Biophysical
The individual indices are integrated in a hierarchical and the Total Indices are computed are presented in
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Application of landscape metrics for assessment of land use/ land cover (LULC) changes in Varjin protected area, Iran
Fig. 1. Table 1 shows the rules associated with the Sea- are computed are presented in Fig. 2, respectively.
Bed, Biophysical, and Total FISs that typify FISs The shapes of the corresponding membership
throughout the hierarchy. The conceptual models functions are triangular (Fig. 3), and the universe of
through which the Biophysical and the Total Indices discourse for all variables is [0, 1].
Fig. 2. The conceptual model associated with the Total Index (FL: Fuzzy logic)
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Givargis et al./Environmental Engineering and Management Journal 17 (2018), 7, 1545-1554
It has to be mentioned that the Sea-Bed and statistical differences between the outputs of both
Biophysical FISs represent all FISs, except for the HFSs.
Total FIS, which is a unique FIS throughout the Linear regression analysis is used to test the
hierarchy. For this study, we use the Centroid linearity of the output function with respect to its input
defuzzification method. The “AND”, implication, and variables. An HFS with linear behavior is equally
aggregation methods are Minimum, Minimum, and sensitive to all inputs, producing a balanced scale for
Maximum, respectively. comparison. The variation between each pair of
adjacent output values is calculated as follows (Eq. 1):
3.2.2. Sugeno HFS
All the same input variables, input membership ∆i = i N − i N −1 , (1)
functions, and rule bases used for the Mamdani HFSs
are used for the Sugeno HFS (developed with the where i is the output value and N is the output number
Matlab R2006b Fuzzy Logic Toolbox), in the systems
developed for the purpose of this study. In a zero order 4. Results and discussion
Sugeno system, the output functions are constants.
Here, the “Poor”, “Mediocre” and “Good” categories The results of diagonal simulation on the Sea-
are mapped onto the constants 0.01, 0.5 and 1.0. The Bed, Biophysical, and Total FISs are shown in Fig. 4.
selected “AND” method is the Product method. The shapes of these curves are typical of all sub-
systems in the hierarchy.
3.3. Data generation
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Application of landscape metrics for assessment of land use/ land cover (LULC) changes in Varjin protected area, Iran
The Mamdani FISs fail to operate at full differently in terms of evaluating the aggregate
capacity, meaning that their output range is narrower performance of decision alternatives. Hence, the
than the input range [0, 1], as reported by other authors comparison among the final outputs of the decision
(Kaur and Kaur, 2012; Liu et al., 2009; Siqueira alternatives will have a different meaning for each
Campos Boclin and Mello, 2006). To put it in another HFS in statistical terms.
way, the Mamdani’s output range is [0.163, 0.837], Linear regression analysis (Table 3)
indicating the fact that the system is biased toward the demonstrates that both the Mamdani (with original or
end of the interval. This means that the degree of bias adjusted output values) and Sugeno HFSs are linear at
(overestimation or underestimation) increases as the a confidence level of 99% (P < 0.01, F > F0.99 (2, 1678)
inputs move farther from the midpoint. This = 4.618), indicating that the transitions between output
phenomenon is especially pronounced in comparison values are fairly constant and continuous in both
with the Sugeno FISs. On the other hand, the Sugeno HFSs. In other words, both systems provide a stable
system operates without any bias toward the endpoints measure for drawing comparisons between decision
of the interval. Hence, further adjustments have to be alternatives. Nevertheless, the F and R2 values
made to the Mamdani outputs here, similar to the associated with the Sugeno HFS are greater than those
method adopted by Siqueira Campos Boclin and belonging to the Mamdani HFS, with the original and
Mello (2006). adjusted output values, indicating that the Sugeno
The results of the non-parametric two-related HFS produces more linear behavior, with a higher
sample Wilcoxon test (Table 2) demonstrate that for percentage of points landing on the regression line.
the Sea-Bed and Biophysical FISs, there are no Consequently, the Sugeno HFS produces a more
statistically significant differences between the output balanced scale for comparison.
values of the Mamdani (with original or adjusted In addition, the input variables’ coefficients for
output values) and Sugeno HFSs (|Z|< Z0.975= 1.96; P the Sugeno system are greater than those for its
> 0.05; PMontecarlo > 0.05). On the other hand, for Total Mamdani counterpart. Therefore, any change in the
FIS, there are significant statistical differences input values will bring about more changes in the
between the output values of the Mamdani (both with output values of the Sugeno system. Hence, besides
original and adjusted output values) and Sugeno HFSs providing a more balanced scale for comparison, the
(|Z| > Z0.975 = 1.96; P < 0.05; PMontecarlo < 0.05). This Sugeno system provides a more sensitive scale for
means that, excepting the Total Index results, both differentiating between decision alternatives, in terms
HFSs perform similarly in terms of evaluating the of both decision criteria and aggregate performance.
performance of decision alternatives with respect to The percentages of negative variation (Eq. 1)
each decision criterion or index. However, with regard for the original and adjusted versions of the Mamdani
to the Total Index, the two HFSs function significantly HFS are identical.
Table 2. Non-parametric two-related samples Wilcoxon test comparing Mamdani and Sugeno FIS outputs
Coefficients
HFSa FISb R2 Fe Pf
Input1c Input2d Constant
Sea-Bed 0.305 0.103 0.296 0.788 3.118exp3 <0.01
Original Mamdani g Biophysical 0.311 0.311 0.189 0.874 5.831exp3 <0.01
Total 0.216 0.319 0.184 0.682 1.802exp3 <0.01
Sea-Bed 0.453 0.153 0.197 0.788 3.118exp3 <0.01
Adjusted Mamdanih Biophysical 0.462 0.462 0.038 0.874 5.831exp3 <0.01
Total 0.320 0.474 0.030 0.682 1.802exp3 <0.01
Sea-Bed 0.736 0.254 0.007 0.934 1.184exp4 <0.01
Sugeno Biophysical 0.736 0.736 -0.233 0.962 2.118exp4 <0.01
Total 0.493 0.736 -0.238 0.824 3.920exp3 <0.01
a: Hierarchical fuzzy system; b: Fuzzy Inference System; c: Sea-Bed Sediment for the Sea-Bed FIS, Physical for the Biophysical FIS, and
Biophysical for the Total FIS; d: Sea-Bed Morphology for the Sea-Bed FIS, Biological for the Biophysical FIS, and Socio-Economic and Cultural
for the Total FIS; e: Fisher Test Critical Value; f: Statistical P value; g: With original output values; h: With adjusted output values
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Givargis et al./Environmental Engineering and Management Journal 17 (2018), 7, 1545-1554
Negative variations are symptomatic of thereafter between two identical values. These
fluctuations in the output surface. On the contrary, this findings provide a practical explanation for the linear
phenomenon is not observed with the Sugeno FISs. regression results (Table 3) while underscoring the
Rather, in the corresponding areas of the Sugeno HFS, fact that the Sugeno system provides a more balanced
the slope of change decreases (Fig. 5) or remains scale for comparison than its Mamdani counterpart.
constant (Fig. 6). Notice in Table 4 that, in most cases, Between points 1 and 21, the outputs of the Sugeno
negative variations happen where the constant system react more sensitively to changes in the input
variable values are within the extreme ranges of [0.0, variable values (Table 5). This phenomenon provides
0.25] and [0.75, 1]. Moreover, it can be inferred that another practical explanation for the linear regression
when an input variable with a higher coefficient is held results (Table 3), demonstrating that the Sugeno
constant (Table 3), the variation of the other variable’s system provides a more sensitive scale for comparison
values spreads the mentioned error into other constant than its Mamdani counterpart.
variable value ranges, with the central value being From the data shown in Fig. 6 and Table 5, it
maintained (i.e. 0.5). can be inferred that in the fluctuating areas between
When the first input variable (i.e. Physical points 21 and 41, the Mamdani system fails to live up
Index) is held constant at 0.85 and paired with all to the expectation that when one input variable is held
values related to the second input variable (i.e. constant, the response to increases in the other input
Biological Index) ranging from 0 to 1 with an should be monotonic. In other words, this
increment of 0.025 (Fig. 5), the slope of variation for phenomenon is construed as pseudo-sensitivity and
the Sugeno FIS increases from point 21 onward. On may distort differentiation between alternatives in
the other hand, the output values for the Mamdani FIS terms of decision criteria or aggregate performance.
(original and adjusted output values) are constant from For example, assume that we have two schemes
point 21 to 27, followed by conspicuous fluctuating respectively named alternative 1 and 2 with an
pattern in the curve associated with the output values. identical Socio-Economic and Cultural input value of
When the second input variable (i.e. Socio- 0.95 using the Mamdani Total FIS with the original
Economic and Cultural Index) is held constant at output values for computation. The biophysical scores
0.950 and paired with all values of the first input of the two alternatives are 0.650 and 0.675,
variable (i.e. Biophysical Index), ranging from 0 to 1 respectively. According to the rule base (Table 1), one
with an increment of 0.025, the Sugeno output values could expect logically that alternative 2 would match
increase at a constant rate of 0.047 between points 1 or surpass the Total Index score of alternative 1.
and 21 and then level out (Fig. 6 and Table 5). On the However, the computed Total scores associated with
other hand, in the Mamdani FIS, with both original alternative 1 and 2 are 0.73 and 0.72, respectively,
and adjusted output values, the output values increase defying logic.
at a varying rate between points 1 and 21 and fluctuate
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Application of landscape metrics for assessment of land use/ land cover (LULC) changes in Varjin protected area, Iran
Fig. 5. Results for one row of row-oriented simulation for the Mamdani and Sugeno Biophysical FISs
Fig. 6. One column of the column-oriented simulation results for the Mamdani and Sugeno Total FISs
In contrast, the Sugeno HFS is reliable over the useful to consider during application. The developed
entire curve. When using the Mamdani HFS, it is systems have the potential to be expanded, revised,
necessary to take into account such areas of validated, and utilized in other EIA studies of similar
fluctuation so as to prevent any misinterpretation. One projects in the region.
way to tackle such problems is to use smoothing
techniques. For example, the fluctuated area of the Acknowledgements
total Mamdani FIS can be smoothed into a shape The present work is a non-commercial research carried out
with the support of the Pouyandegan Mohit Zist Company.
similar to the corresponding area of the Sugeno Total
The authors would like to express their special thanks to the
FIS by applying the linear interpolation method (Fig. management and personnel of the Pouyandegan Mohit Zist
6). Company for their cooperation and support. Also, the first
author expresses his gratitude to Dr. Borhan Riazi, the
5. Conclusions managing director of the company, for providing the
opportunity for him to initiate the study and cooperate as a
This study compares Mamdani and Sugeno guest researcher. The authors thank Dr. Benjamin Mathiesen
HFSs in the context of a non-commercial research- from Write Science Right Co for editing of this article. The
oriented EIA case study of a pipeline project in authors express their thanks to the Editor-in-Chief and the
reviewers for their comments and suggestions.
southern Iran from a multi-criteria decision analysis
perspective. The developed HFSs are binary systems References
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1554
Environmental Engineering and Management Journal July 2017, Vol.17, No. 7, 1555-1562
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
The objectives of this study were to investigate: a) whether the duration of organic farming influences the dimension, shape and
geometry (fractal dimension) of soil micropores (<50μm) and b) for relationships of morphometric traits with certain chemical and
biochemical soil variables (microbial biomass, N- and C-mineralization rates, NH4+, NO3-, organic C and N, extractable P, Mg+2,
K+, Ca+2). We compared soil micromorphometric traits (area, perimeter, compactness, solidity, eccentricity) among fields with
different duration of organic farming (2 (O2), 3 (O3), 5 (O5), and 6 years (O6)): these were planted with Asparagus officinalis and
one was conventional cultivation (CV). Νo significant differences were observed among the morphometric traits of all fields.
However, the soil of the older organic areas (O6, O5 and O3) was characterized by small-sized pores (<10 μm) while the newest
(O1) and the conventional field were characterized by medium-sized micropores (10-20 μm). The fractal dimension D2 of the larger
pores was found to be significantly higher in Ο2 and O3 fields, indicating larger outline irregularity for these particular pores.
Higher fractal dimension could be related to more heterogeneous distribution of the microbial community in space. All micropores
were correlated with the concentration of soil mineral nutrients (Mg+2, K+, Ca+2). In the small pore size category (≤10 μm), N-
microbial and NO3- concentrations, parameters involved in the nitrogen cycle, were found to be correlated to the structure
characteristics. Taking into account that the three older organic fields are characterized mainly by small sized pores (≤10 μm), it is
suggested that improved soil quality is mainly related with the N-cycle.
Key words: fractal dimension, image analysis, micromorphometric traits, soil thin sections
Received: February, 2014; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: nmonokro@bio.auth.gr; Phone: +30 26510 07904; Fax: +30 26510 07064
Monokrousos et al./Environmental Engineering and Management Journal 17 (2018), 7, 1555-1562
achieved to formulate a model adequately describing September 2003 from fields planted with the perennial
the relationship between pore perimeter and surface. Asparagus officinalis (L). All fields were of similar
The change in soil quality because of soil texture (Monokrousos et al., 2006). Five
management practice is a current topic of interest. organically cultivated fields and a conventional one
There is growing evidence that organically cultivated was sampled. The organic fields represented a
systems exhibit improved soil quality than gradient in relation to the duration of organic
conventional ones (Droogers and Bouma, 1996; cultivation; 2 (O2), 3 (O3), 5 (O5) and 6 (O6) years.
Monokrousos et al., 2006). However, very few studies Those cultivated organically for 2 and 3 years were
have been conducted regarding the changes that considered as fields in transition (Stanhill, 1990). All
organic farming might induce to the soil structure organic fields were nearby to each other within a
during the conversion period from conventional to continuous field area of about 30.000 m2. They were
organic farming and afterwards. Among them, conventionally cultivated for several years before
Gerhardt (1997) and Papadopoulos et al., (2006) conversion to organic field. The conventional field
concluded that the management methods associated (CV) covered an area of 9.000 m2 and was located
with organic farming induce the formation of an almost 500 m away from the organic ones. It was
ameliorated soil structure, which is porous, better cultivated conventionally for more than 6 years.
developed and has increased organic matter content
and soil biota presence and activity. Based on 2.2. Soil thin-section preparation
literature review, more studies have been conducted
on pores sized >50 μm in equivalent diameter, The samples were air-dried for a week and then
whereas our research specifically focused our focused were dried in an oven at 350C for 48 h. The first step
on the study of soil micropores (<50 μm) on which included the placement of the boxes in a polyester
relevant information is limited (Menendez et al., 2005; resin system applied under vacuum in the resin
Pachepsky et al., 1996). These micropores play an impregnation process (Crystic17449, MEKP,
important role for agriculture as they are responsible Accelerator ‘G’; Scot Bader) (Sole et al., 1992). The
for water storage in the soil (Pagliai et al., 1981), form resin droplets penetrated the soil pores by capillarity
the soil microaggregates, allowing the growth of root until each soil sample was fully saturated with resin.
hairs, and also form protective micro-habitats which Impregnation time was 7 h and the hardening period 6
will allow the increase of soil microbial biomass weeks. The resinous soil blocks were allowed to dry
(Heijen and Van Veen, 1991). Thus, changes οf over a period of 3 months, after which a thick section
morphological traits and numbers of soil micropores was cut, mounted on a glass slide and polished to a
in organically cultivated fields can be regarded as a thickness of 20-25 μm. Then, the soil blocks were
clear symptom of improved soil structure (Greenland, bonded to polished glass slides (110 mm - 75 mm - 3
1981). mm) with a standardized mass of epoxy (Epoxy 301;
In this paper we studied micromorphometric Logitech), then cut and lapped. Thin sections were
traits of the void phase in four organic areas of then mechanically polished using 3 mm diamond
Asparagus officinalis (L), using image analysis of soil pasted.
thin sections. The areas differed regarding the age of
organic farming, so as to check for. We explore 2.3. Image acquisition and thin section porosity
questions relating as to whether the age of organic analysis
farming influences the dimensions (surface,
equivalent diameter and perimeter), the shape To study the pore and soil particle distribution
(eccentricity, solidity and compactness) and the fractal the soil blocks were photographed using a digital
dimension of soil micropores. Moreover, in an attempt camera coupled with a polarizing microscope. Images
to associate micromorphometric traits with soil (752 x 582 pixels) were taken using a camera with an
biochemistry, we further sought for correlations objective magnification of 20x. Three replicates were
between the whole set of values relating to void phase obtained from each block.
with the corresponding set of values of certain The use of polarized microscopy allowed the
biochemical variables. discrimination of soil pores and matrix by color.
Minerals are represented by various colors, the
2. Material and methods organic material by brown color, while the resin inside
the pores by black color. The segmentation and
2.1. Study area and sampling classification of the digital image to patches was based
on these different colors as well as on differences on
The study area is located in Kria Vrisi 60 km the texture. Each soil section is considered a landscape
north-west of Thessaloniki, northern Greece. The image and for image analysis the eCognition program
parent rock consists of Alluvial deposits (Holocene) was used. The digital photos were transformed from
(IGMR, 1983). In order to evaluate the influence of vector to raster and the results were processed using
management practices on the soil profile, five Matlab. The following pore micromorphometric traits
undisturbed vertical soil samples were collected with were estimated: area, perimeter, equivalent diameter,
cylindrical boxes (3 cm diameter, 4.5 cm high) from eccentricity, compactness and solidity. The first three
each sampling area. The samples were taken in parameters stand for pore dimensions, while
1556
Dimension and structural traits of soil micropores in cultivations differing in the duration of organic management
eccentricity, compactness and solidity for the shape of Log P= α + bLog S (3)
pores. Eccentricity is equal to the ratio of the distance
between the foci of the ellipse to the length of its major where: P stands for perimeter, S is surface, a is
axis. Eccentricity values range between 0 and 1 (zero elevation and b is slope.
eccentricity corresponds to a circle while unity Following Pachepsky et al. (1996) a piecewise
corresponds to a line). To estimate compactness, we nonlinear regression model has been fitted. The
used (Eq. 1) algorithm estimated parameters a1 and b1 for data up
to the breakpoint and a2 and b2 for data beyond the
( perimeter ) 2 breakpoint. To further seek for statistical differences
C= among slopes and elevations an Analysis of
area (1) Covariance (ANCOVA) was performed. Finally, a
Canonical Analysis was performed to assess the
Finally, solidity is equal to the percentage of relationships between the pore micromorphological
the pore which is within a convex hull. The traits and the soil biochemical variables.
relationship between area (A) and perimeter (P2) is
widely used in soil micromorphology to characterize 3. Results and discussion
the shape of pores (Murphy et al., 1997). In this paper
we employed Swartz (1980) shape index (Eq. 2): As it was revealed by estimating the Swartz
index, the large elongated pores contribute 64-72% to
F=4πA/P2 (2) soil porosity, whereas the small rounded pores
participate with 12-17% (Fig. 1).
This index is used to classify pore shapes into Pores were discriminated in three pore size
elongated or planar (F<0.2), irregular (0.2<F<0.5) and categories (≤10 μm, 10-20 μm, 20-50 μm) according
rounded (F>0.5) pores (Bouma et al., 1977, Mermut et to their equivalent diameter. In Table 2 are presented
al., 1992). The pores were further subdivided into the average values of morphological traits in all
three size classes (class 1: ≤10 μm, class 2: 10-20 μm, sampling sites for each pore size category. No
class 3: 20-50 μm) according to either the equivalent significant differences were revealed in relation to
pore diameter for rounded and irregular pores and management type (organic vs conventional farming)
their width for elongated pores (Pagliai et al., 1983). in dimension and shape measurements, for any of the
The soil biochemical variables employed in three pore size categories. A One-Way ANOVA
this paper are described in Table 1. These data relate accompanied by a Bonferroni test showed that
to the sampling period of September 2003 and were elongated pores occupy larger void surfaces in organic
presented in Monokrousos et al. (2008). plots of age 2 and 3 years.
The pores were further subdivided into three
2.4. Statistical analyses classes according to the equivalent pore diameter for
the rounded and irregular pores and their width for the
A correspondence analysis was used to elongated pores up to the size of 50 μm. The
ordinate samples from various sampling areas with percentage contribution of the three size categories is
regard of their relative frequencies of the three pore shown in Fig. 2. The contribution of the small sized
size categories (≤10 μm, 10-20 μm, 20-50 μm). To pores in the total void of the soils is higher than the
estimate the fractal dimension the linear model (Eq. 3) other two categories, varying between 72-77%.
was fitted on data:
Table 1. Mean values (± standard error) of soil chemical and biochemical variables
1557
Monokrousos et al./Environmental Engineering and Management Journal 17 (2018), 7, 1555-1562
Fig. 1. Percentage contribution of the three pore shape categories in surface area in all sampling areas.
Different letters correspond to statistically significant differences, as indicated by ANOVA,
between the % contribution of the elongated pores of the sampling areas (p<0.001)
The results of the correspondence analysis regarded as a clear indication of improved soil
indicated that the first axis explain 84.32% of the structure (Greenland, 1981). Soil structure is known to
samples inertia. Samples from O6, O5 and O3 areas have a large influence on the population dynamics,
were ordinated towards the left end point of the first ecology and activity of microorganisms (Stotzky,
axis. Moreover, the smallest pore size category (≤10 1986). The small sized pores (≤10μm) form protective
μm) was ordinated to the left, while the middle pore micro-habitats which are large enough to allow
sized (10-20 μm) was ordinated in the middle and the bacteria to enter but too small to be colonized by
largest sized (20-50 μm) on the right end point of this predating protozoa (Heijen and Van Veen, 1991). As
axis. These results indicate that the three oldest shown the older organically cultivated fields in Krya
organically farmed areas are characterized by small Vrisi are characterized by the smallest pore size
sized (≤10 μm) pores while the newest organic area category and this is in accordance with the larger
and the conventional one are characterized mainly by amounts of microbial biomass recorded in these soils
medium sized pores (10-20 μm). (unpublished data). An increase of microbial biomass
The changes of microporosity due to different is a clear indicator of improved soil quality and
cultivation management are a very important for therefore, it could be implied that the quality of soil
agriculture in general, because micropores determine structure is improved after three years of continuous
the amount of water available to plants and the soil biological cultivation (Fig. 3). Fractal dimension (D)
capacity for water storage (Pagliai et al., 1981). The describes the geometry of a pore rather than its shape.
micropores whose diameter is about 10 μm form the Dependencies of pore outline perimeter P on outlined
soil microaggregates, allowing the growth of root area A are shown in Fig. 4a-e. In Table 3 are given the
hairs and providing the ground for a good soil values of surface fractal dimension for voids as well
structure. Increase of micropores (0.2-50 μm) can be as the corresponding breakpoints.
Table 2. Mean values (± standard error) of morphological traits in all sampling sites of the three pore categories,
as these are shaped according to their size
1558
Dimension and structural traits of soil micropores in cultivations differing in the duration of organic management
Fig. 2. Percentage contribution of the three pore size categories in the total void in all sampling areas
D1 D2 Breakpoint
O6 1.216 1.474b 18.2 μm2
O5 1.272 1.540a 20.0 μm2
O3 1.242 1.538a 17.8 μm2
Fig. 3. Coordination of the pore size categories (1: ≤10 μm, O2 1.166 1.416b 19.1 μm2
2:10-20 μm, 3: 20-50 μm) and the sampling areas (O6: 6 CV 1.112 1.474b 18.6 μm2
yrs, O5: 5 yrs, O3: 3 yrs, O2: 2 yrs and CV: conventional
field) according to correspondence analysis Table 4. Results of ANCOVA on the lines from which
emerges the fractal dimensions D1 and D2 of the solid
phase of the sampling areas
Furthermore, fractal dimension values reported
for smaller voids (surface lower than that indicated by p-values
the corresponding breakpoint of the model) are lesser D1 D2
(1.112-1.272) than the fractal dimension values Elevation (a) 0.076 0.0001
estimated for their larger counterparts (1.416-1.54) Slope (b) 0.057 0.0001
(Table 3). The fact that the fractal dimension D1 for
the small pores is closer to 1 indicates their rounded To correlate the set of biochemical variables
geometry. with the set of micromorphometric variables of the
Analysis of covariance showed that the voids a Canonical Correlation Analysis was employed
elevations and the slopes of the relation for the for each pore size category separately. In all size
smallest pores did not differ statistically among the categories only the first root of the analysis was
areas (Table 4). Thus, no significant differences were statistically important, which accounts for the 87-96%
detected between fractal dimensions of pore outlines of the between sets correlation. Furthermore, the
among the sampling areas (Table 3). In contrast, analysis showed that the relationship between the
elevations and slopes for larger voids were found to be analyzed sets was indeed linear, while no point clouds
affected significantly by the age of farming (Table 4). are depicted on the relevant graphs (not provided).
Fractal dimension D2 is significantly larger in samples Accordingly, the linear correlation is homogeneous
from the O3 and O5 areas than in samples from the along the whole range of values. For all pore classes,
other areas (Table 3). According to Kampichler and significant are those correlations between
Hauser (1993) the variations in the fractal dimension morphometric variables, which are describing the
may result in variations in the available habitat for structure of the pores such as solidity and
different microbial species. The higher fractal compactness, and biochemical variables such as N
dimension could be related to more heterogeneous microbial, Ca+2, Mg+2, K+ and the rate of C-
distribution of the microbial community in space. mineralization. More specifically, in small sized pores
Highest D2 fractal dimension estimated for O3 and O5 (≤10 μm), a correlation exists between the pore
indicating more favorable biological transformation solidity and compactness and the N-microbial, NO3-,
processes as well as easy infiltration of water in case K+ and Ca+2. In the middle size category (10-20 μm)
1559
Monokrousos et al./Environmental Engineering and Management Journal 17 (2018), 7, 1555-1562
the correlation is noticed between pore solidity and N- In the middle and larger (10-50 μm) pore size
microbial, N mineralization rate, K+, P extractable, categories the correlation between the N- and C-
Ca+2 and Mg+2 concentrations, while in the larger size mineralization rates with the structural morphometric
category (20-50 μm) the correlation is between traits indicate high microbial activity. Strong et al.
solidity and compactness and the rate of C- (2004) also found that the decomposition rate of
mineralization as well as the Mg+2 and K+ organic C is faster in medium sized pores with neck
concentrations. Pores with equivalent diameter of <50 diameter 15-60 μm than in smaller ones. This is due to
μm are considered to be the storage pores of soil. The greater microbial activity since this region supports
root hairs grow along these pore channels and both microbial motility and best oxygen supply. Fungi
sometimes modify and enlarge them, at the same time have been found to be more abundant in this pore class
absorbing nutrients, water and oxygen via the adjoin (Strong et al., 2004) supporting larger numbers of
soil material (De Willigen and Van Noordwijk, 1987). fungal-feeding nematodes (Jones and Thomason,
The correlation between the availability of soil 1976, van der Linden et al., 1989). Thus the fast rate
nutrients and the structure of voids could be explained of decomposition of organic C in the 20-50 μm sized
by the fact that the latter is driven to a large extent by could be enhanced by the nematode activity (Table 5).
growing root hairs.
Fig. 4. Dependencies of the pore outline perimeter (P) on the outlined area (A) for samples from all sampling areas:
(a) O2, (b) O3, (c) O5, (d) O6 and (e) CV
1560
Dimension and structural traits of soil micropores in cultivations differing in the duration of organic management
Table 5. Factor structure of canonical analysis for chemical and biochemical and morphometric variables
In the small pore size category (≤10 μm) N- Bui E.N., Mermut A.R., Santos M.C.D., (1989),
microbial and the concentrations of NO3- are also Microscopic and ultramicroscopic porosity of anoxisol
correlated with the structure characteristics. It is as determined by image analysis and water-retention,
noticeable that these biochemical parameters are Soil Science Society of American Journal, 53, 661-665.
De Willigen P., Van Noordwijk M., (1987), Roots, plant
involved in the nitrogen cycle. Consequently, it seems production and nutrient use efficiency, PhD thesis,
plausible that in this region there are dominant Agricultural University, Wageningen, Holland.
processes that transform nitrogen to absorbable by the Droogers P., Bouma J., (1996), Biodynamic versus
root hairs forms. Taking into account that the older conventional farming effects on soil structure expressed
organic fields (O6, O5, O3) are characterized mainly by simulated potential productivity, Soil Science
by the small sized pores (≤10 μm), we could suggest Society American Journal, 60, 1552-1558.
that the improved soil quality in these field is rather Elliott E.T., Coleman D.C., (1988), Let the soil work for us,
related with the N-cycle. Ecological Bulletins, 39, 23-32.
Greenland D.J., (1981), Soil management and soil
degradation, Journal of Soil Science, 32, 301-322.
4. Conclusions Hatano R., Booltink H.W.G., (1992), Using fractal
dimensions of stained flow patterns in a clay soil to
The duration of organic farming is reflected on predict bypass flow, Journal of Hydrology, 135, 121-
the dimension and structural characteristics of 131.
micropores. Areas organically cultivated for more Heinjen C.E., van Veen J.A., (1991), A determination of
than two years are mainly characterized by small sized protective microhabitats for bacteria introduced into
pores (≤10 μm), while the soil of organic cultivations soils, FEMS MicrobiologyEcology, 85, 73-80.
with duration of three and five years consist of pores IGMR, (1983), Institute of Geology and Mining research,
with higher fractal dimension supporting a more Geological Map of Greece, scale 1:500000, Athens, On
line at
heterogeneous distribution of microbes in space. In the https://www.researchgate.net/institution/Institute_for_
small pore size category (≤10 μm), N-microbial and Geological_and_Mining_Research.
NO3- concentrations, parameters involved in the Jones F.G.W., Thomasson A.J., (1976), Bulk density as an
nitrogen cycle, were found to be correlated to the indicator of pore space in soils useable by nematodes,
structure characteristics. All the changes related to the Nematologia, 22, 133-137.
properties of soil microporosity took place after the 2- Kampichler C., Hauser M., (1993), Roughness of soil pore
3 years’ time period that is necessary for the surface and its effect on available habitat space of
conversion of a cultivation from a conventional to an microarthropods, Geoderma, 56, 223-232.
organic one. These results support the idea that Kooistra M.J., Bouma J., Boursma L., Jager A., (1985), Soil
structure differences and associated physical properties
alternative cultivation practices, such as organic of some loamy typic fluvaqvents in the Netherlands,
farming result in improved soil structure and quality. Geoderma, 36, 215-228.
Livingston S.J., Norton L.D., West L.T., (1985), Effect of
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1563-1573
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Rui Wang1, Yuansong Wei1,3∗, Yulong Wu2, Jiaxi Zheng1, Bofu Zheng2
1State Key Joint Laboratory of Environmental Simulation and Pollution Control, Research Center for Eco-Environmental
Sciences, Chinese Academy of Sciences, Beijing 100085, P.R. China
2Nanchang University, Nanchang, 330031, P.R. China
3Ordos Institute of Solid Waste Technology, Research Center for Eco-Environmental Sciences,
Abstract
Organoarsenic compounds are used extensively as swine feed-additives to promote animal growth and control diseases, e.g.
roxarsone (4-hydroxy-3-nitrobenzenearsonic acid) and arsanilic acid (4-aminophenylarsonic acid) are usually overused in swine
industry in China. As a cost-effective technology for animal manure treatment and reuse, composting is widely used for swine
manure treatment. Therefore, the purpose of this study was to investigate changes of arsenic species and fractions during a full
scale swine manure windrow composting. Results showed that four arsenic species, arsenite (As (III)), arsenate (As (V)),
monomethylarsonate (MMA) and dimethylarsinate (DMA), were detected and varied differently which arsenate was on a slightly
increasing trend and arsenite presented a decreasing trend throughout the composting process. The percentages of arsenite, arsenate
and DMA were 24.10%, 29.68%, 4.87% of total arsenic in the beginning of the composting and 8.19%, 34.13%, 4.75% of total
arsenic respectively at the end of the composting. Arsenate had the similar trend to Fe/Mn oxides arsenic fraction, which decreased
dramatically in the first 10 days and then was on increasing trends during the rest of the composting. The percentages of Fe/Mn
oxides, residual, carbonates, organic arsenic fractions were 55.3%, 25.9%, 18.6%, 0% in the beginning and 46.6%, 22.7%, 19.1%,
11.5% at the end of the composting, respectively. These results demonstrated that the most toxic arsenic species, arsenite, was
declined dramatically during the composting process, and composting was a suitable method for detoxification of arsenic by
changing their forms.
Received: March, 2014; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: yswei@rcees.ac.cn, 15810948239@163.com; Phone: +86 10 62849690, Fax:
+86 10 62849109
Wang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1563-1573
concentrations in pig feeds ranged from 0.02 ~ 13.03 Hanc et al., (2011) demonstrated that bioavailability
mg·kg-1 (Zhang et al., 2012), and average contents of arsenic fractions, such as exchangeable arsenic,
roxarsone and arsanilic acid were at 7.0 and 21.2 As decreased during the kitchen waste composting, and
mg·kg-1, respectively (Yao et al., 2013). Additionally, the order of arsenic fractions in the final compost was
arsenite (As(III)) and monomethylarsonate (MMA) as follows: residual > oxidizable > exchangeable >
were frequently detected due to arsenic impurities in reducible. Although there were several researches
feeds bearing organoarsenic (Yao et al., 2013). related to arsenic species (such as arsenite, arsenate
As a low bioaccumulation potential, roxarsone and so on) and arsenic fractions (exchangeable,
and arsanilic acid are largely excreted unchanged in carbonates and so on) during the composting, the
animal manure (Garbarino et al., 2003). For example, relationship between them is not clear and needs
the distribution of arsenic species in fresh poultry litter further study.
was 91% roxarsone, 1.5% dimethylarsinate (DMA), Composting, one of the most suitable
1.1% arsenate (As(V)), 0.8% arsenite (As(III)) and technologies for treating livestock manures can reduce
5.6% of other unknown arsenic compounds the mass, degrade the organic matter, provide
(Garbarino et al., 2003). Based on broiler production sufficient sanitation effect and produce valuable end
and roxarsone feed dosage, it is estimated that products (Jiang et al., 2011). In general, the chemical
approximately 900 metric tons of roxarsone are speciation of As is particularly important in waste
released into environment in the U.S. annually by the management (Carbonell-Barrachina et al., 2000).
poultry industry alone, an amount that is equivalent to Garbarino et al., (2003) studied the degradation of
250 metric tons of arsenic (Rutherford et al., 2003). roxarsone in a lab-scale composting experiment,
Several literatures reported that livestock and poultry which demonstrated that roxarsone degraded easily
manure contained a great amount of arsenic, e.g. and could enter into the environment in other form of
arsenic concentration in swine manure in different arsenic, such as arsenate. Arsenate is the
regions of China varied significantly from 0.004 thermodynamically stable form under aerobic
mg·kg-1 DW (dry weight) to 194.50 mg·kg-1 DW conditions, of which one or two protons are
(Dong et al., 2008; Li and Chen, 2005; Long et al., dissociated at natural soil/sediment pH value, and
2004; Zhang et al., 2012; Zhang et al., 2005). arsenate is a chemical analogue of phosphate and may
Additionally, other investigation demonstrated that interfere with oxidative phosphorylation (Ter Welle
the annual amount of arsenic input to the soil applied and Slater, 1967). Additionally, arsenite is a neutral
with swine manures as organic fertilizers was 340.60 species at natural pH value and inhibits the activity of
g· hm-2, and the increasing concentrations of arsenic enzymes by binding to thiol groups. MMA and DMA
in arable soils was 0.15 mg·kg-1 (DW) annually (Dong also form anions in soil/sediment (Carbonell-
et al., 2008). With long-term application of swine Barrachina et al., 2000). Arsenic is subject to
manure as organic fertilizers on agricultural lands, chemically and/or microbiologically mediated
organic arsenic could be converted into its inorganic oxidation-reduction and methylation reactions in soils,
form, making it water-soluble and allowing it to seep sediments or other medium (Masscheleyn et al.,
into the surface and groundwater (Garbarino et al., 1991).
2003; Rutherford et al., 2003), which ultimately had a Once the residual arsenic in animal manure is
great influence on plants, soil organisms and human released into the environment with land application of
health (Carbonell-Barrachina et al., 1999). animal manure as fertilizer, arsenic may pose great
As the bioavailability and toxicity of arsenic threat potential to food safety and environment
compounds vary dramatically, the investigation of quality. There are growing interests about the arsenic
arsenic degradation, transformation, migration, residues accumulation in animal manure and the soil
environmental impact and human health risk should be (Luo et al., 2009; Zeng et al., 2007; Zhang et al.,
based on measurement of arsenic speciation as well as 2012), however, little work has been done to
total arsenic concentration (Al-Assaf et al., 2009). investigate the different arsenic species and fractions
Although the toxicity of organic arsenics, such as changed in the process of full scale swine manure
arsanilic acid and roxarsone, is relatively low, their composting. The objective of this study was thus to
degradation and transformation can happen and thus investigate different arsenic species and fractions
form the more toxic metabolites, such as arsenic acid, variation during the full scale swine manure windrow
arsenous acid and monomethylarsonous acid during composting to provide support for arsenic pollution
their exposure to environment (Garbarino et al., 2003). control in animal wastes treatment and disposal.
The toxicity of different arsenic species varies in the
order as following: As (III) > As (V) >> MMA > DMA 2. Material and methods
(Jain & Ali, 2000). Additionally, the bioavailability of
arsenic associated with different fractions have 2.1. Full-scale swine manure composting
dissimilar impacts on the environment and their
phytotoxicity connects to some forms rather the total A full scale of swine manure composting was
content (Hanc et al., 2011). The sequential chemical carried out from May 22 to July 16, 2011 in a windrow
extraction of elements can provide an understanding composting plant located in the suburb of Beijing (N
of chemical fractions and a predicting mobility, 39°42', E 116°38'), to investigate degradation of
bioavailability and leaching rate (Tessier et al., 1979). organic arsenic compounds and its metabolic
1564
Changes of arsenic speciation during swine manure windrow composting at full scale
products. Raw materials for composting were mixed ammonium nitrate (NH4NO3) used as mobile phases
of swine manure and mushroom residues at the ratio of liquid chromatogram, magnesium chloride
of 2: 3 (v/v). Fresh swine manure and mushroom (MgCl2), sodium acetate (NaOAc), acetic acid
residues were sampled and stored at 4ºC before (HOAc), nitric acid (HNO3), hydrogen peroxide
composting for analysis. Parameters of all composting (H2O2), perchloric acid (HCIO4), hydrofluoric acid
materials, including pH, moisture content, organic (HF), hydroxylamine hydrochloride (NH2OH·HCl)
matter (OM), TC, TN, and TP, were determined used as arsenic fraction extraction buffers were of
according to the methods (Bao, 2000) and the results analytical pure grade and purchased from Sinopharm
were shown in Table 1. The size of the windrow pile Chemical Reagent Co. Ltd., China. All solutions were
was about 75 m3, at the length of 85 m, the height of prepared in ultra-pure water from a Millipore Milli-Q
0.9 m and the width of 2 m at the bottom of the pile. system (Millipore, USA).
The full scale windrow composting was operated in Phosphoric acid and ammonium hydroxide
the open air and turned by a turner (BACKHUS 15.30, were used for pH adjustment. Phosphate buffer
Germany) once a week in the thermophilic stage, and solution (PBS) was prepared from ammonium
then the pile was moved and stored in a simple shed in dihydrogen phosphate and phosphoric acid. The daily
the mature stage in which there was no turning. During working standards for arsenic species were made from
the composting process, water was added irregularly standard stock solutions (1000 mg·L-1) prepared from
(almost once a week) to maintain stable moisture the six arsenic chemicals dissolved in ultra-pure water.
content of the composting materials. The pile All these stock solutions of these 6 standards above
temperature, including upper, central and lower part, were kept in the dark at 4 ºC.
was recorded daily. The composting materials was All mobile phases, standards and samples were
sampled by mixing the upper, central and lower sites filtered through 0.45 µm polyethersulfone membrane
of the pile on day 1, 3, 7, 10, 23, 38 and 53, filters prior to analysis.
respectively. All the samples collected were stored at
4oC before analysis. 2.3. Analytical procedures
Table. 1. Characteristics of raw materials in the full scale To determine different arsenic species, all of
swine manure windrow composting composting samples stored at -20 ºC were firstly
freeze-dried (ALPHA1-2LD PLUS, Christ, Germany)
Materials
and then sieved by nylon screen with mesh size of 100,
Characteristics Swine
Mushroom Mixture and finally analyzed by using an improved method
manure
pH 7.69 7.64 7.39 described by Al-Assaf et al. (2009) and Garbarino et
Moisture (%) 72.15 46 47.28 al. (2006). Each sample at 1.0 g was extracted with 5
OMa (%) 68.9 87.0 78.9 mL 0.10 mol·L-1 phosphoric acid solution (H3PO4)
TCb (g/kg) 331.42 395.28 223.62 and 5 mL 0.10 mol·L-1 sodium hydroxide solution
TNc (g/kg) 25.98 22.55 15.05 (NaOH) followed by shaking for 24 hours,
TPd (g/kg) 12.01 4.69 16.77 centrifugation at 7000 r·min-1 for 10 min and filtration
C:N ratio 12.75 17.53 14.86 with 0.45µm filter. The extraction solution of arsenic
a. OM: organic matter; b. TC: total carbon; c. TN: total nitrogen; was used for speciation analysis by high-performance
d. TP: total phosphorus liquid chromatography (HPLC) to inductively coupled
plasma mass spectrometry (ICP-MS) (Agilent 7700x,
2.2. Reagents and standards Agilent Technologies, Japan).
To determine the total arsenic concentrations
Six high purity chemicals, including sodium of compost materials, 1.0 g sample was digested with
arsenite (NaAsO2 99.8%, Fluka, Switzerland), sodium 5mL HNO3 (69%) and 5mL HClO4 for 24 hours and
arsenate (Na3AsO4·7H2O 98.5%, Fluka, Switzerland), filtered through 0.45 µm polyether sulfone membrane
disodium methyl arsenate (MMA, filters for ICP-MS analysis.
(CH3)AsO3Na2·6H2O 99.5%, Sigma-aldrich, USA), In order to determine the extraction efficiency
cacodylic acid (DMA, (CH3)2AsO(OH) 99.4%, of the method mentioned above, samples were spiked
Sigma-aldrich, USA), aminophenyl arsenic acid (4- with the standard mixture solutions of arsenite,
arsanilic acid, C6H4AsO(OH)2NH2 99%, Dr. arsenate, DMA, MMA, roxarsone and arsanilic acid at
Ehrenstorfer Gambh, Germany) and 4-Hydroxy-3- three levels: 0.01 mg·kg-1 DW, 0.1mg·kg-1 DW and
nitrobenzenearsonic acid (roxarsone, 5.0 mg·kg-1 DW, respectively. Samples were extracted
C6H3AsO(OH)2(OH)NO2 97.5%, Dr. Ehrenstorfer and analyzed, and the results showed that recoveries
Gambh, Germany) were purchased and used as of all target compounds varied from 89%±3.27% to
standard substances for determining 6 arsenic species 93.25%±2.38%, which suggested that it is an efficient
(arsenate, arsenite, DMA, MMA, roxarsone and procedure for extracting arsenic species from compost
arsanilic acid) in this study. All of the following materials.
chemicals, including phosphoric acid (H3PO4), For better understanding the phytotoxicity,
sodium hydroxide (NaOH) used as arsenic species bioavailability and mobility of arsenic, five different
extraction buffers, ammonium hydroxide (NH4OH), arsenic fractions were analyzed during the swine
ammonium dihydrogen phosphate (NH4H2PO4), manure windrow composting. The sequential
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Wang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1563-1573
chemical extraction of arsenic was applied according collision cell was utilized for the removal of
to Tessier et al. (1979) for the assessment of different polyatomic interferences of 40Ar35Cl+, which usually
arsenic fractions including exchangeable (1M MgCl2, affect the determination of 75As when using ICP-MS.
pH=7), bound to carbonates (1M NaOAc, pH=5), The method separated the arsenic species within 13
bound to Fe/Mn oxides (0.04 M NH2OH·HCl in 25% min and the limits of detection for different arsenic
(v/v) HOAc), bound to organic matter (0.02 M HNO3 species ranged from 0.1 to 0.2 µg·L-1.
+ 30% H2O2, pH=2), residual (digested with HF-
HClO4) in the swine manure windrow composting 3. Results and discussion
samples. All of the arsenic extraction solutions were
stored at 4 ºC and arsenic concentrations were 3.1. Pile temperature
determined by ICP-MS (Agilent 7700x, Agilent
Technologies, Japan). During 53 days composting, including 23 days
of the thermophilic stage and 30 days of the mature
2.4. Instrumentation stage, the pile temperature increased to approximately
55oC rapidly in the first 10 days (Fig. 1), and then
The arsenic speciation analysis was determined sustained above 55 ºC for more than 7 days, which met
by a coupling of HPLC with ICP-MS. In order to meet with the requirements of sanitary standard for the non-
the separation object, an ion exchange columns hazardous treatment of night soil in China (GB-7959-
(4.6×250 mm) manufactured by Agilent was selected 87). Generally, the pile temperature in the central layer
and isocratic elution using 10 mmol·L-1 ammonium was much higher than those in the bottom and the top.
dihydrogen phosphate (pH=6.2) and 10 mmol·L-1 The pile temperature increased successively up to over
ammonium nitrate as mobile phase was applied. The 60 ºC in the thermophilic stage then kept increasing to
mobile phase was set at a flow rate of 1.0 mL·min-1 70 ºC in the mature stage and decreased slightly but
and the injection volume was 20 µL. still around 60 ºC at the end of the composting.
The ICP-MS has been used to determine The pile temperature is an important factor of
elements in natural-water, biota, sediment, soil affecting composting performance due to its influence
samples and other mediums since the early 1990s on the activity and diversity of microorganisms
(Garbarino et al., 2003). In this study, samples were (Finstein et al., 1986). In general, high pile
analyzed using an Agilent 7700x (Agilent temperatures are consequences of biological activity
Technologies, Japan) at ambient temperature. The and have been considered a necessary condition for
Agilent 7700x is fitted with quartz, low-volume, good composting (de Bertoldi et al., 1983). In the
peltier-cooled, scott-type double-pass spray chamber beginning of composting, mesophilic microorganisms
and a concentric MicroMist (borosilicate glass) are initially present, and their activity raises the pile
nebulizer. temperature (Poincelot, 1975). As the pile temperature
The ICP-MS was tuned daily using a 1 µg·L-1 kept climbing, thermophilic microorganisms
tuning solution containing 7Li, 89Y, 205Tl (Agilent predominated gradually during the thermophilic stage
Technologies, Japan). The ICP-MS was used to and parts of organic matter were decomposed in this
quantify the arsenic species at m/z 75. A helium gas process.
Fig. 1. Changes of pile temperature during the full scale swine manure windrow composting
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Changes of arsenic speciation during swine manure windrow composting at full scale
In the mature stage, the pile temperature transferred to other forms (Pinel-Raffaitin et al.,
decreased, and mesophilic microorganisms kept 2007).
decomposing complex organic matter and the
composting was in an anaerobic condition because of 3.3. Arsenic species and fractions
no turning (Miyatake and Iwabuchi, 2006). In this
study, due to low turning frequency of composting pile To determine changes of arsenic species during
and high ambient temperature in summer, the pile the swine manure windrow composting, 6 forms of
temperature kept increasing and sustained highly arsenic compounds were investigated, including
during the thermophilic stage and the mature stage arsenite, arsenate, MMA, DMA, arsanilic acid and
which was up to 70ºC. However, high pile roxarsone. The results showed that neither arsanilic
temperatures in fact inhibit growth of the majority of acid nor roxarsone was detected in the composting
microorganisms, thus slow down decomposition of process, which demonstrated that these organoarsenic
organic matter. Only a few species of thermophilic compounds were degraded before the swine manure
sporigenous bacteria show a metabolic activity above composting in accordance with results of Garbarino et
70ºC (de Bertoldi et al., 1983). al., (2003). Garbarino et al., (2003) studied that the
rate of roxarsone degradation increased with the
3.2. pH value, moisture content and organic matter temperature. When the temperature was up to 40 ºC,
60% of roxarsone had degraded within 40 hours. In the
The pH values went up from 5.3 to 8.1, present study, raw material of composting was stored
increasing by more than two pH units during the in the open air for a few days before composting and
composting process (Fig. 2). This is attributed to the pile temperature was up to 40 ºC. Therefore,
ammonia nitrogen generation from the organic matter roxarsone and arsanilic acid had already degraded
degradation. During the first 7 days, the pH values before composting. The secondary metabolite was
fluctuated a little, e.g., it rose in the first 3 days and arsenite that decreased from 24% (on the first day) to
then fell rapidly on the 7th day. This was a 8% (on the 53th day) of total arsenic. The organic
consequence of the activity of acid-forming bacteria arsenic forms, including MMA and DMA, fluctuated
which break down complex carbonaceous material a little but maintained a stable low level at
into organic acid intermediates (de Bertoldi et al., approximately 5% of total arsenic. Furthermore,
1983) in the early stage of swine manure windrow unidentified arsenic compounds accounted for
composting. Organic matter and moisture contents approximately 27% to 60% in this process and need
decreased 7.8% and 23.3%, respectively, as shown in further study in the future.
Fig. 2. In the process of composting, complex As shown in Fig. 3a, the main arsenic
physical, chemical, and biological reactions occurred, metabolite was arsenate that varied drastically from
i.e., organic matter was degraded while metals and about 30% to 60% of total arsenic throughout the full
metalloids, such as arsenic, could potentially be scale swine manure windrow composting.
Fig. 2. Changes of moisture content, organic matter and pH value during the full scale swine manure windrow composting
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Wang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1563-1573
As shown in Fig. 3b, arsenate concentration concentration of arsenate dropped down to the
declined roughly from about 400 µg·kg-1 to almost minimum (below the limit of detection).
below the limit of detection during the first 7 days, Composting is an aerobic process which uses
however, it went up dramatically to 727 µg·kg-1 from naturally occurring microorganisms to convert
the 7th day to the 10th day and then increased slowly biodegradable organic matter into a humus-like
until the 40th day and finally dropped a little at the end product (Georgacakis et al., 1996). Arsenic species
of the swine manure windrow composting. It was variation depended on many factors, including
interesting that the variation of arsenite was totally temperature, pH value, moisture content, redox
opposite to that of arsenate, in other words, potential and microorganism activity.
concentration of arsenite went up when that of Additionally, the dominant form of arsenic in
arsenate went down obviously, vice versa. These oxygenated situation is arsenate (Byrd, 1990; Neff,
results showed that concentrations of arsenite reached 1997). This might explain why arsenate was the
to the maximum (437 µg·kg-1) on the 7th day of the primary arsenic species in the full scale swine manure
swine manure windrow composting, while windrow composting process (Fig. 3a.).
Fig. 3. Changes of different arsenic species during the full-scale swine manure windrow composting:
(a) Percentage, (b) Concentration
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Changes of arsenic speciation during swine manure windrow composting at full scale
Moreover, the other inorganic arsenic form, of this study was that the exchangeable fraction of
arsenite, appeared in all of the compost samples. With arsenic kept in a really low level (0~84.9 µg·kg-1 DW)
alteration of some composting factors, including during the composting (Fig. 4). The carbonates
temperature, pH value and moisture content, both fraction of arsenic varied from 18.6% to 45.3%, and
inorganic arsenic forms, arsenate and arsenite, its average value was 30% in the composting process.
transformed mutually in the composting process (Fig. The mobility and bioavailability of Fe/Mn oxides
3b.). Garbarino studied that the moisture content and fraction of arsenic highly depended on Eh and pH
the temperature influenced the rate of arsenic values, and changed dramatically during the swine
transformation (Garbarino et al., 2003). In this study, manure windrow composting process.
the full scale windrow composting was operated in the The organic and residual fractions of arsenic
open air and turned once a week during the were relatively low mobility arsenic forms which
thermophilic stage. Pile turning increased the air flow accounted averagely for approximately 10% and 29%
which could bring more oxygen through the pile and respectively during the whole composting process.
its porosity. Jiang et al. reported that the pile Their concentrations at the end of composting were
temperature risings were observed after turning and not much difference (arsenate at 576.53 µg·kg-1DW
these risings were caused by the degradation of and arsenic bound to Fe/Mn oxides at 637.46 µg·kg-
1
partially decomposed materials which were DW). In general, arsenic presenting as arsenate under
transferred from the anaerobic areas to the aerobic oxic conditions is often adsorbed into organic matter,
areas (Jiang et al., 2011). iron and manganese oxides and oxyhydroxides
In this study, the first turning happened on the (Newton et al., 2006). According to this conclusion,
first day and the second turning happened on the 8th arsenic bound to Fe/Mn oxides to some extent ought
day. Therefore, oxygen content might be deficiency to be a part of arsenate during most of the time of
due to the activity of a great amount of aerobic composting in this study. Furthermore, because
microorganisms and decomposition of organic matter arsenate was the main species and arsenic bound to
in the end of the first week, the pile might probably be Fe/Mn oxides was the main fraction, it seemed they
under anaerobic or anoxic condition. Additionally, were linked. The low frequency of pile turning in the
relatively high moisture content (approximately 50%) thermophilic stage and a relatively low pH value
in the beginning of composting might impede oxygen (around 5.0) at the start of composting might explain
internal diffusion, causing partial anaerobic condition. both of arsenate and arsenic bound to Fe/Mn oxides
The presence of microorganisms in the composting decreasing roughly in the first 10 days. As shown in
pile combined to anaerobic condition might enhance Fig. 5, it is interestingly found that variation of
transformation of arsenic from As (V) to As (III). arsenate had the similar trend to arsenic bound to
These might well explain that the oxidation state Fe/Mn oxides in the first 10 days of composting. In the
arsenic (arsenate) decreased to a low level and environment, As (V) and As (III) are the dominant
reduction state arsenic (arsenite) increased up to a forms of inorganic arsenic, which As (III) is much
relatively high level on the 7th day of composting (Fig. more toxic than As (V) (Jain and Ali, 2000). In this
3b). The mobility of five different arsenic fractions study, the variation of the ratio of As (V) to As (III)
changed in the order as following: exchangeable > reflected their mutual transformation to some extent.
carbonates > Fe/Mn oxides > organic > residual. The The point on the 7th day was extremely low and might
exchangeable fraction was the most toxic and highly be due to low frequency pile turning in the first week
mobility arsenic form. However, the surprising result of composting.
(a) (b)
Fig. 4. Changes of five arsenic fractions during the full scale swine manure windrow composting process:
(a) Percentage, (b) Concentration
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Wang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1563-1573
In this study, it seemed that the influence of the the actual true reason about the ratio of As (V) to As
pile turning on the ratio of As (V) to As (III) was (III) variation in the composting process needs further
obvious. It was thrilling to notice that the ratio of As studies. Compared with As (III) and As (V), the
(V) to As (III) kept increasing along with the concentrations of organic arsenics such as MMA and
composting, which indicated that the proportion of the DMA were relatively lower, in the range of 0~150
more toxic As (III) decreased. In the thermophilic µg·kg-1 DW. Methylation theoretically will not occur
stage, the pile was turned thoroughly once a week and abiotically even if there is a supply of Carbon source,
the composting was almost under aerobic condition. such as protein and other organic compounds because
This might be the main reason that the ratio of the C-C, C-N and C-O bonds are more stable than C-
As (V) to As (III) kept increasing in the first 38 days. As bonds (Williams, 1988). Biomethylation of metals
Nevertheless, there was no pile turning in the mature and metalloids occurs extensively in the environment
stage and the composting was almost under partial and methylated compounds show different properties
anaerobic condition, which might result in the ratio of in mobility, bioavailability and toxicity in comparison
As (V) to As (III) dropping dramatically in the last to their inorganic precursors (Sigel, 2010). Fig. 6
several days. Therefore, one pile turning should be showed that the ratio of As (V) to As (III) kept
added in the mature stage to better control the increasing in the first 38 days and then decreased in
proportion of As (III) for improving detoxification on the last several days of the composting.
arsenic. Moreover, some reports indicated that under It is interesting to point out that the ratio of As
near-neutral conditions (pH=6.5) and different Eh (V) to As (III) in this study achieved maximum value
conditions (Eh=450, 325, 100 and 0mV), the major at pH of about 6.5, and stayed at a very low level at
inorganic arsenic species was always arsenate pH of around 5.5 (Fig. 7). The process of
(Carbonell-Barrachina et al., 2000). biomethylation was regarded as a detoxification
There were some reports on the variation of the process for many years; however, more recent
ratio of As (V) to As (III) in other medium, like the research has indicated that the reverse is in fact the
ocean, coastal waters and estuary (Neff, 1997), case (Sigel, 2010). Fig. 3b showed that the tendency
however, little works have been done about the ratio of DMA was similar to that of arsenate, which both
of As (V) to As (III) during the composting process. declined in the beginning and then climbed smoothly
For example, in open ocean seawater, the ratio of As until the 40th day and decreased a little in the last days
(V) to As (III) may exceed 300 (Li, 1991), and coastal of the composting. The level of MMA was always the
water was influenced by freshwater runoff and high lowest, even lower than the limit of detection in the
primary production, the ratio may be much lower full-scale swine manure windrow composting process.
(Andreae and Andreae, 1989). Different from ocean, The methylated arsenic accounted for 1% to
coastal waters and estuary, high level activity of 9% of total arsenic in the composting process.
microorganisms in the composting process might Recently, Diaz-Bone et al. (2010) indicated that
contribute a lot to the variation of aerobic/anaerobic metalloids, such as arsenic, could undergo intensive
condition, temperature, pH value and so on, therefore biomethylation during composting.
Fig. 5. Correlation between arsenate and Fe/Mn oxides arsenic concentrations during the full scale
swine manure windrow composting process
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Changes of arsenic speciation during swine manure windrow composting at full scale
Fig. 6. The ratio of As (V) to As (III) variation with time during the full scale swine manure windrow composting process
Fig. 7. The relationship between pH value and the ratio of As (V) to As (III) during the full scale
swine manure windrow composting process
Extraordinary high concentrations of up to 150 stable and showed a slightly increasing trend from
mg·kg-1 methylated arsenic species as well as 1.35 mg·kg-1 DW to 1.69 mg·kg-1 DW (Fig. 3b) due to
conversion rates up to 50% were observed. In this the decomposition of organic matter and the reduction
study, the percentages of methylated arsenic were not of bio-mass during the swine manure windrow
so high because of a relatively low level of total composting process. The primary arsenic species was
arsenic in the compost materials. The other reason As (V), increasing from 29.6% of total arsenic on the
might be that DMA and MMA were only a small part first day to 34.1% of total arsenic on the 53th day. A
of methylated arsenic species and other forms of very promising result was that the most toxic arsenic
methylated arsenic species were not detected in this species, arsenite, reduced a lot from 24.1% to 8.1% of
study. The total arsenic concentrations kept relatively total arsenic (Fig. 3a). Additionally, organic arsenic
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Wang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1563-1573
(MMA and DMA) accounted for 4.7% at the end of intensive livestock farms in the suburb of Hangzho,
composting. Acta Agriculturae Zhejiangensis, 20, 35-39.
Finstein M., Miller F., Strom P., (1986), Waste treatment
4. Conclusions composting as a controlled system, Biotechnology, 8,
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Garbarino J.R., Bednar A.J., Rutherford D.W., Beyer R.S.,
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from 325.71 to 138.35 µg·kg-1 DW and arsenate roxarsone in poultry litter. I. Degradation of roxarsone
increased from 401.19 to 576.53 µg·kg-1 DW. The during composting, Environmental Science and
percentages of arsenite, arsenate and DMA were Technology, 37, 1509-1514.
24.10%, 29.68%, 4.87% of total arsenic in the Garbarino J.R., Kanagy L.K., Cree M.E, (2006),
beginning and 8.19%, 34.13%, 4.75% of total arsenic Determination of elements in natural-water, biota,
respectively at the end of the composting. Arsenate sediment, and soil samples using collision/reaction cell
had the similar trend to Fe/Mn oxides arsenic fraction. inductively coupled plasma-mass spectrometry, US
Department of the Interior, US Geological Survey.
During this composting process, the most
Georgacakis D., Tsavdaris A., Bakouli J., Symeonidis S.,
toxic arsenic, arsenite, decreased about 16%. It was (1996), Composting solid swine manure and lignite
proven that composting was a suitable method for mixtures with selected plant residues, Bioresource
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Hanc A., Szakova J., Svehla P., (2011), Effect of composting
Acknowledgements on the mobility of arsenic, chromium and nickel
This work is financially supported by Special Fund for contained in kitchen and garden waste, Bioresource
Agro-scientific Research in the Public Interest (No. Technology, 126, 444-452.
201303091), the National Natural Science Foundation of Hsu J.H., Lo S.L., (2001), Effect of composting on
China (No. 50578156 and No.21077122) and the National characterization and leaching of copper, manganese,
Key Technology R&D Program (2012BAC25B00). and zinc from swine manure, Environmental Pollution,
114, 119-127.
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1575-1581
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Department of Biology and Aquaculture, Agricultural Faculty, Trakia University, 6000 Stara Zagora, Bulgaria
Abstract
One of the main challenges for the development of biomass algal system production is the high operational and capital costs for
these technologies. A great opportunity to overcome these challenges may however exist in the integration of wastewater treatment
with algal biomass production. The algae are used for treatment of industrial wastewater, for purification of effluent originating
from livestock production, while the studies concerning the use of algae species for the treatment of aquaculture effluent are very
few. The aim of our research was to compare the nitrogen and phosphate removal efficiency and the growth of two microalgae
species – Scenedesmus dimorphus and Botryococcus braunii, cultivated in wastewater, originating from freshwater aquaculture
production. A laboratory bioreactor was used for algae cultivation. It consisted of 500 mL Erlenmeyer flasks, containing wastewater
from semi closed recirculation aquaculture system. Light regime was adjusted at 15:9 h light:dark cycle, the air was enriched with
CO2 up to 1% and the water temperature was kept between 25 and 27oC. Samples for water chemical analysis and growth
measurement were taken at the beginning of the trial, at the 24th, 96th and the 168th hour after the start of the experiment. A better
removal efficiency of nitrogen compound from wastewater originate from aquaculture was determined for B. braunii and the
concentration of ammonia, nitrite, nitrate and total nitrogen decreased at the end of trial by 50%, 84.4%, 63.1% and 61.5%
respectively. A better phosphate removal efficiency (77.8%) and better growth rate were found for Sc. dimorphus when aquaculture
effluent was used as a growing media.
Received: March, 2014; Revised final: February, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: ivailo_sir@abv.bg; Phone: +359896669829
Velichkova et al./Environmental Engineering and Management Journal 17 (2018), 7, 1575-1581
30 times in comparison to oilseed crops which are Both microalgae strains were supplied by
cultivated at land (Sheehan et al., 1998). Algae depot (USA) (www.algaedepot.com). The
Botryococcus braunii is a green microalga that microalgae cultures were kept in glass flasks of 5 mL
produces hydrocarbons up to 75% from its dry volume with reseeding for their preservation in a good
biomass and it has already been proven as a renewable physiological condition.
source of fuel (Brown et al., 1969; Banerjee et al., The wastewater originating from the semi
2002; Casadevall et al., 1983; Dayananda et al., 2005; closed recirculation aquaculture system (semi – closed
Velichkova et al., 2012). Many researches have RAS) was used as a growing medium for tested
proven that Scenedesmus dimorphus is one of the most microalgae. Effluent treatment in the semi – closed
promising algae species for biomass and biofuel RAS included a mechanical filter and a biofiltration
production as well (Becker, 1994; Goswami and (nitrifying filter with bio balls) for water purification.
Kalita, 2011; Varsharani and Geeta, 2011; Velichkova Daily, 40% of the water volume in semi - closed RAS
et al., 2013). was replaced with fresh water. The wastewater, used
One of the main challenges for the as medium for the tested microalgae was taken after
development of biomass algal system for biofuels mechanical and biological filtration from the pumping
production is the high operational and capital costs for tank, before daily fresh water replacement (Fig. 1).
these technologies (Alabi et al., 2009; Benemann, The total biomass of raised in the recirculation
2008). A great opportunity to overcome these aquaculture system common carps was 150 kg-1.
challenges may however exist in the integration of
wastewater treatment with algal biomass production. 2.2. Description of the Bioreactor for microalgae
The microalgae are used for treatment of cultivation
industrial wastewater: soya sauce effluent (Shirai et
al., 1998), brewery industries (Simate et al., 2011), A bioreactor consisting of 500 mL Erlenmeyer
dairy wastewater (Danalewich et al., 1998; Woertz et flasks and filled with wastewater from the semi closed
al., 2009), as well as for purification of effluent, RAS was used in the current trial. Three luminescent
originating from livestock production – poultry lamps Sylvania Aqua Star – 18w, 10 000 K, were
(Mahadevaswamy and Venkataraman, 1986; placed at a distance of 30 mm from the flasks. Light
Murugesan et al., 2010), pig farms (Aguirre et al., regime was adjusted at 15:9 h light:dark cycle in an
2011; Po Chung et al., 1978), cattle farms (Ayala and illumination incubator until the end of the experiment.
Vargas, 1987; Lincoln et al., 1996). Until now few The air was enriched with CO2 up to 1%, regulated by
studies concerning the exploitation of algae species for manometric control and injected to the bottom of the
the treatment of effluent in aquaculture have been flasks at a constant flow rate. The water temperature
made (Borges et al., 2005; Dumas et al., 1998; was kept between 25 and 27oC, pH varied between 6.5
Hussenot et al., 1998; Laliberté et al., 1994; Lefebvre and 7.5 and for this reason was not adjusted.
et al., 1996). Nevertheless, these studies are ignored Samples for water chemical analysis were taken at the
(Wang, 2003) and the science publications concerning beginning of the trial and at the 24th, 96th and 168th
them are highly limited. The aim of our research was hour after the start of the experiment. They were
to compare the nitrogen and phosphate removal centrifuged at 300 rpm for 10 min, for precipitation
efficiency as well as the growth of two microalgae and removal of algal cells (Lee and Lee, 2002). Every
species - Scenedesmus dimorphus and Botryococcus variant of the experiment was conducted in six
braunii cultivated in wastewater, originating from replications (Fig. 2). Other analyzed water chemical
freshwater aquaculture production to answer whether parameters were measured spectrophotometrically
it is possible to integrate the treatment of an with spectrophotometer DR 2800 (Hach Lange). The
aquaculture effluent with algal biomass production. methods and range of tests conducted during the
experiment are shown in Table 1.
2. Material and methods
2.3. Growth measurement, chlorophyll and carotenoid
2.1. Algae species and media content of microalgae culture
Two microalgae species were used in the study: Optical densities of microalgal cultures were
- Scenedesmus dimorphus (SKU: AC-1002) measured at 0, 24, 96 and 168 hours after the start of
- Botryococcus braunii (SKU: AC-1006) the experiment, in three repetitions.
Fig. 1. Semi-closed RAS and sampling point: 1. Fish farming tank; 2. Mechanical filter; 3. Biological filter; 4.
Pumping tank; 5. Inlet water; 6. Outlet water; 7. Pump; 8. Sampling point
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Integrated use of two microalgal species for the treatment of aquaculture effluent and biomass production
Table 1. Methods and ranges of tests, used for monitoring Sc. dimorphus the according percentages were 75%
of hydrochemical parameters during experimental period and 44.4%. The pH of wastewater increased in both
tested variants during the trial (Fig. 2).
Determination Measuring
Parameters The differences in nitrite values between the
method range (mg L-1)
tested variants were statistically significant for the
Ammonia Indophenol blue 0.015 – 2
48th and 168th hour samples (P≤0.05). For the last
Nitrite –
Diazotization 0.015 – 0.6 measurement differences were highly significant
nitrogen
Nitrate - (P≤0.01) (Table 2). The differences in the quantity of
nitrogen
2.6 dimethylphenol 0.23 – 13.5 nitrate in wastewater used for the cultivation of B.
Total Koroleff digestion + braunii and Sc. dimorphus were statistically
5 - 40
nitrogen 2.6 dimethylphenol significant for the 96th and 168th hour samples
Phosphorus
Phosphomolybdenum
0.05 – 1.5 (P≤0.05) (Table 2). The total nitrogen decreased in the
(ortho +
blue
PO4-P wastewater containing B. braunii and Sc. dimorphus
total) 0.15 – 4.5 PO4 from the beginning until the end of the experiment by
61.5% and 54.4% respectively and the differences
The samples with a volume of 1 mL, were were statistically significant at hours 96 and 168
appropriately diluted with deionized water and the (P≤0.05) (Table 2). The quantities of removed
average absorbance at 550 nm was recorded with the phosphates from aquaculture wastewater were similar
help of a spectrophotometer DR 2800 (Hach Lange). for both tested strains (Table 2).
The isolation of pigments from algae cells The results varied from 1.4 mgl-1 at the start to
included the following procedures: harvesting 2 mL of 0.38 mg L-1 at the end of experiment for Sc. dimorphus
microalgae cells by centrifugation at 10000 rpm, two and from 1.3 mg L-1 to 0.41 mg L-1 for B. braunii,
times for 3 min and discarding the supernatant, corresponding to 77.8% and 68.4% phosphate
suspending cells in 2 mL methanol/water 90:10 v/v removal efficiency respectively. The differences
and Vortex mixing for 1 min, heating of the concerning phosphate in the wastewater, used as a test
suspension for half an hour, in a water bath at 60ºC, medium for both explored microalgae species, were
cooling of the samples at room temperature, statistically significant for none of the taken
centrifugating the suspension (10000 rpm for 3 min) wastewater samples (P>0.05) (Table 2).
and discarding the supernatant with dissolved
pigments. The absorbance of the pigments extract 3.2. Growth parameters of tested microalgae, using
(665, 652 nm for chlorophyll content (a+b) and 470, aquaculture effluent as a medium for their cultivation
666 nm for carotenoids content) was recorded
spectrophotometrically. The chlorophyll content (mg The optical densities were higher at the 4th day
L-1) was computed according to Porra et al., (1989) since the beginning of experiment (96 hour) for both
method and carotenoids - according to Lichtenthaler microalgae species cultivated in the wastewater and
(1987) method. Data analysеs were conducted by reached 0.95 for Sc. dimorphus and 0.8 for B. braunii
using ANOVA (MS Office, 2010). (Fig. 3). After this day of maximum optical density,
the values of this parameter declinedin both tested
3. Results microalgae strains, as the nutritional compound in
wastewater decreased heavily.
3.1. Efficiency of nitrogen compounds and phosphate The measured optical density in Sc. dimorphus
removal in tested microalgae using aquaculture strains was higher by 10.5%, compared to the value of
effluent as a medium for their cultivation B. braunii at the end of trial, but the differences were
not statistically significant (P≥0.05). At the end of the
The values of this parameter in the experiments experiment the results showed that the contents of
with B. braunii and Sc. dimorphus were similar at the pigments - chlorophyll a+b and carotenoids were
end of the trial and the differences were not higher by 8.6% and 5.15% respectively in Sc.
statistically significant (P≥0.05). dimorphus, compared to their quantity in B. braunii,
The measured nitrogen compounds (ammonia, when they are cultivated in wastewater originating
nitrite, nitrate and total nitrogen) in the wastewater from freshwater aquaculture. However, the
used for cultivation of both experimental microalgal differences were not statistically significant for any of
species decreased significantly during the experiment the measurements made concerning these growing
(Table 2). The concentration of ammonia in the trial parameters (P≥0.05) (Fig. 4).
with B. braunii decreased from 0.302 to 0.158 mg L-1
and for Sc. dimorphus from 0.301 to 0.20 mg L-1. 4. Discussions
These results corresponded to 50% and 33.5%
reduction of ammonia respectively, but differences Many authors stated that algal species
were not statistically significant (P>0.05) (Table 2). B. usually increase pH, due to the photosynthetic CO2
braunii reduced the concentration of nitrite and nitrate assimilation (Borowitzka, 1998; Chevalier et al.,
in wastewater, originating from aquaculture 2000; Larsdotter, 2006). These points are confirmed in
production by 84.4% and 63.1% respectively and for recent research as well.
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Velichkova et al./Environmental Engineering and Management Journal 17 (2018), 7, 1575-1581
Table 2. Changes in nitrogen compounds of Sc. dimorphus and B. braunii in wastewater from aquaculture production during the
treatment period (mg L-1)
Fig. 3. Optical density (OD) of Sc. dimorphus and B. braunii, cultivated in wastewater from aquaculture production
One of the possible consequences of high pH In our opinion pH did not suppress microalgae
in media is the induction of flocculation in algal growth in the current trial, because pH values did not
cultures, which could be a reason for reduction of reach very high levels and varied between 6.5 and
nutrient uptake and growth. 7.43. Because of the low values of ammonia in
If the pH values increase over 9, most of wastewater originating from aquaculture, it could be
inorganic carbon is converted to carbonate, which concluded that this parameter had no negative effect
cannot be assimilated by the algae. on the microalgae growth.
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Integrated use of two microalgal species for the treatment of aquaculture effluent and biomass production
Fig. 4. Chlorophyll (a+b) and carotenoids (mg L-1) concentrations in Sc. dimorphus and B. braunii,
cultivated in wastewater from aquaculture production
Concentrations higher than 20 mg NH4+N per is its slow growth: its doubling time is 7 hours (Qin,
liter in wastewater are not recommended due to 2005). According to Banerjee et al., (2005) the growth
ammonia toxicity (Borowitzka, 1998). The preferred of B. braunii is 20 times slower, compared to fast-
nitrogen compound for microalgae growth is ammonia growing algae so they recommended for its cultivation
and when it is available, no alternative nitrogen a low-cost investment system, like raceway pond, as
sources will be used (Bhaya et al., 2000). The low economically effective. Our results for the hemical
ammonia concentration in wastewater used as a parameters of effluent waters were very similar to
medium for both tested microalgae species could those of previous studies (Borges et al., 2005;
explain the advanced utilization of two other nitrogen Hussenot et al., 1998; Tovar et al., 2000). Namely the
sources – nitrite and nitrate. The higher concentration wastewaters from fish production are distinguished
of nitrite makes it a less convenient nitrogen source for mainly by dissolved inorganic nutrients like nitrogen
algae, because of its toxicity (Becker, 1988). During and phosphorus. This makes aquaculture effluent one
the experiment the values of nitrite were not so high, possible medium for low cost microalgae biomass
which probably excluded the possibility of nitrite production (Laliberté et al., 1994). Ammonia removal
toxicity for tested microalgae species. efficiency of Sc. dimorphus in the current research was
The efficiency in nitrogen removal lower compared to other reports (Gonzalez et al.,
(ammonium, nitrite, nitrate and total nitrogen) from 1997), but higher than the results of Chevalier and De
aquaculture effluent in B. braunii was higher la Noüe (1985), which reported a removal efficiency
compared to the Sc. dimorphus strain in all of 23.31%. Ammonia, total nitrogen and phosphate
measurements. The results for nitrogen and removal efficiency were higher in other algal species
phosphorus removal by B. braunii in the current from genus Scenedesmus – Sc. quadricauda used for
research were found to be better than thosereported for swine wastewater treatment after appropriate dilution
swine wastewater treatment, by using tubular with tap water (Gantar et al., 1991).
bioreactor (Lee et al., 1999). In their research removal At the 8th day, the percent of ammonia, total
rates of swine wastewater nitrogen and phosphorus nitrogen and phosphate uptake varied between 99.5 -
byB. braunii were 43.9% and 41.7%, respectively, 100, 97.9% - 99.4% and 74.3 - 99.9% respectively at
after 14 days of incubation. The results for chlorophyll different tested dilutions. The water samples from
density of B. braunii, cultivated in wastewater as a locations around the Organized Industrial Zone were
growing medium from the current research were found to stimulate the growth of green microalgae
similar with those of other authors (Tsukahara and Desmodesmus (=Scenedesmus) subspicatus (Katalay
Sawayama, 2005) stating that B. braunii could et al., 2012). Charity et al., (2009) evaluated the
effectively remove nitrogen and phosphorus from growth, removal of nutrients and organic matter of
secondary sewage treatement (SST) in the continuous microalgae Scenedesmus sp. in wastewater derived
bioreactor system. from remains of fish for 15 days.
The main factors affecting B. braunii’s growth They established 2.24 mg/L chlorophyll and
are availability of nitrogen and phosphate, light 0.89 mg/L carotenoids, and dry biomass 0.44 mg/mL.
intensity and pH (Qin, 2005). In the current study, In our results a high growth rate of the microalgae
measured growth parameters indicated a better growth culture and high chlorophyll and carotenoid contents
of Sc. dimorphus, compared to B. braunii, when were also observed. Volotina et al. (2004) also
wastewater from aquaculture was used as a growing determined a high biomass after 24 hours cultivation
medium. Among the main disadvantages of B. braunii in artificial wastewater.
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Velichkova et al./Environmental Engineering and Management Journal 17 (2018), 7, 1575-1581
The two tested microalgae are a good option Cyanobacteria - Their Diversity in Time and Space,
for the biological treatment of aquaculture effluent. Whitton B.A., Potts M. (Eds.), Kluwer, Dordrecht, 397-
Both species showed a good nitrogen and phosphorus 442.
Borges M.T., Silva P., Moreira L., Soares R., (2005),
removal efficiency and the current research provides a
Integration of consumer-targeted microalgal production
good alternative technology for B. braunii and Sc. with marine fish effluent biofiltration–a strategy for
dimorphus production - integration of effluent mariculture sustainability, Journal of Applied
treatment from aquaculture and biomass production, Phycology, 17, 187-197.
which could decrease operational costs and will make Borowitzka M.A., (1998), Limits to Growth in Wastewater
the technology for tested microalgae production Treatment with Algae, In: Inland Saline Aquaculture
highly sustainable. Workshop, Wong Y.S., Tam N.F.Y. (Eds.), Springer
Verlag., 203-226.
5. Conclusions Brown A.C., Knights B.A., Conway E., (1969),
Hydrocarbon content and its relationship to
physiological state in the green alga Botryococcus
This research provided a proof of concept for braunii, Phytochemistry, 8, 543-547.
an integrated technology of aquaculture effluent Casadevall E., Largeau C., Metzger P., Chirac C., Berkaloff
treatment process that combines nutrient removal and C., (1983), Hydrocarbon production by unicellular
microalgae production for potential use as a biofuel microalga Botryococcus braunii, Biosciences, 2, 129.
feedstock. Charity E., Andrade R., Alexandra L., Vera B., Carmen H.,
A better removal efficiency of nitrogen (2009), Biomass production of microalga Scenedesmus
compound (ammonia, nitrite, nitrate and total sp. with wastewater from fishery, Revista Téchnica
nitrogen) was determined for B. braunii and better Zulia, 32, 126-134.
Chevalier P., De la Noüe J., (1985), Wastewater nutrient
phosphate removal efficiency as well as better growth
removal with microalgae immobilized in carrageenan,
rate were found for Sc. dimorphus when wastewater Enzyme and Microbial Technology, 7, 621-624.
from aquaculture effluent was used as a growing Chevalier P., Proulx D., Lessard P., Vincent W. F., De la
medium. Noüe J., (2000), Nitrogen and phosphorus removal by
high latitude mat-forming cyanobacteria for potential
Acknowledgements use in tertiary wastewater treatment, Journal of Applied
This study was supported by the Faculty of Agriculture, Phycology, 12, 105-112.
Trakia University (project 3E/2012). We also would like to Danalewich J.R., Papagiannis T. G., Belyea R. L.,
thank Mrs. Maia Andonova and Mr. Alexander Iordanov for Tumbleson M. E., Raskin L., (1998), Characterization
their great help inchecking and editing our manuscript. of dairy waste streams, current treatment practices, and
potential for biological nutrient removal, Water
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1583-1590
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Unlike other vegetables, mushroom production requires several substrate ingredients, energy to sterilize the substrate, water to
humidify the fruiting house and waste management of the spent substrate and used materials. This work studied the environmental
impacts and eco-efficiency of sajor-caju mushroom (Pleurotus sajor-caju (Fr.) Sing.) production in terms of climate change
potential, acidification potential, water depletion potential and fossil fuel depletion potential, using life cycle assessment (LCA)
method. The results showed that the mushroom production in small and large farms had nearly the same environmental
performance. Their environmental impacts were lower and their eco-efficiencies were higher than those for medium-sized farms.
This means the medium-sized farms would cause more environmental impacts in order to obtain the same profit as the other two
farms. It was found that there was inefficient use of both substrate and energy in the medium-sized farms. This is probably because
the medium-sized farm had relatively low financial limitations, compared to the small farms, and relatively less concern over
efficient use of resources, compared to the large farms. The reduction of sawdust and rice bran, used as substrate ingredients, as
well as wood, used as energy source for sterilization, to the same amounts as those used in the small farms could reduce
environmental impacts (5-25%) and improve eco-efficiencies (10-40%) of the medium-sized farms to be close to those for large
and small farms.
Key words: climate change, environment, farm size, life cycle assessment, mushroom
Received: May, 2014; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
1. Introduction that energy and water are required and air emissions
are released from these processes. Emissions of CO2,
Sajor-caju mushroom (Sajor-caju (Fr.) Sing.) CH4 and N2O contribute to climate change potential
is in the oyster mushroom family. It is a common while SO2 and NOx can cause terrestrial acidification.
mushroom with the second largest production volume The production of substrate ingredients, energy and
in Thailand (DOAE, 2012a). In 2012, the total other raw materials used in the farms also consumes
production was 5,679 ton (DOAE, 2012b). Unlike fossil and water resources as well as releases
other vegetables, mushroom production requires emissions to air. Although these environmental
preparation and sterilization of substrate which burdens take place outside the farms, they arise from
comprises several ingredients. After mixing and the sajor-caju production and thus their environmental
putting substrate ingredients in a plastic bag, the impacts should be included.
substrate is sterilized by steam. Then spawn is put Life Cycle Assessment (LCA) methodology is
inside the substrate bag and incubated in a humidified an efficient tool to evaluate environmental impacts
house. After harvest, the spent plastic bags and quantitatively. It considers the use of resources and the
substrate are burnt or left unmanaged. It can be seen emissions from a product’s life cycle, i.e., from the
∗
Author to whom all correspondence should be addressed: e-mail: rungnapatongpool@gmail.com; Phone: +66 25646500; Fax: +66 25646404
Ueawiwatsakul et al./Environmental Engineering and Management Journal 17 (2018), 7, 1583-1590
stages of raw material provision, production, use, to the large farms were relatively low due to better
disposal and recycling. Data on resources used and management. However, Manjunatha et al. (2013)
emission substances under the scope of the study are found that, in the southern part of India, small farms
collected and then classified according to their (up to 1.01 ha) showed better resource use efficiency
environmental impact potential. For example, CO2, than large farms (> 1.01 ha). In Slovenia, small farms
CH4 and N2O are classified as climate change (up to 5 ha) were relatively more profitable and the
substances. Each substance is given a characterization large farms (> 20 ha) were more technically efficient
factor according to its impact potential. For example, (Bojnec and Latruffe, 2013). It was reported that the
characterization factors of 1 kg CO2, 1 kg CH4 and 1 number of medium-sized farms (5-20 ha) in Slovania
kg N2O are 1, 25 and 298 kg CO2 eq, respectively has been decreasing because they were too small to be
(BSI, 2008). Then the characterization factor of each economically efficient but they were too large to be
substance is multiplied by the amount of the profitable.
substance. The sum of the multiplication is the impact Environment, economic and social factors are
of the concerned category. The methodology of LCA concerned in sustainable development. The indicator
has been explained in detail elsewhere (Dong et al., measuring progress toward economic and
2016; ISO, 2006a, 2006b; Finnveden et al., 2009; environmental sustainability is eco-efficiency. It was
Tongpool et al., 2010). Using LCA, Gunady et al. defined as the value of the product or service, divided
(2012) studied greenhouse gas emissions from by environmental influence (Blengini et al., 2017;
production of button Agaricus bisporus mushroom in Verfaillie and Bidwell, 2000). The environmental
Western Australia. They found that life cycle impact, economic benefit and eco-efficiency of
greenhouse gas emissions of the button mushroom different sizes of mushroom farms have not been
was 2.8 kg CO2eq/kg and that the main impact reported elsewhere.
contributor was the transport of raw materials such as Therefore this work compared the
peat, compost and spawn. environmental performance of sajor-caju production
While the farm activities affect the of small, medium and large farms. The concerned
environment, the environment influences farm environmental impact categories were climate change,
productivity and economy. Kanellopoulos et al. terrestrial acidification, water depletion and fossil fuel
(2014) illustrated that future farming systems were depletion. The key impact contributors were also
challenged to adapt to changes in climate, market and investigated and measures to reduce environmental
environment in order to remain competitive and to impacts as well as increasing eco-efficiency proposed.
meet increasing demand for food. To remain viable,
smaller farms were said to require technological 2. Case studies presentation
development to increase yields and compensate for
substantial increase in price of inputs. Technology and 2.1. Environmental impact assessment
resource management in different sizes of farms were
shown to have impacts on performance and economic As shown in Fig. 1, the production processes at
viability of the farms. Pishgar-Komleh et al. (2012) sajor-caju farms include mixing and sterilizing
reported that, in Esfahan province of Iran, the energy substrates, inoculating with spawn, maintaining
input for potato production of large farms (larger than environmental controls for spawn run and fruiting, as
5 ha) was relatively low while the total energy output well as harvesting and managing wastes. Wastes are
was relatively high, compared to small (up to 1 ha) and burnt in the open air or used as fuel for steam
medium-sized (1-5 ha) farms. They also found that the generation or left unmanaged or sent to landfill,
amounts of seeds and chemical fertilizers applied in depending on individual farm practice.
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Environmental performance of sajor-caju mushroom production based on farm sizes in Thailand
The data of inputs (such as substrate higher amount of substrate while the large farms used
ingredients, plastic bags, and fuel) and outputs (such more electricity than the others. It can be seen that, due
as air emissions, wastes) of each process were to the use of machinery, the amount of electricity used
collected by interviewing the farmers in Ratchaburi in the large farms was about two and eleven times of
province, Thailand. Sizes of mushroom farms were that used in the medium and small farms, respectively.
divided into small, medium and large farms, having an In the sterilization process, the medium and small
annual production of less than 20-ton, 20-40 ton and farms used only wood as an energy source. The large
more than 40 ton, respectively (DOA, 2012). The farms used both wood and LPG. It was reported that
obtained data came from fifteen large farms, eight energy content of wood and LPG was 15.99 and 49.3
medium farms and eight small farms that together MJ/kg, respectively (DEDE, 2011). Therefore the
contributed 22 % of total sajor-caju production of the energy applied for the sterilization process in the
country in 2012 (DOAE, 2012b). Then the inputs and medium-sized farms was the highest (94.5 MJ),
outputs (inventory) for each farm size were weight compared to the small (71.3 MJ) and large (76.6 MJ)
averaged according to the annual production to obtain farms. Water consumption for steam generation in all
the averaged inventory of 1 kg sajor-caju production. farms was nearly the same but the water applied to
Amounts of air emissions from urea fertilizer and humidify the fruiting houses of the large farms was
combustion of wood, LPG, gasoline and burning of only half of that used in the small and medium farms.
wastes were calculated using emission factors of IPCC This is because every large farm used sprinkler
2006 (Eggleston et al., 2006) and EMEP/EEA 2013 system, providing a better control of water usage,
(EEA, 2013). Carbon dioxide from wood combustion which is not the case for small and medium farms.
was not counted due to carbon neutral rule. The inputs The environmental impacts of 1 kg sajor-caju
applied to sajor-caju production processes are are shown in Fig. 2. The impacts from production,
produced outside the farms and then transported to the transportation and mixing of the substrates were
farms. Therefore the data of resources consumption denoted as “substrate”. The impacts from the
and emissions due to transportation and production of production and transportation of fuel and water used
the inputs were included in the environmental impact for sterilization, as well as air emissions from fuel
assessment. These data were obtained from the Thai combustion during sterilization were denoted as
National LCI database (MTEC, 2013) and the “sterilizing”. The environmental burdens from
Ecoinvent database (Ecoinvent Centre, 2007). inoculating spawn and environmental controls for
Then the total resources and emissions were spawn run and fruiting were shown as “inoculating”
classified and multiplied by characterization factors and “fruiting”, respectively. The contribution of
according to their environmental impact potential, “harvest” came from the production and transportation
using the methodology of ReCiPe midpoint (H) of plastic bags used during harvesting. The
(Goedkoop et al., 2009) in order to quantify impacts in contribution of “waste” came from management of
the categories of climate change (unit: kg CO2 wastes after the harvest.
equivalent (eq)), terrestrial acidification (unit: kg SO2 It is shown that the sajor-caju production of the
eq), water depletion (unit: m3) and fossil fuel depletion medium-sized farms caused the highest environmental
(unit: kg oil eq). SimaPro 7.3.3 software (Pre impacts. The main impact contributors in all
Consultants, 2013) was used to facilitate the categories were “sterilizing” and “substrate”. The
calculation and to reduce any possible mistakes. climate change potentials of the large, medium and
small farms were 1.1, 1.4 and 1.2 kg CO2 eq/kg sajor-
2.2. Eco-efficiency caju, respectively. This was much lower than the level
obtained for button mushroom (Agaricus bisporus)
The cost of raw materials, energy, production in Australia (2.34 kg CO2eq/kg) reported
transportation and labor used for the production of by Gunady, et al. (2012). In the category of fossil fuel
sajor-caju in each farm was obtained by interviewing depletion, about 0.2 kg oil eq was consumed by the
the farmers and suppliers. The sale price at sajor-caju production of 1 kg sajor-caju which was one third of
farm was 30 Baht/kg (about 1 US$/kg) in 2013. The shiitake production (0.6 kg oil eq/kg) (Tongpool and
profit at the farm was equal to the difference between Pongpat, 2013). However, the impacts of sajor-caju in
the sale price and the total cost. Eco-efficiency of these two categories were higher than those for normal
sajor-caju production was derived from the profit of 1 produce, such as tomato, onion, bush bean, baby corn
kg sajor-caju divided by the environmental impact of and potato (0.1-0.5 kg CO2 eq/kg, 0.03-0.07 kg oil eq)
1 kg sajor-caju production. (Tongpool et al., 2011).
“Sterilizing” was a major impact contributor in
3. Results and discussion the categories of climate change and terrestrial
acidification, while the “substrate” was the main
3.1. Environmental impact assessment contributor in the categories of water depletion and
fossil fuel depletion. Both “sterilizing” and “substrate”
The inventory for production of 1 kg sajor-caju recorded for the medium-sized farms were higher than
is shown in Table 1. The medium-sized farms used those of small and large farms.
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Ueawiwatsakul et al./Environmental Engineering and Management Journal 17 (2018), 7, 1583-1590
Farm size
List Unit
Large Medium Small
Input Mixing of substrates
Sawdust kg 2.0725 2.4779 2.3343
Rice bran kg 0.1084 0.1495 0.0969
Urea fertilizer kg 0.0015 0.003 0.0015
Other ingredients kg 0.0583 0.04845 0.0392
Pakaging e.g. bag, neck ring kg 0.0256 0.0274 0.0269
Total weight of substrate kg 2.2663 2.7063 2.4988
Electricity kWh 0.0042 0.0030 0.0014
Transportation ton-km 1.4711 1.7131 1.5100
Sterilizing of substrates
Wood kg 4.7650 5.9070 4.4527
Liquefied petroleum gas (LPG) kg 0.0084 0 0
Transportation ton-km 0.1236 0.1673 0.1533
Tap water m3 0.0008 0.0010 0.0020
Water from well or river m3 0.0012 0.0013 0.0001
Inoculation with spawn
Transportation ton-km 0.0002 0.0002 0.0002
Spawn kg 0.0091 0.0102 0.0101
Environmental control for spawn run and fruiting
Pesticides kg 2 x 10-5 4 x 10-5 2 x 10-5
Water from well or river m3 0.0031 0.0065 0.0016
Tap water m3 0.0018 0.0060 0.0094
Gasoline m3 2 x 10-7 5 x 10-7 5 x 10-7
Electricity kWh 0.0226 0.0117 0.0011
Transportation ton-km 0.0001 0.0002 0.0002
Harvesting
Transportation ton-km 0.0042 0.0041 0.0041
Plastic bag kg 0.015 0.015 0.015
Output Sajor-caju in plastic bag kg 1 1 1
Unmanaged solid wastes kg 1.2832 1.8662 1.6520
NOx kg 0.0070 0.0087 0.0065
SO2 kg 0.0008 0.0010 0.0008
NH3 kg 0.0030 0.0038 0.0028
CO2 kg 0.0466 0.0298 0.0194
CH4 kg 0.0230 0.0284 0.0215
N2O kg 0.0003 0.0004 0.0003
(a) (b)
(c) (d)
Fig. 2. Environmental impacts of 1 kg sajor-caju production of the large, medium and small farms, in the categories of:
(a) climate change, (b) terrestrial acidification, (c) water depletion and (d) fossil fuel depletion
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Environmental performance of sajor-caju mushroom production based on farm sizes in Thailand
Fig. 3 shows components contributing to the burdens from the milled rice production were
impact of “sterilizing” in the medium-sized farms. It allocated to all products according to their economic
can be seen that the emissions from “sterilizing” values; 71% to milled rice, 23% to broken rice, 4% to
contributed almost 100% in the categories of climate rice bran and 2% to rice husk. This ratio was derived
change and terrestrial acidification. These emissions from the multiplication of the market price and the
came from wood combustion which releases relatively amount of each product obtained from rice milling.
high amounts of CH4, N2O and SOx, compared to LPG The amounts of rice products from the rice milling
combustion, considering the same given energy were obtained from Nadsathaporn (2007). Sawdust
(Eggleston, et al., 2006; EEA, 2013). and slab are also by-products of lumber production.
Fig. 4 shows components that caused Since all products can be sold, the environmental
“substrate” of the medium-sized farms to have high burdens from the lumber production were allocated to
environmental impacts. It can be seen that the all of them according to the mass ratio; 50% to lumber,
production of sawdust, rice bran, packaging and 10% to sawdust and 40% to slab (MTEC, 2013).
transportation of sawdust were the main sources of the Although Table 1 shows that water used for
impacts. This corresponded to the data shown in Table humidifying fruiting houses of the small and medium
1 that the medium-sized farms used relatively large farms was 2-3 times of that used in the large farms,
amounts of sawdust, rice bran and packaging. Fig. 2e (water depletion category) reveals that its
Although rice bran, broken rice and rice husk are by- contribution to life-cycle water depletion of sajor-caju
products of milled rice production, they have was insignificant compared to the water consumption
economic values. As a result, the environmental of “substrate” dominated by rice bran production (Fig.
4).
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Ueawiwatsakul et al./Environmental Engineering and Management Journal 17 (2018), 7, 1583-1590
Fig. 5. Components of wastes from the production of 1 kg sajor-caju in the large, medium and small farms
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Environmental performance of sajor-caju mushroom production based on farm sizes in Thailand
3.3. Improvement of environmental performance of National Science and Technology Development Agency
(NSTDA) Thailand, under the Thailand National LCI
It was shown that, in the medium-sized farms, Database Project, Thailand Advanced Institute of Science
a relatively large amount of substrate was used and and Technology and Tokyo Institute of Technology
subsequently left after the harvest. This implies that it (TAIST-Tokyo Tech), and Faculty of Engineering,
Kesetsart University. We acknowledge the department of
is possible for these farms to reduce the substrate
agriculture and farmers in Ratchaburi province, Thailand,
amount while still achieving the same production for data provision. We thank Dr. John Thomas Harry Pearce
yield. As sawdust and rice bran largely contributed to for proof reading the article.
environmental impacts (Fig. 4) and total cost (Table 2)
of the sajor-caju production, it is proposed that the References
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1591-1597
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
The article presents a study on indirect environment-related effects of electric car vehicles use. Although electric vehicles are
considered zero emission vehicles, their use may be linked to indirect pollution of environment caused by energy sources used for
electricity production and also other sources of pollution such as poor recycling procedures. A computer simulation was performed
to determine the energy consumption of electric vehicles available on the Romanian car market. The values obtained were
correlated with emissions of CO2, NOx and SOx pollutants. Furthermore, a supplementary analysis was performed to determine the
necessary combination and related management of energy sources to minimize the environmental impact of electric vehicles, in
order to increase their use for a future sustainable transportation domain. The study shows that SOx emissions in particular will
increase in Romania alone, as a result of the implementation of electric cars, unless alternative and renewable energy sources are
implemented in the society. This study reports crucial statistics and information which outline that legislative policies must be in
place before a full implementation of electric vehicles is carried out, in order to avoid increase in emissions countries without the
direct access to renewable energy resources.
Key words: electric vehicles, energy sources, environment, management, pollutant emissions, modeling
Received: June, 2014; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July, 2018
∗
Author to whom all correspondence should be addressed: e-mail: florin.mariasiu@auto.utcluj.ro; Phone +040730011747; Fax +040264415950.
Varga and Mariasiu/Environmental Engineering and Management Journal 17 (2018), 7, 1591-1597
cars). Mariasiu (2012) and Liu et al. (2008) consider the structure of primary energy sources for electrically
that the main technologically barriers for increasing energy production comparatively for Europe and
the car market share for EVs are considered to be the Romania. The coal remains an important primary
following factors: source of electrical energy production with direct
- the average EV purchase price is 100% greater than implications on the level and structure of pollutant
for a new IC engine car; emissions in atmosphere, both for EU 28 and
- there are serious limitations regarding the EVs Romania. In Romania, the use of coal for energy
autonomy and charging time (average value for production is with 14.3% higher than the EU average,
autonomy is considered to be 130 km and mostly EVs indicating that Romania must adopt energy policies
need 6 hours for a complete charging cycle); that lead to achieving at least EUs average value. As
- the low capacity of electric battery; major issue of energetic strategy, the Romanian
- the usable energy depending directly on many factors government makes efforts to complete units 3 and 4 of
(type of battery, type of powertrain, driving style, Cernavoda nuclear power plant, together with the
traffic conditions, ambient temperature and charging massive development of renewable energy production
technology); units. The reducing CO2 (and also GHG) emission
- proper recycling schemes for car batteries policy is also highlighted by government policies to
throughout the cradle-to-grave life cycle. support the increase of EVs market. Thus, for each EV
Given the above-presented barriers, at present, purchased, government offers a subsidy from purchase
the EU countries and authorities are taking numerous price for a new EV acquisition.
political, economic and social measures, to promote Currently, in Romania, there are only four EV
and increase the penetration of electric vehicles in manufacturers that offer to customers a total of six
transportation domain. To achieve a target of models (Table 1). There are important differences in
4,752,100 EVs for the end of 2015 at European level EVs models, between values pertaining to the
measures as: free parking, right to use bus-lanes, free autonomy for a full battery charge cycle. For these
entry to city-centers, financial subsidies and EVs, models available on Romania’s car market, a
incentives, exempts from registration tax, VAT, computer simulation process was used to identify the
annual car tax and congestion charges are some of EVs with minimum and maximum electric energy
adopted measures (Reiner et al., 2010; Nemry and consumption during a standard NEDC test. Further,
Brous, 2010). the electric energy consumption was converted to
It is also interesting to highlight that measures pollutant emissions, considering the particular
aimed at increase number of EVs include many structure of primary energy sources (POST, 2006).
subsidy programs in EU, most of which refer to The scenario-based analyses were conducted in order
taxation of CO2 emission level (“CO2-based car to establish whether the indirect pollutant emissions
taxes”). It can be easily to see that the indirect CO2 (CO2, NOx and SOx) could achieve the limits imposed
emissions from energy production are not perceived to by contemporary pollution norm (Euro 6), and
be a major barrier to EVs use and are not taken into evaluation in terms of their environmental impact.
consideration (Brinkman et al., 2010; Jansen et al., Besides major influence on air pollution of CO2
2010). Unfortunately, on closer analysis, it is evident emissions (by increasing the greenhouse effect), and
that EVs must be powered with electricity (to charge other pollutant emissions from road transport have
battery), which is not obtained only from direct influence on the environment, and their
environmentally friendly sources (or at least from magnitude when using electric vehicles is a novelty
renewable sources) (Varga, 2013). Europe-wide presented in this paper. SOx emissions were
primary sources for obtaining electricity rely heavily considered to be dangerous due to their contribution to
on coal, oil, gas and nuclear energy. In Fig. 1 is shown the direct creation of smog and acid rain.
1592
Indirect environment-related effects of electric car vehicles use
Those negative effects on environment and calculate the amount of the each considered pollutant
human health have been drastically eliminated by emission is presented below, in the case of CO2 (but
international norms that involving the use of fuels with applicable also for NOx and SOx emissions). After
low sulfur content. To present date (pending the obtaining data related to energy consumption for an
introduction of Euro 6 pollution norm), NOx emissions electric vehicle, the transformation into the amount of
were not a major concern in terms of limiting by law pollutant emitted into the atmosphere has been
to certain emission limit values. achieved, taking into account the characteristics of
The advent of well-documented studies Romania’s primary energy sources mix used for
regarding the effects of direct and indirect NOx electricity production in power stations. In case of CO2
emissions on the environment and human health, were pollutant, the following relation was used (Mariasiu,
determined their influence. From an environmental 2012) (Eq. 1):
perspective, the negative effects associated with NOx
emissions are soil nitrification with immediate
detrimental effects on plant growth and soil (1)
microorganisms’ life. Also, the toxic effect of NOx
emissions on human health manifests (especially in were EVCO2/km is the amount of CO2 emitted by energy
big cities) with respiratory and cardiovascular consumption per km, LNEDC is the length of NEDC
problems (Gustavsson et al., 2000; Weiss et al., 2012). cycle (11.008 km), EVCO2/NEDC is the amount of CO2
For these reasons the present work shows a broad emitted by energy consumption during a NEDC cycle,
approach on to the quantity and composition of CO2energy_source is the amount of CO2 emission function
pollutant emissions emitted indirectly, in case of use of energy source and the Plosses = 1.15-1.22 are the
of an electric vehicle. losses caused by electric distribution grid and internal
EVs electrical circuits (Tesla Motors, 2010).
2. Material and methods
3. Results and discussion
Analysis and computer simulation are research
tools widely used in many scientific fields. An The input data required to perform computer
immediate advantage of using computer simulation is simulation are presented in previous sections. To
the opportunity to obtain, at a relatively low cost, a obtain accurate results, the technical and operational
multitude of experimental data and possible cases of particularities of each model of EV were taken into
studied phenomena. In the present work, to obtain the account (total weight of the vehicle, wheel diameter,
EVs CO2 emission level for the standardized cycle transmission type, aerodynamic coefficient, battery
(NEDC - testing procedure recommended by the type, energy efficiency and losses).
European Union) conditions, CRUISE simulation Further, the pollutant emission levels obtained
environment were used. CRUISE software package for EVs operation, considered in the study, was
was developed and implemented successfully in the correlated with energy sources pollutant emissions
automotive industry by AVL List GmbH (2006) used to produce the electricity. The results analysis
(Varga, 2012). indicates that the lowest energy consumption is
Major benefit of CRUISE simulation software obtained for EV2 (Chevrolet Volt) and the highest for
is its modularity and interactive process of simulation EV3 (Renault Zoe). Fig. 2 depicts battery energy
and design of model for a various type of vehicles. For consumption for Chevrolet Volt during the NEDC
brevity, specific details of using CRUISE, how to cycle and related cumulative results for considered
build a vehicle model and how each function is used EVs and obtained from computer simulation are
are given in AVL User Manual (2009) and Varga presented in the Table 2. The amount of pollutant
(2012). Primary data used as input for the simulation emissions corresponding to each source of energy for
model, are technical data of considered electric electricity production and distribution of these sources
vehicles presented in Table 1. The method used to for EU28 and Romania are presented in the Table 3.
Table 1. Technical data of EVs models available on Romanian car market (Fuhs, 2009; Brooke, 2011)
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Table 2. EVs energy consumption vs. CO2 emissions (for NEDC test)
Table 3. CO2 emissions depending on the nature and distribution of energy sources
EU 28 Romania
Electrical Generation Grams of CO2
Share of energy CO2 emission Share of energy CO2 emission
Sources emissivity (g/kWh)
sources (g/kWh) sources (g/kWh)
Coal 1000 18% 180 22% 220
Oil 650 35% 227.5 25% 162.5
Natural Gas 500 23% 115 31% 155
Renewable 15 10% 1.5 14% 2.1
Nuclear 5 14% 0.7 8% 0.4
Total - 100% 524.7 100% 540
Table 4. NOX emissions depending on the nature and distribution of energy sources
EU 28 Romania
Electrical Grams of NOX
Share of energy NOX emission Share of energy NOX emission
Generation Sources emissivity (g/kWh)
sources (g/kWh) sources (g/kWh)
Coal 6 18% 1.08 22% 1.32
Oil 4 35% 1.4 25% 1
Natural Gas 1.7 23% 0.391 31% 0.527
Renewable 0.006 10% 0.006 14% 0.008
Nuclear 0 14% 0.00 8% 0.00
Total - 100% 2.877 100% 2.855
Table 5. SOX emissions depending on the nature and distribution of energy sources
EU 28 Romania
Electrical Generation Grams of SOX
Share of energy SOX emission Share of energy SOX emission
Sources emissivity (g/kWh)
sources (g/kWh) sources (g/kWh)
Coal 13 18% 2.34 22% 2.86
Oil 12 35% 4.2 25% 3
Natural Gas 0.1 23% 0.023 31% 0.031
Renewable 1.22 10% 0.122 14% 0.17
Nuclear 0 14% 0.00 8% 0.00
Total - 100% 6.685 100% 6.061
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Indirect environment-related effects of electric car vehicles use
Considering Romania’s future policy and If we consider the most favorable case of EV2
strategy in energy production and following the above type use, the CO2 emissions (from energetic source
considerations and presented algorithm for mix) are shown in the Fig. 3, in line with considered
calculations, the results and related discussions are scenarios (reducing the share of energy from coal and
presented below. CO2 emission decreases 5.5% in increase in same time the energy share from renewable
scenario A, 12.9% in scenario B and 19.1% in scenario sources and nuclear).
C, compared to the present situation. The target of
below 95 g/km of CO2 emissions (future Euro 6
pollution standard) is achieved in all cases of proposed
scenarios (Fig. 3).
Comparative analysis of NOx emissions
(compounded emissions of N2O and NO2) depending
on the energy source used for electricity generation
and selected scenarios are presented in the Table 7. It
is worth mentioning that with the introduction of Euro
6 emission norms for road vehicles (EC, 2007), NOx
emissions are taken into account in evaluating the
performance of a car (pollutant emissions). The
maximum accepted by Euro 6 norm is considered to
be 0.06 g/km for passenger cars. By using electric
vehicles considered in the study, a maximum level of
emissions of SOx (1.1 g/km) results, considering the
current structure of energy sources used to produce
electricity. Fig. 3. EV2’s CO2 emission function of scenarios
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Varga and Mariasiu/Environmental Engineering and Management Journal 17 (2018), 7, 1591-1597
Note that using electric vehicles, the accepted zero-emission vehicles; however, electricity (used to
level is exceeded more than 8 times (Fig. 4), with recharge the EV’s battery) produced in power plants
values between 0.49 g/km (scenario A) and 0.41 g/km is still predominantly based on the fossil fuel usage
(scenario C). and thus directly affects the quantity (amount) of
pollutant and greenhouse gases emissions.
Given the structure of energy sources mix (in
particularly, for Romania’ case) used for electricity
generation, the major pollutant emissions originating
from the combination of these energy sources (related
to energy consumption of available EVs on Romanian
market) was determined.
In terms of compliance with future European
standards of pollution emissions (95 gCO2/km –
2020), the calculated CO2 indirect emissions of EVs
use, failed to achieve the imposed limits, considering
the actual mix of Romania’s energy sources for
electricity production (scenarios A and B). If a part of
coal share (only 4%) will be replaced with renewable
and non-fossil (nuclear) sources, the EVs use indirect
Fig. 4. EV2’s NOx emission function of scenarios CO2 emission is with 2% lower than the future EURO
6 pollution standards. Worryingly are the high values
SOx emissions are directly responsible for the of indirect NOx and SOx emissions that occur when
existence of acid rain, rain that present an immediate using electric vehicles, which can lead to increasing
danger potential on the environment and human the frequency of occurrence of acid rain, with
health. SOx emissions are high due to the high immediate adverse effects on the environment and
proportion of use of coal in electricity production, both human health.
for Romania (22% of total energy production), as well As a major conclusion, it can be said that,
as in the case of Europe (18% of total energy before introducing EVs on car market, economic
production). policies and management of energy sources mix used
In case of programs and / or policies to improve for electricity production must take into account the
the structure of energy sources through intensive use indirect environmental effects that may occur as a
of renewable and/or non-fossil (Table 8, scenario C), consequence of this initiative. Prior to make major
emissions of SOx emissions may reach a minimum investments in recharging infrastructure of EVs
estimated value of 0.89 g/km, but still remain a great batteries and related policies to encourage the EVs
value considering that actually the emission of a market penetration, it is necessary to invest in
passenger car is limited to 0.02 g/km (Fig. 5). modernization of actual power plants (increasing
production efficiency and reducing pollutant
emissions) and the structure of energy sources used
(renewable and/or non-fossil sources).
However, even if electric vehicles use poses
certain problems of indirect pollutants emissions high
levels, there is the possibility of better management
regarding technologies applied to reduce pollution.
Reduction may be made directly to the source (power
plants) as a whole, with much better results than
implementing clean technologies (catalytic converter)
for each vehicle that uses an internal combustion
engine. It can thus achieve an economic cost
optimization in the reduction process of pollutant
emissions; differences can be used and/or directed to
Fig. 5. EV2’s SOx emission function of scenarios other programs to increase environmental quality.
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Indirect environment-related effects of electric car vehicles use
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1599-1611
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Real estate is an industry sector with high potential to increase energy efficiency. However, many of the existing green building
investment opportunities (GBIO) are not utilized because economic valuation tools are complex and oftentimes difficult to
understand. For this reason, we develop a formal, but comprehensible bottom-up model to determine the optimal investment amount
from an economic perspective, placing particular emphasis on the descriptive valuation of risk, and point out the applicability of
GBIO as insurance against energy price volatility. We also give examples of the model’s potential application. Our work shows
that considering the insurance effect will increase the optimal investment amount and that certain investment amounts lead to both
economic and ecological benefits in properties and property portfolios. Our findings can be used for a comprehensible enhancement
of existing valuation methods and tools to reduce the energy efficiency gap (EEG). They constitute a quantitative basis for the
adaption of laws to counteract the current underinvestment in the real estate sector.
Key words: energy efficiency gap, energy price risk, green building, investment valuation
Received: September, 2012; Revised final: July, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: mette@mail.de; Phone: + 49177 599 7011
Buhl et al./Environmental Engineering and Management Journal 17 (2018), 7, 1599-1611
also state intervention (e.g. taxes and subsidies) Dowlatabadi, 2007). The real estate sector is one of
influence the market price of energy. These distortions the largest consumers of energy and is responsible for
complicate conclusions about the ‘real’ height of the approximately 40% of global energy use (Pinkse and
EEG, which is also dependent on energy prices Dommisse, 2009) and 40% of all carbon emissions
(Levine et al., 1994). (Apgar, 2009). Energy consumption of properties is
Information problems: A variety of responsible for more than 30% of global final energy
information problems also influences the EEG. In demand and one-third of energy-related CO2
addition to the lack of information (e.g. on current emissions and is feared to increase by further 33%
energy consumption patterns and ways to reduce this until 2050 (compared to 2005) in a sub-optimal
consumption) (Levine, 1994), the principle-agent scenario (Global Energy Assessment, 2012). A study
problem is particularly important: In the context of by the McKinsey Global Institute (2007) revealed that
investments in green buildings this problem occurs, if the largest potential for reducing energy demand and
one party (the landlord) chooses the level of the negative effects on the environment (commonly
investments in energy efficiency measures, but the quantified in the emission of CO2 equivalents, CO2-eq)
energy bills are paid by the other party (the tenant) lies in the real estate sector. Existing technologies
(Brown, 2001; Jaffe et al., 2005). In general, could be integrated into so-called “green buildings”,
information problems lead to an underinvestment in thereby increasing energy efficiency by 35%
energy efficiency (Gillingham et al., 2009; Jaffe and (WBCSD, 2007). Although the ecological advantages
Stavins, 1994). of green buildings to significantly improve their CO2-
Transaction costs: In our context, transaction eq footprint are evident (Edwards and Naboni, 2013;
costs can be defined as costs of gathering, assessing Teng and Wu, 2014) and even net zero energy (NZE)
and applying information on the characteristics and buildings are possible from a technical perspective
performance, making decisions as well as enforcing (Kibert, 2014), the investment rate in higher energy
contracts relating to the purchase and installation of efficiency is only 1–1.5 % in non-residential buildings
technologies, which reduce the energy demand of a and only 0.07% in residential buildings (Rottke,
building (Hein and Blok, 1995; Levine et al., 1994). 2009). These figures demonstrate the existence and
The existence of transactions costs (which increase the high relevance of EEG especially in the real estate
total cost of energy efficiency measures) results in sector.
lower – and/or later – investments in energy efficiency Various strands of research try to reduce the
measures than it would be assumed from a purely neo- EEG in the building sector. So, for example, a macro-
classical perspective (Golove and Eto, 1996). economically oriented strand examines the impact of
Capital market imperfections: Especially in government programs to increase energy efficiency
capital intensive industries like the real estate (Abadie et al. 2012; Clinch and Healy, 2001; Dixon et
business, liquidity constraints complicate the al., 2010; Hull et al., 2009). Another line of research
quantification of the ‘real’ EEG. Limited access to evaluates and ranks the variety of technical devices,
financing for energy-efficient investments is resulting which are available for energy efficiency measures in
in underinvestment and therefore in an increasing the real estate sector, in terms of their economical
EEG (Gillingham et al., 2009). appropriate use (Jakob, 2006; Kobos et al., 2006). This
In current literature, the existence of these includes tools such as MAKRAL and RETScreen: The
barriers (and the difficulties resulting from their International Energy Agency (2001) uses a detailed
quantification) (Golove and Eto, 1996; Hein and Blok, and technology-specific linear programming approach
1995) lead to disagreements over the actual extent of to connect individual energy use to macroeconomic
the EEG. One of the main reasons for this it that effects. In this way, an optimal combination of
different scales are used: To demonstrate the problems technologies can be determined, which holds energy
related to the quantification of the EEG, Jaffe and service demands stable while minimizing energy
Stavins distinguish (already in 1994) between the system total costs. Software-based solutions like
“economist’s economic potential”, the “technologist’s RETScreen provide the opportunity to compare
economical potential” (which, in comparison, is different technologies with regard to their energy
higher than the first scale), the even higher generation, savings, life cycle costs, emission
“hypothetical potential” and the “narrow social reduction, financial figures and technology-specific
optimum” and the “true social optimum”. To illustrate risks.
these differences, we refer to Cullen and Allwood Against this background, it is not our goal, to
(2010), who argue that – from a purely technical correctly determine the actual amount of the EEG in
perspective – the global demand for energy could be the real estate sector, nor to quantify or integrate the
reduce by almost 90%, if energy conservation devices effects of market failures (like the above-mentioned
were entirely employed. In contrast, other authors like energy price distortions, information problems
Allcott and Greenstone argue that „the actual including principle-agent problems between landlord
magnitude of the EEG is small relative to the and tenant, transaction costs, capital market
assessment from engineering analyses“ (2012). No imperfections) or behavioral failures (Gillingham et
matter how big the EEG actually is – it plays an al., 2009), nor to develop a selection algorithm to
important role in scientific discussions on real estates classify or rank specific technical devices in terms of
(Jakob, 2006; Myers, 2014; Shove, 1999; Wilson and their ability to reduce the EEG. Rather, we first
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The “insurance effect”: How to increase the investment amount in green buildings
develop a rudimentary optimization model, by which model-based referring to its effective implication.
we quantified an “optimal investment amount in green Furthermore, most existing literature does not address,
buildings” in the setting of rented buildings and that investments in the real estate area are – caused by
building portfolios. In the context of focused the capital intensity for the landlord – characterized by
abstraction – and without loss of generality – only a a specific type of risks, which prohibits conventional
potential trade-off between the two factors “ecologic beta pricing. Thus, an isolated consideration of the
potential savings” and “economic investment amount” investment’s idiosyncratic risk – on the basis of
(necessary to attain the first factor) is modelled. On the established capital market-theoretical methods – is not
basis of this basic model, we want to formally derive possible.
the impact of the so-called „insurance effect” in the We will focus in detail on this issue and its
second part of this paper. The insurance effect impact on our modelling approach in section 3.1.1. If
describes the effect that reduced energy demand leads risk is discussed in existing publications, it is often
to reduced volatility of energy costs – an added value restricted to the statement, that due to risks, less
to risk-averse tenants, who can use GBIO as insurance measures to increase energy efficiency are useful or
against the impact of a possible damage event (energy can be performed (Hirst and Brown, 1990; Szabó et al.
price volatility) by paying a premium (rent increase). 2010; Thompson, 1997); an increase of risk leads – so
Correctly integrating this effect an increase of the it is concluded – (analogous to other market
initial optimal investment amount in green buildings imperfections) to an increase of the EEG in the real
can be derived. We would like to point out that factors estate sector.
such as the location of the property, its age, the Extending our above-mentioned basic model,
original level of its technical equipment, etc. are we will be showing in the second part of the paper,
consciously disregarded in our model-theoretic that, as a result of uncertainty about the future energy
considerations. These factors, in reality, play an price and unlike the above-mentioned common
important role in determining the optimal level of integration of risks, more measures to increase energy
investment in EEG. However, our paper primarily efficiency are meaningful. By working out this
focuses on the “insurance effects” and its insurance effect, which is new and so far unconsidered
consequences on the investment level. both in scientific discourse and business, a
Since the “insurance effect” can be worked out contribution to the future reduction of the EEG in real
even without additional factors (such as location, etc.), estate sector can thus be brought off.
we have decided to abstract from these effects. In the We believe that the capability of energy
main part of the paper, we will show that it is possible efficiency investments to work as an insurance against
to reduce the EEG if this insurance effect is taken into energy price volatility is a comprehensible benefit,
account, which in fact is a novelty in the scientific which should be used by means of awareness-raising
discussion of the EEG. It should be noted that the and informative actions, which are needed to
further use of the term “optimal” only refers to the accomplish behavior / social change (Vedung, 1998).
model-theoretic considerations outlined in this paper, As a consequence, our approach may contribute to
as potential market and behavioral failures (already counteract the energy efficiency gap by overcoming
discussed in the first part of the introduction) remain associated barriers like uncertainty and, first and
unattended. Against this background, the ‘model- foremost, information gaps (Hirst and Brown, 1990).
theoretic optimum’ differs from the ‘real’ optimal To illustrate our approach, the paper is structured as
level of investments in green buildings. Since the follows: In section 2, we develop our formal valuation
existence of an EEG can be regarded as proved and model with regard to specific characteristics of GBIO
since the gap is likely to be even greater if the already and determine the optimal economic investment
discussed failures are included, the model-theoretic amount under certainty in section 3. In section 4, we
optimality considerations lead in the right direction show the impact of the insurance effect when the
(i.e. towards the ‘real live optimum’). landlord has a real estate portfolio with several
Existing literature, which refers to EEG in the tenants. We use an example to illustrate the model’s
context of the real estate sector, only sporadically practical applicability in section 5 and conclude with
addressed uncertainty and the associated risks to the a summary of results as well as directions for future
EEG. If uncertainty/risk is focused, it is for example research in section 6.
related to uncertainty about future government We would like to point out that we already used
intervention (such as support programs and subsidies some of the assumptions and the modeling approach
or stricter regulations to internalize external effects) of section 2 and 3 in an earlier version of the paper
(Hirst and Brown, 1990), uncertainty about the future (Buhl et al., 2011). This paper builds upon our
energy price (Bristow and Kennedy, 2010), weather- preliminary groundwork and extends it significantly
related uncertainty effecting different amounts of with regard to the modeling of property portfolios
future energy use (Wang et al., 2012), uncertainty on (section 4), the demonstration of the model’s practical
the energy usage patterns of tenants (Silva and Ghisi, applicability (section 5) and inferable results (section
2014) or uncertainty about the actual long-term impact 6). Furthermore, this significantly extended version of
of new (and unproven) devices (Mills et al., 2006). the paper contains a comprehensive review of existing
In existing publications, often one of these literature regarding the energy paradox, EEG
risks is considered in detail and quantified, but without investments and uncertainty (section 1).
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The “insurance effect”: How to increase the investment amount in green buildings
Fig. 1. Investment in green buildings and its economic and ecological results
However, bottom-up models are also criticized identify the economical optimal investment amount.
to lack the ability to portray both broader Investing this amount of money will lead to
macroeconomic effects (Rivers and Jaccard, 2006) economical optimal and at least ecologically
and microeconomic decision-making by businesses advantageous results. In the framework of our model
and consumers when selecting technologies. In this the optimal (private) investment amount in green
vein, it has long been argued that bottom-up models buildings is derived. This single, private investment
provide only “an unrealistic portrait of microeconomic simultaneously contributes to reach the overall
decision-making frameworks for technology choice” economic optimum while being ecologically
(Mundaca et al., 2010). Despite the criticism, bottom- advantageous.
up models can be used to describe current and
prospective competition of energy technologies in 2.2 Main definitions and assumptions
detail on the supply and on the demand side. In fact,
also the aforementioned McKinsey study (McKinsey We consider a setting with a property being
Global Institute, 2007) is based on a bottom-up rented and used by a tenant from time T0 until T1. The
approach arguing that macroeconomic phenomena are tenant pays a constant periodic basic rental charge
“really nothing more than the sum of demand from (excluding energy costs) at the specific amount RC to
hundreds of microeconomic sectors”. the landlord. Furthermore, the tenant has to pay energy
Thus, bottom-up models can provide valuable costs EC to a gas/electricity supply company, which is
insights in radically different technology futures and necessary for the property’s operation. These energy
enable decision making which may help to take full costs are the product of the property’s energy demand
advantage of the benefits of energy efficiency d and the effective energy price at time t, P(t).
technologies in general, and GBIO in particular Additional expenses like, for example, expenses for
(Hourcade et al., 2006). Gallinelli (2008) uses a water supply are irrelevant for this analysis and are not
discounted-cash-flow approach, which discounts an considered. The landlord receives the periodic basic
investment’s expected future cash flows using a rental charge RC from the tenant. At the end of the
discount rate to reach a present value. In this letting in T1, the landlord sells the building and
connection, Keown et al. (1998) recognized the receives the resale return RR. The amount of RR can
particular importance of risk for energy-efficiency be considered the net present value of all future
investments and suggested a basic approach to achievable rental charges (as already motivated in the
integrate risk into a discounted-cash-flow valuation. introduction, the value of the land and other factors
They suggested the adaption of the discount rate like location, condition or technical equipment of the
depending on the height of the risk. However, Johnson building shall be disregarded at this point shall be
(1994) realizes that the use of the adapted discount rate disregarded at this point). Hence, it is irrelevant for our
is broadly discussed in literature, but is not a satisfying consideration whether the property is actually sold. In
way to take risk into consideration adequately. the following account, we assume the resale of the
property in T1 for the sake of simplicity. The
2.1. Key rationale property’s energy demand can be reduced with the
help of a green building investment, which is
The potential of green buildings to lower determined by the amount of its necessary investment
carbon emissions and energy consumption is payout I, with . However, many energy-
estimated to be 35% (WBCSD, 2007). In order to saving measures of green buildings require energy
achieve this amount, all possible GBIO have to be themselves. The net present value of these costs, as
implemented. This might be advantageous from an well as further costs (e.g., for possible breakdown) is
ecological perspective, but not necessarily from an integrated in I. The property’s energy costs can be
economic perspective. For a meaningful combination lowered permanently through GBIO to a level of
of ecological and economic perspectives (cp. Figure ECafter < ECbefore by reducing the energy demand from
1), we develop a quantitative optimization model to dbefore to dafter. Moreover, the resale return RR can be
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Buhl et al./Environmental Engineering and Management Journal 17 (2018), 7, 1599-1611
raised to RRafter > RRbefore. This relationship is verified 2.3 Objective function
by an empirical survey, assuming that the demand for
energy-efficient properties is on the rise because of the Energy prices have increased sharply during
expected long-term increase in energy prices. the last few decades. The price for light fuel oil
Consequently, increased resale returns can be realized increased from ~8€ ct/l in 1970 to 80€ ct/l in 2008 (i.e.,
(Bienert, 2009). For our model, we assume a ~6.2% p.a.). Furthermore, the world population will
diminishing marginal resale return. continue to rise (Tucker, 2007), and the consumption
The necessary investment payout occurs in T0 level of many nations will approach Western
and has to be paid completely by the landlord initially, standards. Hence, we can forecast a rising energy
although the landlord has the possibility of turning demand. Because of the inevitable excess demand, we
over a certain portion of the investment payout to the can assume exponentially rising energy costs in the
tenant (see next section). On account of this, the basic future. This forecast is supported by Buhl and Jetter
rental charge rises to RCafter > RCbefore. (2009), who stated that the price of each non-
Thus, GBIO generate economic benefits for renewable resource, – depending on the specific
both tenant (energy cost reduction) and landlord availability and demand, rises exponentially. One
(resale return increase). However, these benefits are possibility to formalize the exponential rise of the
not necessarily equally high. Often, energy-efficiency considered energy price P(t) is P(t ) = P0 ⋅ (1 + r ) t .
investments are not made because of the above- Here, P0 is the energy price in its initial state in T0. The
mentioned landlord-tenant dilemma (The Climate parameter r is the periodical growth rate of the energy
Group, 2008), that is, the landlord decides on the price compared to the previous period. The time
investment amount, but only the tenant benefits from dependence of the energy price is implied by the
the resulting energy cost savings. In contrast, tenants exponent t. We obtain the objective function through
do not have the right to claim GBIO from the landlord. pretest-posttest study, that is, by comparing all cash
Since this paper focuses on the derivation of the flows of the landlord-tenant unit after GBIO, CFafter,
“insurance effect”, we can consider the landlord and to all cash flows before any investment, CFbefore, and
tenant as one and do not analyze the division of the maximizing the (positive) difference between the two.
investment amount. At this point, game theory can This maximal difference is obtained through
provide some important directions for research, for optimization of the objective function Eq. (1).
example, as done by Bengtsson (1998) and also the
WBCSD (2009) drill on this in their simulation study.
∆CF ( I ) = CFafter ( I ) − CFbefore =
To proceed, the following assumptions are considered
T1
necessary for further analysis: ∆RR( I )
= − I + ∑ ∆EC ( I ) +
(1)
A.1: Landlord and tenant decide on the =
t =1 (1 + i )T1
investment amount together and evaluate GBIO
T1
P0 ⋅ (1 + r ) t ∆RR( I )
= − I + ∆d ( I ) ⋅ ∑
according to their willingness to pay.
A.2:
+
Landlord and tenant calculate with
t =1 (1 + i ) t (1 + i )T1
the identical risk-free discount rate i.
A.3: The energy price increases in the
long run.
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The “insurance effect”: How to increase the investment amount in green buildings
As mentioned above, the resale return rises evident that an investment for the integration of a
with the investment amount. One cannot assume that modern roof insulation material has a different impact
GBIO can raise the resale return of a property linearly. on a property’s energy demand and its resale return
Hence, we can assume that investments’ effects than an investment of the same amount to integrate an
decline. Thus, we can use a strictly monotone information system-based heating and air-
dRRafter d 2 RRafter conditioning management system. Furthermore,
increasing ( > 0 ), concave ( < 0) properties have individual cost functions, which are
dI d 2I
determined by specific prevailing conditions
course of the function for RRafter (starting from the
(Atkinson et al., 2009). We approach this problem by
resale return without any GBIO RRbefore). This can be
using only generic functions that encompass a general
formalized exemplarily for I ≥ 1 as
case to illustrate basic interdependencies. Our model
RRafter ( I ) = RRbefore + s ⋅ ln I . The parameter s
can be tailored to specific GBIO by simply adapting
determines the inclination of the resale return curve. the course of the functions. To sum up, we can
The higher s we choose, the more GBIO increase the formalize the induced effects of GBIO in properties to
building’s resale return. Hence, the achievable raise energy efficiency using Eq. (2).
increase of the resale return with GBIO is
∆RR( I ) = RRafter − RRbefore = ( RRbefore + s ⋅ ln I ) − T1
P0 ⋅ (1 + r ) t s ⋅ ln I
∆CF ( I ) = − I + v ⋅ I ⋅ ∑ + (2)
RRbefore = s ⋅ ln I . The second element of the objective t =1 (1 + i ) t (1 + i )T1
function describes the development of the property’s
energy demand dafter(I) depending on the investment Setting the objective function’s first derivative
amount. As mentioned above, the energy demand to 0 and verifying the second-order condition shows
decreases permanently when the investment amount that the objective function is strictly concave in the
dd domain and reaches its maximum at the investment
rises ( after < 0 ). At this point, we use a linear amount.
dI
relation between energy demand and investment T1 P ⋅ (1 + r ) t
s
amount in the relevant region. One possible function I RiskNeutra
*
l = + v ⋅ ∑ 0 (3)
for this is d after ( I ) =d before−v ⋅ I . dbefore is the property’s (1 + i )T1 t =1 (1 + i ) t
energy demand in the initial state, that is, before any
Consequently, it is reasonable to raise the
investment. v determines the curve’s inclination and
equates to the marginal energy demand of the I*
investment amount up to RiskNeutral Eq. (3). Below this
property: If the investment amount is raised by one investment amount, an elevation of the investment
monetary unit, the energy demand of the property falls sum leads to a higher resale return increase and energy
permanently by approximately v units. This cost reduction than the necessary payout. In contrast,
observation is in line with Christen et al. (2002), who the positive effects above the investment amount
found that the energy-efficiency gain of GBIO has a I RiskNeutra
*
l , in fact, exceed the incidental payouts, but
linear connection with the hence emerging costs. Note
that our model also allows for negative energy disproportionally high capital expenditure is
demand, which can be realized with sufficiently high necessary. These relationships are depicted in Fig. 2
investment amounts and energy generation devices, (like before, we assume the potential of green
such as solar panels. It is important that these buildings to lower carbon emissions and energy
relationships are technology-dependent. It is self- consumption to be 35% (WBCSD, 2007)).
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Buhl et al./Environmental Engineering and Management Journal 17 (2018), 7, 1599-1611
3. Optimal investment amount under uncertainty capital market theory, which help to differentiate
between market and project specific risks, this is not
Resources and commodities are ever more the case for the investor/landlord in the context of real
subject to speculative transactions. Investment in estate. Investments in real estate use up a very large
commodity indexes increased by a factor of 20 from part of a private investor’s capital. Since it is not
US $13 billion in 2003 to US $260 billion in 2008 possible in this case to diversify the market risk,
(Masters, 2008). As shown by Shiller (1981), individual pricing of risk by means of a preference
increased speculation and trading of commodities and functional appears to be appropriate. This approach is
energy sources cause an increase in price volatility consistent with Johnson (1994), who draws attention
(Duffie et al., 1999). Other sources of uncertainty, for to boundaries of established investment theories – like
example, a volatile resale return due to market price the capital asset pricing model (CAPM) and arbitrage
changes, are irrelevant for our consideration and are pricing theory (APT) – in the context of energy
thus excluded. In order to account for energy price technology choices and rather proposes variations of
volatility, the following assumptions and definitions the net present value (NPV).
are necessary. Considering energy price volatility in our
valuation, we discover a particular effect: Taking into
3.1.1. Assumptions and definitions account the rules of linear transformation of random
variables (in our consideration, the present value of the
For this consideration, we assume normally energy savings), the reduced energy demand results in
distributed energy prices. As mentioned above, the reduced volatility of the energy costs (Greene, 2008).
energy cost savings are composed of the product of the Thus, green buildings operate like insurance: By
energy prices at time t with the demand reduction ∆d paying a premium (rent increase), the insurance holder
and are thus normally distributed, too. Then, the time- (tenant) can insure himself against the impact of a
dependent, volatile energy savings can be discounted possible damage event (energy price volatility). The
to an expected present value of the savings, which is tenant’s willingness to negotiate such insurance and
also normally distributed. Because of the volatility of the amount of premium he is willing to pay depends
energy prices, the calculated present value of the on his individual risk attitude:
energy cost savings is volatile, too. Here, we interpret Tenants who negotiate insurance want to avoid
the volatility of the present value as the possible (or lower) risk. They prefer to pay a certain amount of
positive or negative deviation of the present value money (here, the rent increase) rather than accept an
from the expected present value of the savings. We uncertain, more volatile payout. In this manner, we
measure this deviation with the variance σ2 (σ2 > 0). can mentally divide the rental charge RCafter into three
σE2 is the variance of the energy price. In order to parts: The first part is the basic rental charge RCbefore.
integrate measures for risk (σ2) and return (μ), we use The second part is the counter value for the achievable
a preference function: energy cost savings. The third part is the insurance
A.4: The risk-adjusted value of the premium, which is the value of the achievable risk
investment is determined by both parties with reduction (Buhl et al., 2011). This (over all periods of
Bernoulli’s theory of expected utility (Bernoulli, the letting) accumulated value equates to the
1954) and the preference function Eq. (4): difference of the second part of Bernoulli’s preference
function before and after the investment. As
α mentioned in A.4, we assume risk-averse (and
Φ(µ , σ ) = µ − ⋅σ 2 (4)
2 consequently insurance-affine) decision makers
(Bamberg and Spremann, 1981). For them, the risk-
We assume risk-averse decision makers, that reducing effect of green buildings creates added value.
is, the present value of the investment’s cash flow is
valued lower if its variance is higher (assuming a fixed 3.1.2. Optimization model
expected value μ).
The risk-adjusted value corresponds to a Valuating all cash flows and risks of the
preference function, which is developed according to landlord-tenant unit before and after GBIO with
established methods of decision theory and integrates Bernoulli’s preference function, we obtain the new
an expected value, its deviation, and the decision objective function to be optimized Eq. (5):
maker’s risk aversion. This preference function is
based on the utility function U ( x) = −e 2αx and is ∆Φ ( µ , σ ) = Φ after ( I ) − Φ before =
compatible to the Bernoulli principle (Bernoulli, Φ ( µ after ( I ), σ after ( I )) − Φ ( µ before , σ before ) =
1954). The Arrow-Pratt characterization of absolute
α 2 α 2
risk aversion (Arrow, 1971) is with , = µ after − ⋅ σ after − ( µ before − ⋅ σ before ) = ∆Φ ( I ) =
modeling a risk-averse decision maker. It seems 2 2
T
P ⋅ (1 + r ) t ∆RR( I ) α
= − I + ∆d ( I ) ⋅ ∑ 0
1
reasonable for us to choose this approach to + + ⋅ ∆σ 2 ( I )
adequately include energy price risks in our specific t =1 (1 + i ) t (1 + i ) T 2 1
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The “insurance effect”: How to increase the investment amount in green buildings
The first three terms are similar to Eq. (2) in similarities in the prices, for example, for domestic
our consideration under certainty. The last term fuel oil and domestic gas in the past. Many drivers for
corresponds to the volatility reduction of the energy energy prices, such as global demand or inflation, are
costs weighted with the risk-aversion parameter α and present across all energy sources. As theoretical and
that can be increased with the investment amount. empirical research affirms (Da Silva, 2007), energy
To sum up, we can formalize the induced prices are not independent of each other, but are
effects of GBIO in properties under consideration of correlated, that is, they are systematically associated
risk as shown in Eq. (6). with each other (Eydeland and Wolyniec, 2003). In
order to accurately determine the optimal investment
P0 ⋅ (1 + r ) t s ⋅ ln I α
T1
amount for a property portfolio, we have to account
∆Φ( I ) = − I + v ⋅ I ⋅ ∑ + + ⋅ for the impact of energy price dependencies on the
t =1 (1 + i) t (1 + i)T1 2 (6) overall risk and the manner in which it is affected by
⋅(d 02 − (d 0 − v ⋅ I ) 2 ) ⋅ σ E2 GBIO. If energy price dependencies were disregarded,
the computed optimal investment amounts would not
The objective function is strictly concave in the account for possible diversification effects and would
domain again and reaches its maximum at the consequently be false. For this reason, we want to
investment amount in Eq. (7). adapt our model and add the following assumption:
A.5: All n properties are supplied by
T1
P0 ⋅ (1 + r ) t energy sources whose prices depend on each other.
−1 + v ⋅ ∑ + α ⋅ v ⋅ d 0 ⋅ σ E2 The measurement for the energy price dependencies is
t =1 (1 + i ) t
I* + the correlation coefficient kij. We consider these
2 ⋅ α ⋅ v 2 ⋅ σ E2
correlations coefficients to be given. All other possible
T1
P0 ⋅ (1 + r ) t (7) dependencies among the properties are disregarded.
(1 − v ⋅ ∑ + α ⋅ v ⋅ d 0 ⋅ σ E2 ) 2
t =1 (1 + i ) t As mentioned above, energy price
s dependencies affect the overall volatility of a property
+4 ⋅ ⋅ α ⋅ v 2 ⋅ σ E2 portfolio. According to Keown et al. (2008), the
(1 + i )T1
+ overall variance of a portfolio is determined by
2 ⋅ α ⋅ v 2 ⋅ σ E2 summing up the stand-alone risks of each property σi
and considering the dependencies between the energy
By comparing the computed optimal investment prices with the help of the correlation coefficient.
amount considering the insurance effect to the optimal Hence, the overall energy costs’ variance of a property
investment amount of a risk-neutral decision maker, portfolio (without any GBIO) is shown in Eq. (8)
we can see that the optimal investment amount
considering energy price volatility is always higher n n
than assuming a non-volatile energy price. σ overall
2
= ∑∑ σ iσ j kij (8)
Considering the energy price and the insurance effect i =1 j =1
accurately will consequently lead to an increase of the
actual optimal investment amount. Consequently, If we consider the properties being supplied by
valuating GBIO correctly will lead to economic energy sources whose prices do not show perfect
decisions that will generate more benefits also from an positive correlation (i.e., kij = [−1;+1[ ), we can see
ecological perspective.
that the overall property portfolio’s variance is smaller
4. Addressing the ‘insurance-effect’ in multiple than its variance with perfect positive correlation
properties ( kij = +1 ). This risk-reducing effect is called the
diversification effect and can be interpreted in the
In this section, we transfer our presented following manner: If the considered properties are
analysis to an approach with multiple properties and supplied by the same energy source, kij equals +1 since
analyze how the insurance effect takes effect in an energy price is always fully positively correlated
building portfolios. with itself. If this energy price increases, the overall
payouts for energy will then increase in equal
4.1.1. Assumptions and definitions proportion since energy costs only depend on one
stochastic factor. However, if the landlord and tenants
Now assume a landlord with n ≥ 2 properties i decide on properties supplied by different energy
and multiple tenants. The landlord and his tenants sources, kij is likely to take on a value of k ij = [−1;+1[
together decide on the investment amount to be spent
on GBIO. For this, they need to determine the overall , that is, the energy prices will not show perfect
positive correlation with each other. If one of the
optimal investment amount I overall
*
for the entire
energy prices increases, the payouts for energy will
property portfolio as well as the optimal allocation of then increase in a smaller proportion since the risk of
this investment amount to each property. If we a possible price increase is diversified on multiple
consider the properties to be supplied by different stochastic factors. Consequently, the resulting overall
energy sources (e.g., gas, oil etc.) and compare their portfolio risk is lower than the aggregate stand-alone
prices, we discover a special characteristic: There are risks of the properties.
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Buhl et al./Environmental Engineering and Management Journal 17 (2018), 7, 1599-1611
Since the stand-alone risks of each property of GBIO, another potential of green buildings becomes
a portfolio codetermine the value of the portfolio’s visible: In certain cases, GBIO positively affect the
diversification effect, GBIO also indirectly affect the value of the diversification effect and are consequently
value of the diversification effect. As a well-grounded able to reduce the overall risk in a property portfolio
investment valuation has to account for all investment- in two ways: reducing the stand-alone risks of each
caused consequences on financial figures, we need to property due to energy demand reduction and reducing
consider the investment’s effect – as well as the the portfolio risk due to a positively affected
insurance effect – on the value of the diversification diversification effect. Consequently, a correctly
effect in our valuation, too. conducted economic valuation will lead again to an
increased overall optimal investment amount and to a
4.1.2. Optimization model higher ecological contribution to energy efficiency.
Despite not computing higher overall optimal
Eq. (9) is the objective function for multiple investment amounts in all cases, it is evident that the
properties accounting for all aforementioned GBIO- high economic and resulting ecological potential of
caused effects: GBIO only becomes visible, if risk is considered
correctly.
∆Φ overall ( µ , σ ) = Φ overall , after ( I i ) − Φ overall , before =
= Φ ( µ overall , after ( I i ), σ overall , after ( I i )) − 5. Example of potential application and results
Φ ( µ overall , before , σ overall , before ) = ∆Φ overall ( I i ) =
A building society wants to design a block of
n n T1, i
P ⋅ (1 + ri ) t ∆RRi ( I i ) offices in an energy-efficient manner. Therefore, the
= −∑ I i + ∑ ∆d i ( I i ) ⋅ ∑ 0, i + +
(1 + i ) 1, i company wants to exploit the high potential of GBIO.
T
i =1 i =1 t =1 (1 + i ) t
For this example, we consider the following situation:
α n n 2 The duration of the letting is 30 years (T1 = 30). The
⋅ ∆ ∑∑ σ i ( I i )σ 2j ( I j )kij company receives a one-time resale return for the
2 i =1 j =1 property after 30 years and calculates (like their
(9) tenants) with a discount rate of i = 3%. The resale
This function consists of the following terms: return can be raised by an energy-efficiency
The negative sum of the investment amounts in each investment, beginning from an amount of 1,000,000
property (first term) and the sum of the achievable monetary units (MU) in a form that can be described
energy cost savings and resale return increases for by the following function:
each property (second term). Additionally, the third
RRafter ( I ) = 1000000 + 10000 ⋅ ln I . The property’s
term considers the individual risk reductions for each
property as well as the investments’ effect on the value demand for domestic fuel oil can be lowered by
of the diversification effect. approximately 0.06 l p.a. with each invested MU
In order to obtain the overall optimal starting from a basic demand of 3000 l p.a. Hence, we
investment amount as well as the individual optimal use the following relationship for the energy demand:
investment amounts for each property, this objective d after ( I ) = 3000 − 0.06 ⋅ I . We assume an energy
function has to be optimized. At its maximum, the price increase of 7% p.a. with an initial price of P0 =
necessary (but not sufficient) conditions shown in Eq. 0.85 MU/l. We determined the optimal investment
(10) are fulfilled. amount to be 4,604 MU. Hence, the company should
invest exactly this amount to maximize its economic
(10) profit and thus contribute to energy efficiency.
Investing more than the computed optimal amount is
advantageous from an ecological perspective, but not
For the verification of the second-order from an economic perspective. In order to account for
condition, we test the Hessian matrix to be negatively risk and determine the optimal investment amount
definite in the domain. Since the multiple unknown from an economic viewpoint under uncertainty, we
decision variables cannot always be separated, an simply assume the energy price to be volatile (σE2 =
explicit solution for the objective function cannot 0,006). For the parameter of risk aversion, we assume
always be determined. However, a numerical solution α = 1. All input values are summarized in Table 1.
of the optimization model at hand with a limited Considering risk and the insurance impact of
number of properties can be computed in most cases. green buildings, we determine an optimal investment
The authors made several model calculations amount of I* = 18,748 MU. Considering the insurance
and compared the calculation results of the presented impact clearly raises the optimal investment amount
model to results of calculations disregarding the and energy demand, and thus the carbon footprint can
impact of diversification. In this manner, we be reduced much more. The company in this example
ascertained that the overall optimal investment will save 37.5% of its periodic energy demand if it
amount of a portfolio under consideration for the chooses the optimal investment alternative, whereas
diversification effect can be higher or lower than the the company would only save 9.2% of energy if it
optimal investment amount disregarding price disregarded the insurance impact and conducted a
dependencies. If the diversification effect is raised by valuation under certainty.
1608
The “insurance effect”: How to increase the investment amount in green buildings
Imagine the building society together with their theoretic) optimal investment amount can be increased
tenants planning to invest in GBIO for n = 2 by considering the so called “insurance effect” of
properties. Both properties are under possession of the green buildings. The model-theoretic conception of
building society and used by their tenants. Property 1 this effect (and the impact on the EEG) is a novelty in
is the familiar block of offices. All given input values the scientific literature, which is examining the energy
remain unmodified. Property 2 is a production site for efficiency gap in the real estate sector. Furthermore,
commercial uses. All input values given are we pointed out that a diversification effect is a further
summarized in Table 2. possible benefit of GBIO in property portfolios. Of
We can determine an optimal investment course, a theoretical model gives only limited
amount for property 1 of I1* = 41,064 MU and for information about real world impacts. Thus, it cannot
property 2 of I 2* = 74,529 MU. By summing up the be concluded with certainty that planning tools and
businesses considering the insurance effect lead to a
two optimal investment amounts, we obtain the practical reduction of the EEG in every case. The
overall optimal investment amount I overall
*
= 115,593 practical effectiveness of the insurance effect must be
MU. Compared to a consideration without price proven in real world settings, for example in pilot test
dependencies, we can observe significantly different versions of planning tools which may give insight
results: In the current example, the overall optimal about user acceptance and the actual EEG impact of
investment amount is only 65,121 MU if energy price GBIO investments considering the insurance effect.
dependencies are disregarded. Here, the consideration Moreover, several assumptions and conditions
of energy price dependencies leads to a further of this paper have to be examined critically, which
increase in the optimal overall investment amount. opens up possibilities for further research. First, the
Hence, we could model-based show that an accurate landlord-tenant dilemma might be an investment
economic valuation raises the ecological contribution barrier and identified economical and ecologically
again. meaningful investments are not being made because
As already stated in the introducing section, it landlord and tenant are not willing to share the
is not the aim of this fictional example, to determine investment amount.
the optimum level of investment in devices to reduce Furthermore, existing legislation can impede
energy consumption in green buildings (for which we reasonable investments if the investment amount
once again refer to the application of established cannot be divided equitably (e.g., German landlords
tools). Instead, we focus on deriving the relevant can only pass on 11% p.a. of the costs of certain
cause-effect relationships particularly resulting from energy-efficient refurbishment measures to the
the effect insurance: If this – as shown in our tenant). In that case, it is possible that the investment
numerical example – is taken into consideration, there amount to be spent is limited. Second, it is obvious that
is an increase in the optimal level of investment. the value (and thus the resale return) of properties
depends on many more factors than the investment
6. Conclusions amount of GBIO and energy price dependencies (e.g.
location, condition, technical equipment). A model
In the first part of this paper, a rudimentary integrating these factors should be the subject of
optimization model is developed to determine the further research.
optimal investment amount in green building
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1613-1620
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Leilei Pi1, Chunhua Xiong1∗, Jianxiong Jiang2, Xuming Zheng3, Rongrong Zhao1,
Caiping Yao1, Qing Chen1, Yaqin Fu4, Yaofeng Zhu4
1Department of Applied Chemistry, Zhejiang Gongshang University, No.149 Jiaogong Road,
Hangzhou City, Zhejiang Province, 310012, China
2Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University,
Abstract
Adsorption, desorption, and kinetics behavior of Gd(III) ion on chelating resin were investigated in this paper. Batch adsorption
studies were carried out with different pH, contact time, and temperature. The adsorption of Gd(III) follows the Langmuir model
better than the Freundlich model. The apparent activation energy Ea and adsorption rate constant are k308 4.16 kJ/mol and 6.01×10-
5 s-1, respectively. Thermodynamic parameters such as ∆H, ∆S and ∆G indicated that Gd(III) ion adsorption by D418 resin was an
endothermic and spontaneous process in nature. Column adsorption experiments indicated the maximum dynamically adsorption
capacity of 281mg/g for Gd(III). The desorption rate of Gd(III) was 98.3% when the elution agent is 2.0 mol/L HCl solution and
the chelating resin can be regenerated and reused. Analysis of IR spectroscopy for D418 resin before and after adsorption of Gd(III)
ions and after desorption indicated the attendance of coordination and good regenerative ability of resin. Thermo gravimetric
analysis for D418 resin before and after adsorption of Gd(III) ions proved the adsorption of Gd(III) ions.
Received: July, 2013; Revised final: September, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: xiongch@163.com, Phone: +86 13357196703
Pi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1613-1620
materials such as bamboo charcoal, zeolite, pH of solutions. The sample was shaken in the DSHZ-
polystyrene beads and resins have been used in these 300A and the THZ-C-1 temperature constant shaking
techniques (Awual et al., 2013c; Khalil et al., 2016; machine. The water used in the present work was
Xiong et al., 2014). Amongst those, resins were purified using Molresearch analysis-type ultrapure
studied as available material in industrial wastewater water machine. The IR spectra were recorded on a
because of their high removal efficiency, feasibility in Nicolet 380 FT-IR spectrometer. Thermo gravimetric
application, as well as the potential to extract toxic or analysis was performed on Mettler Toledo
valuable metals from the waste water (Li et al., 2016; TGA/DSC1 STARe.
Lin et al., 2018; Shen et al., 2016). D418 resin, as a
typical ion exchange resin, possesses the advantages 2.3. Adsorption experiments
of polymeric adsorbents, such as the relatively low
cost and effectiveness in removing metal ions. D418 Experiments were run in a certain range of pH,
chelating resin is a polymeric microporous material temperature, contact time and adsorption isotherms.
which contains aminophosphonic function group of [- The operations for the adsorption and desorption of
NHCH2PO3Na2]. It could be adopted to the adsorption Gd(III) were carried out in batch vessels and glass
of metal ions from aqueous solutions. columns.
In this work, study of the adsorption of Gd(III) Batch experiments were performed under
on D418 resin is carried out in the form of batch and kinetics and equilibrium conditions. A desired amount
column methods. Some factors to affect the of treated D418 resin was weighed and added into a
adsorption, such as contact time, initial pH of solution, conical flask, followed by the addition of a desired
and temperature were examined. Kinetics and volume of buffer solution with pH 5.5. After 24h, a
isotherm adsorption experiments were carried out, and required amount of standard solution of Gd(III) was
thermodynamic parameters of adsorption for Gd(III) put in. The flasks were shaken in a shaker at constant
were calculated. The experimental results present a temperature. The upper layer of clear solution was
path for the removal of Gd(III) in the environmental taken for analysis until adsorption equilibrium
protection. reached. The procedure of kinetic tests was identical
to that of the equilibrium tests. The aqueous samples
2. Experimental were taken at preset time intervals and the
concentrations of Gd(III) were similarly measured.
2.1. Materials In the column experiments, continuous packed
bed studies were performed in a fixed bed mini glass
The chelating resin (D418) was provided by column of 0.3 cm inner diameter with resin and filled
Nankai University, China and the properties are with Gd((III) solution. The Gd(III) ion solution was
shown in Table1. The standard solutions of Gd(III) ion fed from the top at a fixed flow rate. The Gd(III)
was prepared from Gd2O3 (AR). HOAc-NaAc buffer solutions at the outlet of the column were collected at
solution with pH 4.50-6.50 and C6H15NO3-HNO3 regular time intervals and the concentrations of Gd(III)
buffer solutions with pH 7.20 were prepared from were measured till the outlet and inlet concentrations
acetic acid (HOAc), sodium acetate (NaAc), became equal.
triethanolamine (C6H15NO3) and Nitric acid (HNO3) 2.4. Desorption experiments
solutions. The chromophoric reagent of 0.1%
arsenazo-I solution was obtained by dissolving 0.1000 Desorption experiments were performed
g arsenazo-I powder into 100 mL purified water. All immediately following the completion of the
other reagents were of AR grade. adsorption experiments.
Batch desorption: at the end of adsorption
Table 1. General description and properties of D418 resin
experiments, the exhausted resins were separated from
the aqueous solution by filtration, washed by
Items Properties
Functional group -NHCH2PO3Na2
deionized water and were stirred with eluent solutions
Specific surface area (m2/g) 400-440 of various concentrations, oscillating to balance at
Pore diameter (Å) 8.0-9.0 constant temperature. After equilibrium reached, the
Pore volume (mL/g) 1.0-1.1 concentration of Gd(III) in aqueous phase was
Mass capacity (mmol/g) ≥14 determined and then the percentage of elution for
Moisture (%) 50-60 Gd(III) was calculated.
Wet apparent density (g/mL) 0.70-0.80 Column desorption: after equilibrium was
True wet density (g/mL) 1.10-1.18 reached, D418 resins which were separated from the
Particle size (≥95%) 0.4-1.25mm aqueous solution was washed five times with optimal
Whole bead after osmotic attrition ≥95 pH HOAc-NaAc buffer solution. Then column
desorption experiments carried on by use the preferred
2.2. Apparatus desorption conditions obtained in the batch desorption
experiments. The samples in the outlet were taken at
The Gd(III) ion was determined with Shimadzu the preset volume intervals and the concentrations of
UV-2550 UV-visiable spectrophotometer. Mettler Gd(III) were determined, until the concentration of
Toledo Delta 320 pH meter was used for measuring Gd(III) in the effluent is zero.
1614
Adsorption behavior of gadolinium(III) from aqueous solution by D418 resin
Linearity relation
T(K) k × 10–5 (s–1) R2
of-ln (1-F) and t
288 y=0.1934x-0.1761 5.37 0.993
298 y=0.2093x-0.1457 5.66 0.992
308 y=0.2165x-0.0857 6.01 0.996
Ea (4)
lg k = + lg A
2.303 RT
1615
Pi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1613-1620
1
lg Qe = lg C e + lg K F (6)
Q(mg/g)
n
288K
298K where KF and n are the Freundlich isotherm constants
308K related to adsorption capacity and intensity of
adsorption, respectively.
The isotherm constants of all the previous
equations are very useful parameters for predicting
t(h)
adsorption capacities and also for incorporating into
(a)
mass transfer relationships to predict the design of
batch reactors. According to the results that show in
Fig. 3, higher R2 values (R2288K = 0.9993, R2298K =
0.9998, R2308K = 0.9998) were obtained from
Langmuir model for Gd(III) than from the Freundlich
model (R2288 K = 0.9679, R2298 K = 0.9575, R2308 K =
0.9513). It is evident that the adsorption of Gd(III) ion
onto D418 resin is fitted better to the Langmuir
isotherm model than that of the Freundlich isotherm
models. This indicates that the adsorption of Gd(III)
ions by D418 resin is monolayer-type.
(b)
Ce = 1 + Ce (5)
Qe Q0 K L Q0
(b)
where Qe is the equilibrium Gd(III) ions adsorption
capacity (mg/g), Ce is the equilibrium Gd(III) ions Fig. 3. (a) Langmuir isotherm and (b) Freundlich isotherm
concentration in solution (mg/mL), Q0 is the curves of Gd(III)
maximum adsorption capacity corresponding to
complete monolayer coverage (mg/g), KL is the 3.4. Thermodynamic parameters
Langmuir constant and related to the free energy of
adsorption. In any adsorption procedure, both energy and
The Freundlich isotherm model assumes entropy considerations should be taken into account in
heterogeneous surface energies in which energy term order to conclude whether the process is spontaneous
in Langmuir equation varies as a function of surface or not.
1616
Adsorption behavior of gadolinium(III) from aqueous solution by D418 resin
The amounts of Gd(III) adsorbed at The experimental results of elution show that
equilibrium at 288, 298 and 308K have been examined 2.0 mol/L HCl is the most efficient. In order to show
to obtain thermodynamic parameters for the the reusability of the adsorbent, adsorption-desorption
adsorption system. Thermodynamic parameters of cycle of metal ion was repeated six times by using the
adsorption have been determined by using classical same beads. The adsorption capacities for the D418
thermodynamic equations under the conditions of resin did not noticeably change during the repeated
15.0mg D418 resin and C0=10.0mg/30.0 mL at pH adsorption-desorption operations. These results show
5.5, 100 rpm. that the D418 resin has good regeneration ability.
Thermodynamic parameters such as Gibbs free
energy change (ΔG), enthalpy change (ΔH) and 3.6. Dynamic adsorption and desorption
entropy change (ΔS) can be estimated using
equilibrium constants changing with temperature. The 3.6.1. Dynamic adsorption curve
slope and intercept of lgD vs. 1/T was used for the The performance of packed beds is described
calculation of ΔH and ΔS using the Eq. (7) (Ünlü and through the concept of the breakthrough curve. The
Ersoz, 2006): breakthrough curve shows the dynamic adsorption
capacity of Gd(III) adsorbed on D418 resin and is
∆H ∆S usually expressed in terms of adsorbed Gd(III)
lg D = − + (7)
2.303 RT 2.303 R concentration [Cad = inlet Gd(III) concentration (C0) -
outlet Gd(III) concentration (Ce)] or normalized
Gibbs free energy ΔG calculated by using concentration defined as the ratio of effluent Gd(III)
equation given below (Eq. 8): concentration to inlet Gd(III) concentration (Ce/C0) as
a function of time or volume of effluent for a given
∆G = ∆H − T∆S (8) bed height (Xiao et al., 2009). The area under the
breakthrough curve obtained by integrating the
where R is the gas constant and T is the absolute adsorbed concentration (Cad; mg/mL) vs the
temperature. throughput volume (V; mL) plot can be used to find
The linear equation was y = -0.978x + 6.934, the total adsorbed Gd(III) quantity (maximum column
the correlation coefficient of the straight line R2= capacity). Total adsorbed Gd(III) quantity (Q; mg/g)
0.9765 was achieved. ∆H and ∆S values can be in the column for a given feed concentration and flow
estimated from slope and intercept value of this plot rate is calculated using Eq. (9):
lgD vs. 1/T and the ∆G values at different temperatures
v C0 − C e
were calculated using the Eq. (8), respectively. The Q=∫ dV (9)
values of ΔS, ΔH and ΔG are ΔH 18.7 kJ/mol; ΔS 0 m
132.8 J/(K·mol); and ΔG (–)19.5 kJ/mol for 288K, (–
)20.9 kJ/mol for 298K, and (–) 22.2 kJ/mol for 308K. where m (g) is the mass of the adsorbent. The capacity
The values of ∆G were negative, and confirm value Q was obtained by graphical integration as 281
that the spontaneity of the adsorption process with mg/g. Traditionally, the Thomas model is used to
increasing temperature. The positive value of ∆H fulfill the purpose. The model has the following form
suggests that the adsorption is endothermic in nature. (Eq. 10)(Min Min et al., 2017):
In addition, the values of ∆S were found to be positive
due to the exchange of Gd(III) ions with more mobile 1 (10)
Ce / C0 =
ions (-NHCH2PO3Na2) present on the exchanger, 1 + exp[K T ( Qm - C 0 V ) / θ ]
which would cause increase in the entropy, during the
adsorption process. where KT [mL/(min·mg)] is the Thomas rate constant;
and θ (mL/min), the volumetric flow rate. The
3.5. Elution and regeneration tests linearized form of the Thomas model is (Eq. 11):
1617
Pi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1613-1620
Ce(mg/mL)
y = -0.0471x + 2.2304
R² = 0.9642
T(h)
(a)
V(mL)
D41
8
Weight(%)
Temperature (℃)
(a) (b)
Fig. 6. (a) FTIR spectra and (b) TGA of D418 resin before and after being loaded Gd(III)
1618
Adsorption behavior of gadolinium(III) from aqueous solution by D418 resin
3.8. Thermo gravimetric analysis Balan C., Robu B., Bulai P., Bilba D., Balan C., Robu B,
(2017), Modeling equilibrium data for Cd (Ⅱ) adsorption
TGA were carried out at a heating rates by peat using non-linear regression analysis,
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569-580.
the present work, according to the TGA curves, the Boyd G.E., Adamson A.W., Myers L.S., (1947), The
residue of D418 resin before and after Gd(III) ion exchange adsorption of ions from aqueous solutions by
adsorption is about 30.7wt.% and 48.1wt.%, organic zeolite II kinetics, Journal of American
respectively. The difference of residue (17.4 wt.%) is Chemical Society, 69, 2836-2848.
the weight of adsorptive Gd(III) ion, and it approaches Brykina G.D., Marchak T.V., Krysina L.S., Belyavskaya T.A.,
the experimental value (16.9 wt.%), which can be (1980), Ion sorption of copper and nickel by AV-17X8
calculated from the maximum adsorption capacity anion-exchanger, modified with 1-(2-thiazolylazo)-2-
(281 mg/g). These results prove the adsorption of naphthol-3, 6-disulfonic acid disodium salt, Journal of
Gd(III) ion on D418 resin. Analytical Chemistry, 35, 2294-2299.
Chen Y.Y., Zhao Y., (2003), Synthesis and characterization
of polyacrylonitrile-2-amino-2-thiazoline resin and its
4. Conclusions sorption behaviors for noble metal ions, Reactive and
Functional Polymers, 55, 89-98.
Gd(III) can be optimally adsorbed on D418 Chen X.Y., Xiong C.H., Yao C.P., (2014), Evaluation of the
resin in pH 5.5 HOAc-NaAc system. At 298K, the adsorption of Copper(II) from aqueous solution by D151
dynamic saturated adsorption capacity of Gd(III) is resin, Environmental Engineering and Management
281mg/g. The dynamic adsorption curve of D418 Journal, 13, 783-790.
resin for Gd(III) obeys the Langmuir isotherm. El-Sofany E.A., (2008), Removal of lanthanum and
The analysis of the thermodynamic parameters gadolinium from nitrate medium using Aliquat-336
impregnated onto Amberlite XAD-4, Journal of
(ΔS, ΔH and ΔS) of Gd(III) adsorption showed that the Hazardous Materials, 153, 948-954.
adsorption process was spontaneous and endothermic. Freundlich H.M.F., (1906), Over the adsorption in solutions,
The Gd(III) adsorbed on D418 resin can be effectively Journal of Physical Chemistry, 57, 385-470.
eluted by using 2.0mol/L HCl solution. FTIR and Jaafarzadeh N., Teymouri P., Babaei A.A., Alavi N.,
TGA of D418 resin adsorbed Gd(III) show that the Ahmadi M., (2014), Biosorption of cadmium(II) from
functional group of resin is coordinated with Gd(III) aqueous solution by NaCl-treated ceratophyllum
to form coordination compound. D418 resin has very demersum, Environmental Engineering and Management
good potential for utilization as an adsorbent for Journal, 13, 763-773.
Junk G.A., Richard J.J., Grieser M.D., Witiak D., Witiak
Gd(III) from aqueous medium.
J.L., Arguello M.D., Vick R., Svec H.J., Fritz J.S.,
Calder G.V., (1974), Use of marcoreticular resins in the
Acknowledgements analysis of water for trace organic contaminants,
The work is supported by the National Natural Science Journal of Chromatography A, 99, 745-752.
Foundation of China (No.21276235), The Key Research and Kondo K., Kamio E., (2002), Separation of rare earth metals
Development Program of Zhejiang Province with a polymeric microcapsule membrane,
(No. 2017C03049), and The Program of Science and Desalination, 144, 249-254.
Technology of Zhejiang Province, China (No. 2017C311, Langmuir I., (1918), The adsorption of gases on plane surfaces
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313-320. yellow in drink and jelly samples, Food Analytical
Awual M.R., Kobayashi T., Shiwaku H., Miyazaki Y., Methods, 1-14.
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(2013b), Evaluation of lanthanide sorption and their Chemical precipitation of heavy metals from acid mine
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using novel hybrid adsorbent, Chemical Engineering Min M., Shen C., Fang L., Zhu B., Li J., Yao L., (2017), Design
Journal, 225, 558-566. of a selective regenerable cellulose microcolumn for
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Engineering Journal, 228, 327-335. Selective removal of copper with polystyrene–1,3-
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diaminourea chelating resin: synthesis and adsorption 2-amino-1,3,4-thiadiazole chelating resin: batch and
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1620
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1621-1634
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Hexavalent chromium Cr(VI), a constituent of wastewater from many industries, is regulated by the Environmental Protection
Agency (EPA) as one of the priority pollutants. Adsorption is an important technique that can be used for Cr(VI) removal from
wastewater. The challenge in adsorption techniques is to find a cheap, widely available adsorbent that has a high adsorption
capacity to Cr(VI). Dates stones (DS) and palm fiber (PF) are two agricultural wastes that are produced from palm trees. These
adsorbent materials were tested in batch systems to investigate the different factors that may affect the adsorption process, e.g.
adsorbent dose, initial adsorbate concentration, pH of aqueous solution and agitation time. Equilibrium models tested include
Langmuir, Freundlich, Temkin and Dubinin-Radushkevich. Freundlich adsorption isotherm was found to best fit the
experimental data. The maximum adsorption capacities obtained for DS and PF were 16 and 6 mg/g, respectively. Kinetic studies
indicated that the adsorption of Cr(VI) on both DS and PF was fast in the first stage of the adsorption process. The equilibrium
was reached in less than 2 h for both adsorption systems. The adsorption process was found to be second order with both
adsorbent and adsorbate concentration to affect the adsorption process. Film diffusion and intraparticle diffusion models were
found to simultaneously influence the adsorption. The adsorption process was found to be favorable and of physical nature.
Key words: adsorption, chromium (VI), dates stones, kinetics, palm fiber, thermodynamic
Received: August, 2013; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
1622
Removal of hexavalent chromium using two innovative adsorbents
2.2.1.4. Specific surface area, apparent density, groups and sodium hydroxide neutralizes carboxylic,
moisture and ash content lactonic and phenolic groups.
The specific surface area was determined by
using Sears method (Sears, 1956). According to this 2.3. Adsorption equilibrium studies
method, 1.5 g of the adsorbent was added to 100 mL
dilute HCl to reach a pH value in the range 3 - 3.5. The adsorbate uptake at equilibrium, qe
Sodium chloride (30 g) was added to the acidic (mg/g), was determined by (Eq. 1).
solution with continuous stirring. The mixture (Co − Ce )V
volume was made up to 150 mL using distilled water. qe = (1)
W
The suspension was titrated with standard 0.1 M
NaOH to reach a pH 4 and then 9. The added volume where Co and Ce (mg/L) are the initial and final
(V) required to raise the pH from 4 to 9 was concentration of the dye, respectively, W (g) is the
recorded. The test was made in triplicate and the mass of the adsorbent used, and V (L) is the volume
value of surface area (S) was determined depending of the solution. Percentage dye removal (R) is
on the average of the three obtained value. determined according to (Eq. 2).
The apparent density of each adsorbent was
determined by filling a 10 mL measuring cylinder Co − Ce
with the adsorbent. Gentle tapping was applied on the R= × 100 (2)
Co
cylinder wall to fill the gaps between adsorbents
particles. The apparent density was determined as the
The adsorbent capacity towards chromium
mass of the adsorbent required to fill the cylinder
removal (effect of adsorbent mass) was investigated
divided by the volume of the cylinder.
by adding fixed volumes (0.05 L) of the working
To determine the moisture content of the
solution of chromium of known concentration (50
adsorbent, 10 grams of the adsorbent (weighed to the
mg/L) to 125 mL conical flasks containing different
fourth decimal point) were placed into weighing
masses of adsorbent. The flasks were stoppered and
watch glass. The watch glass was then placed inside
shaken for 300 min at a rate of 300 rpm. The
an oven at 105 oC. After 5 hours of drying, the watch
solutions were filtered using 0.45 µm membrane
glass was cooled in desiccator. The mass of the dried
filters and the residual hexavalent chromium in the
adsorbent was then measured. The average moisture
filtrate was determined using the dipheny carbazide
content of the samples was assumed to be the mass
method as described before. To investigate the other
loss from the adsorbent sample. The experiment was
factors that may affect the adsorption process (pH,
repeated five times and the average was calculated.
initial concentration and time of agitation), the
For determination of ash content, three clean
previous procedure was conducted several times. In
empty crucibles were ignited at 550oC for 30
every experiment all factors were kept constant and
minutes, cooled in a desiccator and then weighed.
the studied factor was changed. All experiments were
Accurately weighed 10g of each adsorbent were
conducted at room temperature (20 ± 2oC). Other
placed in each crucible. The samples were ignited at
experimental conditions are summarized in Table 1.
550oC for 2 hours. The difference in weight of
crucibles before and after ignition represented the ash 2.4. Mathematical models
content. The experiment was repeated three times
and the average was considered. 2.4.1. Adsorption isotherms
The linear form of Langmuir isotherm is given
2.2.1.5. Determination of the functional groups by (Eq. 3).
(Boehm’s titration)
The surface functional groups of the two Ce 1 C
= + e (3)
adsorbents were determined using Boehm’s titration qe q m . K L q m
procedure (Boehm, 2002). This method includes
acid-base titration of the adsorbent to identify the where Ce (mg/L) is the equilibrium concentration, qm
nature of functional groups on the surface of (mg/g) is the maximum adsorption capacity, qe
adsorbent. Twenty-five milli-grams of date stones or (mg/g) is the adsorption capacity at equilibrium, and
palm fibers were placed in 25 ml of 0.1 M solution of KL (L/mg) is a constant related to adsorption rate.
each of sodium bicarbonate, sodium carbonate or The favorability of the adsorption is determined by
sodium hydroxide. The mixtures were shaken for 24 the dimensionless separation factor RL which is given
h then centrifuged at 6000 rpm. A given amount of by (Eq. 4).
each supernatant (5 ml) was titrated with 0.1 M
hydrochloric acid solution. Similar procedures were 1
RL = (4)
performed with blank samples. Triplicate of this 1 + K L Co
experiment was conducted and the average was
calculated. The number of acidic sites was where Co (mg/L) is the initial dye concentration and
determined under the assumptions that sodium KL is Langmuir constant.
bicarbonate neutralizes carboxylic groups, sodium The value of separation factor indicates the
carbonate neutralizes both carboxylic and lactonic favorability of the adsorption process as follows:
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Abubeah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1621-1634
Unfavorable (RL > 1), linear (RL = 1), R is the universal gas constant in J/mol. K and
favorable (0 < RL < 1), and irreversible (RL = 0). The T is the temperature (K).
linear form of Freundlich model is given by (Eq. 5).
2.4.2. Kinetic models
1 Many kinetic models have been introduced to
ln qe = ln k f + ln Ce
n (5) examine the mechanism of adsorption processes.
Some of the commonly used kinetic models were
where qe and Ce have the same definition as applied. These kinetic models are pseudo first order,
Langmuir equation, kf (mg/g(mg/L)1/n) is constant pseudo second order, Boyd model, intraparticle
related to the bonding energy. Kf is defined as the diffusion model and Elovich equation.
adsorption coefficient, and 1/n identifies the The linear form of pseudo first order model is
adsorption intensity of adsorbate onto adsorbent. If given by Eq. (11):
the value of exponent n is greater than 1, the
adsorption represents favorable adsorption ln(qe − qt ) = ln qe − k1t (11)
conditions.
The linear form of Temkin isotherm is given where qe (mg/g) and qt (mg/g) are the amounts of dye
by Eqs. (6-7). adsorbed on the surface of the adsorbate at
equilibrium and at any time t (min), respectively; and
qe = BT (ln KT ) + BT ln(Ce ) (6) k1 (min-1) is the rate constant of the pseudo first order
equation.
RT The linear form of the pseudo second order
BT = (7)
b model is given by Eq. (12):
where qe is the amount of adsorbate adsorbed onto where Bt is the mathematical function of F and F
adsorbent surface (mg/g), qm represents the represents the fraction of solute adsorbed at time t (h)
maximum adsorption capacity of adsorbent (mg/g), and F = qt / qe
and B is a constant related to the mean free energy of According to the model, if the plot of Bt
adsorption per mole of adsorbate. versus t passes through the origin, pore diffusion is
The Polanyi potential (ε) is given by Eqs. (9- the rate determining step. Otherwise, the adsorption
10): process is film diffusion controlled.
Intraparticle diffusion model considers the
1
ε = RT ln (1 + ) (9) intraparticle diffusion as the rate controlling step for
Ce adsorption. It is given by Eq. (14):
1
E= (10) qt = k id t 0.5 + C (14)
(2 B) 0.5
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Removal of hexavalent chromium using two innovative adsorbents
where qt (mg/g) is the amount adsorbed at time t dominant peaks at 3426 and 3430 cm-1 respectively
(min) and kid (mg/g.min0.5) is the rate constant for the for palm fibers and date stones, are attributed to O–H
intraparticle diffusion model. stretching vibrations in hydroxyl groups and appears
A simplified linearized form of Elovich in this lower region where these groups are involved
equation (Malkoc and Nuhoglu, 2007) can be in hydrogen bonds.
introduced by Eq. (15): The FTIR spectra of date stones and palm
fibers waste are in good agreement with the results of
1 1 Yang (Yang et al., 2007) who studied the
qt = ln(αB) + ln t (15)
B B characteristics of cellulose, hemicellulose and lignin.
This result is in accordance with the composition of
where α (mg/g min) is the initial adsorption rate and lignocellulosic material such as date stones and palm-
B (g/mg) is the adsorption constant related to the trees waste, which are essentially composed of
extent of the surface coverage and activation energy cellulose, hemicellulose and lignin (Bouchelta et al.,
for chemisorption. 2008). Consequently, the FTIR results indicate that
the biosorbents presented different functional groups
2.5. Thermodynamic study
such as hydroxyl, carboxyl and carbonyl, which may
The thermodynamics data obtained from the be potential biosorption sites for the removal of
adsorption process can be used to introduce the chromium.
adsorption mechanism. The Gibbs free energy 3.2. Scanning Electron Microscope (SEM)
change ∆G can be calculated by Eq. (16):
The results of the scanning electron
∆G = − RT ln K L (16) microscopy are shown in Figs. 2-3. It is quite clear
that the morphology of the two adsorbents is quite
where KL is the Langmuir adsorption constant, R is different except for one feature which is the
the universal gas constant and T is the absolute macropores position. The macropores seem to be on
temperature. The enthalpy change and the entropy the surface of the two adsorbents.
can be obtained from Van’t Hoff equation (Eq. 17): Also, these macropores are connected to meso
∆S ∆H and micropores through channels. The surface of DS
ln K L = − (17) is very porous and the pores are irregular and have
R RT
different dimension. Layers of adsorbent can be
The enthalpy change and entropy change can clearly seen. On the other hand, the surface of PF
be obtained from the slope and intercept of the line showed relatively smooth regions. The pores on the
obtained by plotting ln KL against 1/T, respectively. surface of PF seem to be more regular and
homogeneously distributed all over the surface.
3. Results and discussion
3.3. Specific surface area, moisture, ash content and
3.1. Infrared (FTIR) Spectral Analysis apparent density
FTIR spectra for both adsorbents are The proximate analyses are shown in Table 2.
illustrated by Figs. 1a-b. The figures indicate a The percentage moisture content (%MC) was
number of absorption peaks suggesting complex computed as follows (Eq. 18):
properties of the adsorbents. Spectra are similar for
loss in weight on drying
both samples. The peaks in the region 1200–1000 % MC = × 100 (18)
cm-1 may represent C–O stretching vibrations (Sain initial mass of sample before drying
and Panthapulakkal, 2006). The band at 1261 cm-1 in
the spectrum of palm fibers is ascribable to the The moisture content is relatively high and
bending modes of O–C–H, C–C–H and C–O–H indicates the necessity of drying the adsorbent before
(Bouchelta et al., 2008). The peaks at 1377 and 1379 use or otherwise, taking the moisture content into
cm-1 are due to C–H bending vibrations. The peaks at consideration during calculation. The ash content was
1516, 1523 and 1426, 1441 cm-1 may be ascribed to calculated using (Eq. 19)
C=C stretching of aromatic skeletal mode (Pavan et ash weight
al., 2008; Sain and Panthapulakkal, 2006). The bands Ash content = × 100 (19)
oven dry weight
at 1641 and 1631 cm-1 may represent C=C stretching
vibration of alkenes or C=N vibrations in aromatic
Ash content can affect the adsorbent
region. The peak at 1743 cm-1 in the spectrum of date
efficiency, i.e. it reduces the overall affinity of
stones is assigned to C=O stretching vibration of
adsorbent towards adsorbate. The ash content is low
carboxylic groups of lignin and/or hemicelluloses
and it indicates that the adsorbent could be used in
(Pavan et al., 2008; Sun et al., 2005). The bands
further studies for production of activated carbon.
observed at 2924 and 2860 cm-1 are assigned to
The specific surface area was calculated using Eq.
asymmetric and symmetric C–H and symmetric C–H
(20), where S and V signification is explained in the
bands, respectively, present in alkyl groups. The
section 2.2.1.4.
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Abubeah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1621-1634
(a)
(b)
Specific surface area, m2/g Ash content, % Moisture content, % Apparent density, g/cm3
DS PF DS PF DS PF DS PF
399 237.4 3.19 3.62 3.03 3.3 0.47 0.34
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Removal of hexavalent chromium using two innovative adsorbents
3.5. Effect of adsorbent dose on adsorption 3.6. Comparison of adsorption capacity of DP and
performance PF with other adsorbents
One very important factor when designing an The adsorption capacity of Cr (VI) on both
adsorption system is the optimum adsorbent dose dates stones and palm fibers compared with other
required for this system. Fig. 4 and 5 indicate that agricultural wastes adsorbents reported in literature is
increasing the dose of adsorbent increased the illustrated in Table 4. It can be noticed that the
adsorption efficiency of adsorbate. Increasing the adsorption capacity of DS (16 mg/g) is higher than
dose from 1 to 6 g/L resulted in an increase of some of these adsorbents and similar to others. The
adsorption removal efficiency from 23 to 69%. adsorption capacity of PF (6 mg/g) is lower than DS
However, the adsorption capacity decreased from and most of the other adsorbents. Many reasons can
11.4 to 5.7 mg/g. On the other hand, for PF, the same explain the difference in adsorption capacity among
increase in adsorbent dose (from 1 – 6 g/L) had a these adsorbents including the difference in specific
lower effect. The corresponding increase in surface area, the surface functional groups, and the
adsorption removal efficiency was from 15 – 35 %. pore size distribution of these adsorbents.
The adsorption capacity for this system increased
from 3 – 7.5 mg/g. 3.7. Effect of pH and point of zero charge on
These results can be attributed to the effect of adsorption performance
the mass of adsorbent on the number of adsorption
sites. Increasing the mass of adsorbent increases the The effect of aqueous solution pH on the
number of active sites available for adsorption, thus adsorption capacity of chromium ion is depicted by
resulting in increasing removal efficiency. Fig. 6.
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Abubeah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1621-1634
As shown in Fig. 6, the adsorption capacity of positive charge, while the adsorbate will be present
both DS and PF increased with decreasing the pH of mostly in its anionic form.
the solution. The highest adsorption capacity was
obtained at pH 2. This result is supported by the work
of other researchers (Karthikeyan et al., 2005;
Malkoc and Nuhoglu, 2007; Sarin and Pant, 2006).
The effect of pH is due to the surface
properties of the adsorbent and properties of
chromium ions in solution (Jain et al., 2009).
Hexavalent chromium may be present in various
species in aqueous solutions, e.g.
− 2− 2−
H 2 CrO4 , HCrO4 , CrO4 and Cr2 O7 according to the
solution pH.
The point of zero charge gives a good Fig. 7. Zero point of charge; A: DS, B: PF
indication about the surface charge of adsorbent.
When the pH of the aqueous solution is below the Attraction of these opposite charged species
pHzpc, the surface charge of the adsorbent is will take place. So, it is expected to have higher
positive. Meanwhile, the surface of the adsorbent is adsorption capacity at lower pH. In the pH range 2-6,
negatively charged when the pH of the solution is both HCrO4− and Cr2 O72− species are present in
greater than the pHzpc. The values of point of zero 2−
charge on the surface of DS and PF are 5.5 and 6.5, equilibrium. At lower pH ranges, Cr3O10 and
2−
respectively as illustrated in Fig. 7. These values Cr4O13 are produced. The adsorption of Cr(VI) may
represent the points at which the initial and final pH
values of the system are equal. Below these pH take place through different mechanisms. The
values the surface of the adsorbents will carry electrostatic attraction between the dominant
1628
Removal of hexavalent chromium using two innovative adsorbents
chromium species ( HCrO4− ) present in solution with adsorption sites are not occupied by adsorbate
positively charged sites on the adsorbent is an molecules which lead to less adsorption capacity.
important mechanism. Chelation with acidic groups Second, aggregation of the adsorbent particles may
on the adsorbent surface and exchange with anions take place which lead masking of some of the
loaded on the residues are two other common adsorption sites, thus decreasing the total surface area
mechanisms (Gandhia et al., 2010). of the adsorbent in the solution (Yasemin and Tez,
2007).
3.8. Effect of initial concentration on adsorption
3.9. Adsorption equilibrium
The initial concentration of the metal ion is
one of the important factors that may affect the The experimental data were tested with
adsorption of metal ions in aqueous solution on the adsorption models namely Langmuir, Freundlich,
surface of a certain adsorbent. The initial Temkin and D-R. The characteristic parameters from
concentration provides the driving force required to the slope and intercept of the plots are determined
overcome the mass transfer resistance of the metal using regression analysis. The parameters are
between aqueous solution and solid phase (Aksu and reported in Table 5. The dimensionless separation
Akpinar, 2000). Fig. 8 illustrates the effect of initial factor RL values (calculated according to Langmuir
Cr(VI) concentration on the adsorption into both model) for both DS and PF systems, being less than
adsorbents. For DS, the adsorption capacity increased unity, indicate that adsorption of Cr(VI) on both
from 1.99 mg/g to 74.5 mg/g when increasing the adsorbents to be favorable. The maximum adsorption
initial concentration from 15 to 450 mg/L. For PF, capacity of DS is much higher than PF. However,
the increase was from 0.93 mg/g to 62.6 mg/g for the their values are not consistent with the experimental
same concentration range. values as indicated by the relatively low R2 for both
adsorbents.
Freundlich is an empirical expression. It
assumes that adsorption takes place on multilayers on
the surface of adsorbent. As illustrated by the results
in Table 5, the Freundlich model fits the data for both
DS and PF systems better than the Langmuir model,
this is demonstrated by high correlation coefficient
(R2) for the data obtained from Freundlich model.
The value of 1/n for DS is 0.772 which indicates high
favorability of the adsorption of Cr(VI) on DS. On
the other hand, 1/n value in case of PF system is
0.362. Comparing these results indicates that the DS
adsorption system is more favorable than PF
Fig. 8. Effect of initial concentration on chromium adsorption system. Analysis of the adsorption data
removal, contact time 300 min, adsorbent mass 0.15 g, using D-R model has a significant Importance. It
stirring rate 300 rpm, particle size < 250 μm gives an indication about the nature of the adsorption
process; physical or chemical.
For a fixed adsorbent dose, the number of
The mean adsorption energy of the D-R model
active adsorption sites to accommodate adsorbate
gives information about the nature of the adsorption
ions remains unchanged but with increasing
process; physical or chemical. If E<8 kJ/mol, the
adsorbate concentration, the adsorbate ions to be
adsorption process is physical, and if 8<E<16, the
accommodated increases and hence many of the sites
adsorption process is ion exchange, and if E > 16
available for adsorption will be occupied. It can be
kJ/mol the adsorption process is chemical. As
noticed from the figure that adsorption saturation was
indicated in Table 5, the correlation coefficients of
not reached due to high availability of free adsorption
adsorption system for DS and PF are high (0.989 and
sites on both adsorbents compared to the number of
0.957 for DS and PF, respectively). The maximum
chromium species to be adsorbed. The increase in
adsorption capacity for DS is 15.441 mg/g and that
adsorption capacity accompanied by the increase in
for PF is 21.22 mg/g. The first value agrees well with
initial ion concentration indicates increasing
experimental data, while the other one is not
occupation of available binding sites. As was stated
consistent. The E values being less than 8 kJ/mol
before, the initial concentration provides an
suggest the physical adsorption to be the mechanism
important driving force to overcome all mass transfer
of adsorption.
resistances of all molecules between the aqueous and
Temkin isotherm fits well to the experimental
adsorbents. Another effect of high initial
data as indicated by correlation coefficients. Its
concentration of the adsorbate molecules is the
constants are given in Table 5. The Temkin
probable increase of contact between chromium
adsorption potential, KT, of DS is 0.159 compared to
molecules and adsorbent particles. Some factors must
0.034 for PF indicating a lower PF-metal ion
be taken into account when studying the effect of
potential than DS.
initial ion concentration. First, some of the active
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Abubeah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1621-1634
Adsorbent
Isotherm Parameters
DS PF
R2 0.916 0.929
qm, mg/g 35.7 2.24
Langmuir 20 oC
KL, L/mg 0.013 0.017
RL 0.61 0.547
R2 0.986 0.955
Freundlich 20 oC n 1.295 0.362
Kf (mg/g)(mg/L)1/n 0.71 1.7x10-4
R2 0.997 0.923
Temkin 20 oC BT, mg/g 6.385 11.07
KT, L/mg 0.159 0.034
R2 0.989 0.957
Dubinin-Radushkevich 20 oC qm, mg/g 15.441 21.22
E, kJ/mol 0.1 0.016
This is probably due to the difference in pore For both adsorbents equilibrium is reached
diameter and pore shape of both adsorbents. As it is within the first two hours. The adsorption took place
depicted by Figs. 2-3, the shape of the DS pores is in two different stages. The first one was very fast.
irregular in contrast to the regular shape of PF pores. This is illustrated by the fact that for DS, 86 % of the
The pore radius must be close to the ionic radius for chromium ions was removed within the first 10 min
adsorption to take place.The Temkin constants, b (maximum removal efficiency was 94%). The next
related to heat of sorption for DS and PF are 0.381 stage was a slow stage ending with equilibrium. A
and 0.22 kJ/mol, respectively. It has been reported similar behavior could be observed for PF. Within
that the typical range of bonding energy for ion- the first 10 min, 21 of the chromium ions were
exchange mechanism is 8-16 kJ/mol (Kiran and removed compared to 34% removal efficiency at
Kaushik, 2008). The low values in this study equilibrium. The rapid uptake of the metal ions at the
indicates a weak interaction between sorbate and early stage of the adsorption process may be
sorbent, supporting a physical adsorption mechanism. attributed to the availability of active adsorption sites
This result is in agreement with that obtained from on the adsorbent surface. With time, these sites got
D-R isotherm. occupied and the remaining adsorbate ions would
compete for the remaining unoccupied sites which
3.10. Kinetic study results in slower adsorption rate (Ozdes et al., 2011).
Another reason is the concentration gradient. As was
Adsorption kinetics describes the solute mentioned before the high initial concentrations
uptake rate, which governs the residence time of provide a driving force for chromium ions
sorption reaction. It also describes the reaction adsorption. At early stages, a great concentration
pathway along times until reaching equilibrium. Fig. gradient is present between the adsorbate in the bulk
9 depicts the adsorption rate of hexavalent chromium of solution and on the surface of adsorbent which
ions on both DS and PF. The adsorption of chromium easily overcomes the mass transfer resistance. With
ions on both DS and PF displays a fast adsorption time, the concentration gradient decreases which
rate. decrease the driving force. The kinetic data were
evaluated using pseudo-first and second order
models. The results of fitting the experimental data to
the model are illustrated in Table 6. The data in the
table shows that the experimental data had its best fit
with the pseudo second order model with higher R2
value (0.999 and 0.995 for DS and PF, respectively)
compared with pseudo first order.
Furthermore, the values of qt predicted by the
model agree closely with those determined
experimentally. Therefore, it can be concluded that
the rate of hexavalent chromium ions adsorption is
influenced by both the metal ion concentration and
adsorbent dose (Abramian and El-Rassy, 2009). The
prediction of the rate controlling mechanism is
important in adsorption processes since it affects the
Fig. 9. Effect of contact time on the adsorption of design and scale-up of the adsorption system. The
chromium on DS and PF adsorption process in an aqueous solution is
1630
Removal of hexavalent chromium using two innovative adsorbents
characterized by either external mass or intraparticle layer for the former. These results support the finding
diffusion or both. obtained before from fitting the data to film diffusion
model.
Table 6. Kinetic parameters for adsorption of chromium on
DS and PF
Adsorbate
Kinetic model Parameters
DS PF
R2 0.619 0.503
Pseudo first order K1 0.029 0.026
qm 5.474 7.374
R2 0.999 0.995
Pseudo second order K2 0.032 0.018
qm 15.873 5.714
R2 0.984 0.947
Elovich B 2.513 1.835
α 2.31 46.64
R2 0.958 0.91
Intraparticle diffusion Kid 0.104 0.131
C 14.14 3.387
Boyd R2 0.956 0.88
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Abubeah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1621-1634
temperature will decrease the viscosity of the The positive values of ∆S may suggest that
aqueous solution containing chromium ions. Cr(VI) ions replace some water molecules from the
solution previously adsorbed on the surface of
adsorbent. These displaced molecules gain more
translation entropy than is lost by the adsorbate ions,
thus allowing the prevalence of randomness in the
system. The positive values of ∆S may also show the
increased disorder and randomness at the solid
solution interface during the adsorption process for
both systems. In addition, the positive value of ∆S
reflects the affinity of the adsorbents for the Cr(VI)
ions (Najm and Yassin, 2009).
Fig. 12. Elovich model for adsorption The two agricultural wastes used in this study
of chromium on both DS and PF are widely available with low cost. These two
substances have no significant industrial and
This will resilt in increasing the rate of commercial uses but become an issue and contribute
adsorbate diffusion across the external boundary to environmental problems. Hence, the utilization of
layer and in the internal pores of the adsorbent. such agriculture solid waste for wastewater treatment
Temperature may also affect the equilibrium of the is beneficial. The alternative of using agricultural
adsorbate depending on the nature of the adsorption waste as adsorbent is activated carbon. Activated
process; whether it is endothermic or exothermic. carbon has better adsorpitivity but its cost of
Finally, it has an effect on the stability of the metal production is very high.
ion species initially placed in solution. Dates stones collected from dates processing
The adsorption capacity increased from 6.803 plant are given away for free. Its use in other
mg/g to 28.6 mg/g for DS and from 0.062 mg/g to purposes is negligible. The cost of processing
5.16 mg/g for PF (Figures not shown) when the including transportation, washing, drying, crushing,
temperature was increased from 10 to 40oC, sieving, and labor is SR 200/ton. No chemical
indicating that the adsorption process is endothermic treatment is required for its processing. PF is
in nature for both adsorbents. collected during the trimming the palm tree. It is less
The thermodynamic parameters ∆H and ∆S available. However, its cost of processing is less; SR
are introduced in Table 7. These data were calculated 100/ton. Compared with the cheapest commercial
from the slope and intercept of the plot between ln Kc activated carbon available in the local market (SR
and 1/T. The values of ∆G indicate the favorability of 4000/ton), the two adsorbents studied are very good
physical adsorption. The positive values of ∆H replacement.
indicate the endothermic nature of adsorption and
this governs the possibility of physical adsorption 4. Conclusions
which was also supported by the increase in
adsorption capacity with increasing temperature. The Tis study indicates that DS has a better
negative values of ∆G in case of adsorption on DS adsorption capacity to hexavalent chromium than PF.
suggest the high favorability of Cr(VI) adsorption on The adsorption of Cr(VI) on both DS and PF was
DS. They also indicate that the metal ion adsorption found to be pH-dependent. The highest removal
was spontaneous. On the other hand, the positive efficiency was obtained at pH 2. The initial
values of ∆G in case of PF system indicate that this concentration of the metal ion in solution was found
adsorption system is less favorable. Furthermore, the to have a pronounced effect on the adsorption
low values of ∆G suggest physical adsorption process. Increasing the initial concentration resulted
(Kumar and Kirthika, 2009). in higher adsorption capacity. Freundlich model was
found to be the best adsorption equilibrium model
Table 7. Thermodynamic parameters of Cr(VI) adsorption
onto DS and PF
that can interpret the experimental data.
The mechanism of adsorption involves both
∆G ∆H ∆S liquid film diffusion and intraparticle diffusion as the
T (K)
(kJ/mol) (kJ/mol) (J/mol.K) rate determining mechanisms. It can be concluded
283 0.71 from the results demonstrated here that DS is a
Dates 293 -2.54
31.06 108
potential effective adsorbent for removal of Cr(VI)
stones 303 -2.03 from aqueous solutions.
313 -2.33
283 4.67 References
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Removal of hexavalent chromium using two innovative adsorbents
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1634
Environmental Engineering and Management Journal June 2018, Vol.17, No.7, 1635-1644
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Malik Anju
Department of Energy and Environmental Sciences, Chaudhary Devi Lal University, Sirsa-125055, Haryana, India
E-mail: anjumalik27@yahoo.com; Phone: +91-9466733030
Abstract
Sulfide bearing mine tailings generated through mining and processing of mineral ores is one of the serious problems around the
world due to their potential environmental hazards. Current study focuses on vertical distribution and potential mobility of metals
in New and Old tailings of a Lead and Zinc mining area of India. Mine tailing profiles sampled from New (0-500mm) and Old
tailing (0-400mm) dams were chemically (pH, EC, Carbonate content, Cd, Pb, Zn and Mn levels) and mineralogically (using X-
ray Diffraction) characterized. Both the new and old tailings are alkaline having high carbonate content. However, the pH of old
tailings is less than the new tailings. The vertical profile distribution of metals in new tailings indicate a decrease in Pb levels with
depth up to 200 mm and a substantial increase in Zn and Cd levels were noted below 200 mm depth. However, no differences were
observed for Mn levels with depth. In case of Old Tailings, no discernible pattern for Cd, Pb, Zn and Mn levels with depth was
observed. These chemical and mineralogical observations confirm that the new tailings are undergoing oxidation and weathering
in the surface layers, however, the old tailings are sort of stabilized at least up to sampling depth. To estimate the potential mobility
of Cd, Pb and Zn in New and Old tailings, single extraction (EDTA 0.05 mol/L) was applied to surface tailings. The correlation
coefficients between total and EDTA extractable Cd and Zn (r values for Cd and Zn being 0.965 and 0.976, respectively, and P
value being 0.001) indicate statistically significant relation. The results of EDTA extraction show that out of the three metals, Pb
has maximum extractability in new tailings, whilst Cd has the maximum mobility in old tailings, and Zn has the least potential
mobility in both types of tailings.
Key words: correlation coefficient, heavy metal, mine tailing, single extraction, vertical distribution
Received: March, 2014; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: June 2018
weather and leach metals into tailing profile and surrounding old surface and subsurface mine
ground water for several hundreds of years after workings, earthen retorts and slag heaps. Modern
mining activities have ceased. So, field studies of mining, however, commenced in 1942. Zawar lies
metals in vertical profile of tailings can be useful for within a belt of Aravalli system. The ore is confined to
predicting the pollution risk to groundwater from the the main dolomite horizon (Chakrabarti, 1967; Smith,
sulfide tailings. 1964). Sphalerite (ZnS) is the predominant sulphide
The shift in paradigm from mere determination mineral in the ore, second most abundant being pyrite
of total elemental concentration to a more advanced in a gangue of dolomite and quartz. Galena (PbS) is
fractionation-based approach points to the general more locally concentrated. Native silver, chalcopyrite,
recognition that information about the physiochemical arsenopyrite, pyrolite, and magnetite are also known
forms of trace elements is required for understanding to occur (Mookherjee, 1964). The conventional froth-
their environmental fate and behavior, including flotation technology is adopted to produce separate
mobility, pathways and bioavailability. A variety of lead and zinc concentrates. On an average the ore
standardized leaching tests with variable reagents, and contains 5% metal (both Pb and Zn) and 95% of the
experimental conditions are used to mimic differing total mined ore is pumped out as tailings. Fine-grained
environmental conditions. Strong acids are used to tailings generated during the beneficiation of sulphide
determine total concentrations of potentially harmful ores are directed to the New Tailing Dam. Prior to
elements, whereas weaker solutions are used to 1980's, tailings were dumped in an area called Old
determine compounds that are relatively soluble and Tailing Dam, which has been stabilized by plantation.
bioavailable (Salminen and Sipila, 1996). Various The volume of tailings generated is normally in far
extraction schemes have been developed for excess of the liberated resource and the tailings often
discerning individual geochemical phases, ranging contain potentially hazardous contaminants (Kossoff
from simplistic methods for distinguishing the “labile” et al., 2014). Thus, both tailing dams represent by far
and “residual” fractions (single extractions), to more the biggest accumulations of environmentally
sophisticated approaches enabling the sequential dangerous waste materials in Zawar area.
removal of water soluble, exchangeable, adsorbed, The purpose of this study was to investigate the
carbonate bound, phosphate, Fe/Mn oxide bound, vertical distribution of metals (viz. Cd, Pb, Zn and Mn)
sulphide and organic bound and silicate fractions in tailing profiles from New and Old Tailing Dams.
(sequential extraction procedures). In single Additionally, the potential mobility of Cd, Pb and Zn
extractions a large spectrum of extractants have been in New as well as Old tailings was estimated by using
used to extract the “mobile” or “bioavailable” forms single extraction (EDTA 0.05 mol/L).
of metals (He and Singh, 1995; Karczewska et al.,
1998), viz. 2. Material and methods
Very strong acids such as aqua regia (Vidal et
al., 1999), nitric acid (Sutherland et al., 2001), HCl 2.1. Sample collection and preparation
(Filipek and Pawlowski, 1990; Rieuwerts et al., 2000;
Sutherland and Tack, 2000; Sutherland et al., 2001; Tailing profiles were sampled as undisturbed
Taylor et al., 1993). core, by using a specially designed cylindrical
Chelating agents like EDTA (Anju and stainless-steel corer from New tailing dam (n = 5,
Banerjee, 2011; Diaz-Barrientos et al., 1999; Filipek NTD1 to NTD5, 0-500mm) and Old tailing dam (n =
and Pawlowski, 1990; McGrath, 1996; Sanders et al., 4, OTD1 to OTD4, 0-400mm). Soon after collection,
1987; Sutherland et al., 2001; Tokalioglu and Kartal, the core samples were cut into 100mm sections and
2005; Vidal et al., 1999), DTPA (Taylor et al., 1993), carefully transferred to clean and dry self-sealing
CH3COOH (Filipek and Pawlowski, 1990; Vidal et polyethylene bags for transport to laboratory. The
al., 1999). tailings were air-dried at room temperature,
Buffered salt solutions e.g. ammonium acetate disaggregated with a wooden roller and then sieved
(pH 7) (Ure et al., 1993). through 2 mm sieve. The samples were homogenized
Unbuffered salt solutions e.g. CaCl2 (Diaz- by coning and quartering and stored in tightly sealed
Barrientos et al., 1999; Sanders and Adams, 1987; polyethylene bags for further analysis.
Vidal et al., 1999), NaNO3 (Gupta and Aten, 1993;
Hani and Gupta, 1982), BaCl2 (Juste and Solda, 1988) 2.2. Analytical techniques
etc.
These extractants are hypothesized to extract The pH and electrical conductivity (EC) of
exchangeable or weakly bound “available” metals in the tailings were measured in solid/liquid ratio of 1:
the solid matrices viz. soils, sediments etc., which are 2.5 with distilled water (Okalebo et al., 1993). The
believed to be bioavailable. The content of extractable carbonate content analysis involved the dissolution of
forms of heavy metals is a more precise index of their carbonates in an excess of standard hydrochloric acid
ability to migrate (Anderson, 1976; Haynes and Swift, and back titration of excess acid with standard sodium
1986; Wiklander and Wahtras, 1977). hydroxide (Rowell, 1994). Total metal content of the
The present study is centered on Zawar, a tailings was determined after tri-acid digestion (using
historical Zn-Pb mining community in India. The a combination of HClO4, HNO3 and HF) as described
relics of the historical mining can be seen as hillocks by Agemian and Chau (1975).
1636
Vertical distribution and potential mobility of heavy metals in new and old tailings of a lead/zinc sulfide mine
Only surface (0-100mm) samples from both 2000). The pH of old tailings was less than the new,
the locations were considered for single extraction which could be because of the ability of sulphide
analysis. Measurement and Testing Programme tailings to generate acid upon weathering. The
(formerly BCR) of the European Commission had carbonate content of both the New and Old tailings
launched a project aiming at harmonizing was quite high, indicating calcareous nature of these
measurements for extractable trace metal contents in tailings and hence the alkaline pH.
soil. EDTA, acetic acid and ammonium acetate with The color of the new tailings was gray,
DTPA were the three extractants selected for sometimes brownish silty material, but the colour of
harmonization and validation of single extractions old tailings was always yellowish brown. The
(Quevauviller et al., 1997). EDTA 0.05 mol/L (pH 7) formation of efflorescent salts (ocherous and white
has been used for the certification of soil reference deposition) on the surfaces of old tailings was also
materials by BCR. observed. Mineralogical analysis indicated the
This test is assumed to extract both carbonate presence of Dolomite, Quartz, Ankerite and other
bound and organically bound fractions of metals and sulphide minerals in New and Old tailings.
was hence considered to be suitable for calcareous soil
analysis (Quevauviller, 1998). To assess the potential 3.2. Profile distribution of metals in tailings
mobility of Cd, Pb and Zn in tailings, a single
extraction scheme using EDTA as described by The flotation tailings profiles were
Quevauviller (1998) was preferred for the present investigated for Cd, Pb, Zn and Mn levels at two
work as it has been extensively tested in previous dumping sites called New tailing dam and Old tailing
studies also. All the vessels in contact with samples or dam, which represent by far the biggest accumulations
reagents were cleaned by soaking in HNO3 4 Mol/L of environmentally dangerous waste materials in the
(overnight) and rinsed repeatedly with distilled water. area. The mean concentrations of Pb, Zn, Mn and Cd
EDTA extractions were conducted in triplicate in 100 in New tailings (0-100mm, n=5) were 1099, 1908,
mL centrifugation tubes with tight lids by using a 2932 and 13.96 mg kg-1 and in Old tailings (0-100mm,
mechanical end-over-end shaker. All chemicals used n=4) were 1903, 5098, 2271 and 22.93 mg kg-1,
were of analytical grade, and double distilled or Milli. respectively. The results indicate high levels of Cd,
Q. water was used throughout. Pb, Zn, and Mn in both types of tailings. The levels of
Cadmium, lead, zinc and manganese in metals present in the tailings are comparable with the
digests as well as extracts were determined by flame levels observed in many previous studies on tailings in
atomic absorption spectrometry (FAAS) using a similar kind of mining areas (Table 1).
Shimadzu AA-6800 system with air/acetylene flame. The vertical profile distribution of Cd, Pb, Zn
Calibrants were prepared from 1000 µg/mL and Mn in New Tailings (0-100, 100-200, 200-300,
Spectrosol standard solutions from Merck as well as 300-400 and 400-500 mm) and Old Tailings (0-100,
from standard solutions prepared in laboratory 100-200, 200-300 and 300-400 mm) is shown in Fig.
following APHA (1995) standard methods. Multi- 1(a-d) and Fig. 2(a-d), respectively. In case of new
level standards were prepared in the same matrix as tailings, the depth-wise distributions indicate a
the extracting reagent to minimize matrix effects. decrease in Pb levels with depth up to 200 mm and a
Blanks were run simultaneously for background substantial increase in Zn and Cd levels were noted
correction and other sources of error. Mineralogical below 200 mm depth. However, no differences were
analysis of New and Old tailings was done by using observed for Mn levels with depth.
Philips X’Pert model XRD instrument. Samples were The contrasting trend noted for Pb is
scanned from 50 to 900 2θ. The peak analysis was done explained by the formation of highly insoluble
by using X’Pert data collector. anglesite (PbSO4) in the surface layer as confirmed by
XRD analysis of surface samples. Shu et al. (2001)
3. Results and discussion have also observed significantly lower concentrations
of Zn and Cd in surface (0-10cm) and subsurface layer
3.1. Physicochemical and mineralogical analysis (10-20cm), than those of deep layers (20-50cm and
50-100cm) in their study on Pb/Zn mine tailings at
pH, EC, Carbonate content, Cd, Pb, Zn and Lechang, China. Morrell et al. (1996) in their study on
Mn levels in surface tailings (0-100mm) have already mine tailings from New Zealand and Hofmann and
been discussed in previous publication (Anju and Schuwirth (2008) in a study on sphelarite bearing
Banerjee, 2010). Briefly, the pH of both type of mine waste tailings from Adolf-Helene mine,
tailings was alkaline, which contrasts with the other Germany have also observed increase in Zn and
studies in similar type of metal mining areas, where decrease in Pb concentration with depth.
the pH is usually acidic (Grimalt et al., 1999; Morrell The occurrence of anglesite in surface layer
et al., 1996; Shu et al., 2001; Simon et al., 1999). In and a substantial increase in concentration of Zn and
general, sulfide rich and carbonate-poor materials Cd below 200mm depth are two chemical and
produce acidic conditions in areas having metal mineralogical observations confirming that oxidation
sulphide as the ores. In contrast, alkaline-rich and weathering have been largely confined to surface
materials, even with significant sulfide concentrations, tailings in new tailing dam.
often produce alkaline conditions (Skousen et al.,
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Anju/Environmental Engineering and Management Journal 17 (2018), 7, 1635-1644
Table 1. Heavy metal levels in surface tailings (µg/g) of mining areas as reported in literature
Pb Zn Cd Cu As
Location Mean Mean Mean Mean Mean Reference
Range Range Range Range Range
(Median) (Median) (Median) (Median) (Median)
Adolf-Helena Schuwirth
mine, Germany 27 10 0.035 3.5 0.5 et al., 2007
(former tailing mmol/kg mmol/kg mmol/kg mmol/kg mmol/kg
pond)
Aznalcollar Lacal et al.,
300mg/k 2.05 5.33
spill, Spain 7.05mg/g 14 mg/g 2003
g mg/g mg/g
Boleslaw, Krzaklewsk
Cracow, Poland 735- 1578- i&
4039 1.5% 9-371 1-390
19555 36000 Pietrzykow
ski, 2002
Wiesloch, Stuben et
188mg/k
Germany 0.72% 3.13% - 2.1% al., 2001
g
Lechang Pb/Zn Shu et al.,
2784 2029 12 132
mine, China 2001
Aznalcollar Alastuey et
spill, pyrite al., 1999
7141 9448 31 1968
mud, Agrio
river, Spain
Pyrite mine Simon et
Aznalcollar, (9507.3) (7183.5) (28.6) (3749) al., 1999
Spain
Baxter Springs Zhu et al.,
in Cherokee 1999
County, 351 17850 125
southeast
Kansas
Aznalcollar, Vidal et al.,
Spain 7957 10707 40 2126 5321 1999
Aznalcollar, Lopez-
Spain 8091 8832 33 1323 4692 Pamo et al.,
1999
Guadiamar, Cabrera et
Spain 7888 7096 25.1 1552 2878 al., 1999
Montevecchio(S Fanfani et
ardinia) Coarse 17200 16400 150 700 - al., 1997
material (C)
Montevecchio(S Fanfani et
ardinia) fine 20900 21300 140 570 - al., 1997
material (F)
Montevecchio(S Fanfani et
ardinia) al., 1997
19000 16300 120 520 -
Very fine
material (VF)
Tui base metal Morrell et
mine, Te Aroha, 10568 486 113 al., 1996
New Zealand
Southeast Abdel-
Kansas 1370 13700 90 Saheb et
al., 1994
Old Lead Belt, Clevenger,
Missouri (400 1990
3867 1329 33.9 88.6
mesh size)
1638
Vertical distribution and potential mobility of heavy metals in new and old tailings of a lead/zinc sulfide mine
However, no discernible pattern for Cd, Pb, Zn in Cd, Pb and Zn concentration was observed at 30-
and Mn levels with depth (Fig. 2a-d) was observed for 40cm depth. This indicated that acidification
Old Tailing Profile (except profile 4), indicating that accelerated metal solubility, which resulted in
these tailings are sort of stabilized for weathering at depletion of Cd, Pb and Zn in surface tailings and
least upto a depth of 400 mm. For profile 4, an increase relative enrichment in deep layers (30-40cm).
(a)
(b)
(c)
(d)
Fig. 1. (a) Depthwise distribution of Cd in New Tailings; (b) Depthwise distribution of Pb in New Tailings;
(c) Depthwise distribution of Zn in New Tailings; (d) Depthwise distribution of Mn in New Tailings
1639
Anju/Environmental Engineering and Management Journal 17 (2018), 7, 1635-1644
(a)
(b)
(c)
(d)
Fig. 2.(a) Depthwise distribution of Cd in Old Tailings; (b) Depthwise distribution of Pb in Old Tailings;
(c) Depthwise distribution of Zn in Old Tailings; (d) Depthwise distribution of Mn in Old Tailings
1640
Vertical distribution and potential mobility of heavy metals in new and old tailings of a lead/zinc sulfide mine
Kartal, 2005; Viro, 1955), road sediments (Sutherland Cd>Cu=Pb>Ni=Zn>Cr. EDTA extracts of soils tend
et al., 2001), municipal and industrial sludges (Lo and to correlate well with plant contents, in particular with
Chen, 1990) and is increasingly being used in the the plant-available fraction for Cd, Cu, Ni, Pb and Zn
reclamation of contaminated soils and sediments (Sanders et al., 1986), Cd (Lag and Elsokkary, 1978)
(Cline and Reed, 1995; Mench et al., 1994; Sun et al., and Cu (Sanders et al., 1987). Therefore, complexants
2001). Table 2 shows the EDTA extractable like EDTA are frequently used to extract mobilizable
concentrations and percentage of total metal extracted (potentially bioavailable or potentially leachable)
by EDTA in both type of tailings. Relative EDTA metal fraction in soil (Gupta et al., 1996).
extractability of Cd, Pb and Zn in New tailings (Table
3) followed the order: Pb (96.53 ± 4.43) >>Cd (55.98 3.3.2. Correlation
± 4.81) >>Zn (33.16 ± 7.57). The EDTA extractability Correlation coefficients between the EDTA
was maximum for Pb followed by Cd in all the extractable Cd, Pb and Zn vs their ‘total’ elemental
profiles. Out of the three metals, Zn was least contents in Tailings are given in Table 4. The amount
mobilizable. Vidal et al. (1999) in their study on of Cd, Pb and Zn extracted by EDTA and their total
Aznalcollar (Spain) toxic spill have also observed concentrations showed a linear positive correlation,
similar order i.e. Pb>Cd>Zn, of EDTA extractability which are statistically significant (r values for Cd, Pb
of metals from mine sludge (tailings). Many other and Zn being 0.965, 0.638 and 0.976, respectively and
investigations have demonstrated the ability of EDTA P values being <0.001). The correlation coefficients
to extract a large proportion of total soil Pb (Abdel- indicate a strong relation between EDTA extractable
Saheb et al., 1994; McGrath and Cegarra, 1992; and total Cd and Zn. Anju and Banerjee (2011) has
Pichtel et al., 2001; Sposito et al., 1982; Tsadilas et al., also observed statistically significant linear positive
1995). Clayton and Tiller (1979) observed that EDTA correlations between EDTA extractable and total
extracted 74-93% of total Pb from soils contaminated concentrations of Cd, Pb and Zn (r values for Cd, Pb
by smelter emissions, but only 20-60% and Zn being 0.901, 0.971 and 0.795, respectively, and
uncontaminated soils. P values being <0.001), in soils of a lead and zinc
Relative EDTA extractability of Cd, Pb and Zn mining area, India. These findings are in agreement
in Old tailings (Table 3) followed the order: Cd (61.94 with other studies such as McGrath’s (1996) work on
± 25.09) ≥ Pb (55.42 ± 10.54) > Zn (36.23 ± 6.14). The Cd, Cu and Ni; Boon and Soltanpour’s (1991) work
relative extractability of these metals is consistent with on Cd, Zn and Pb and Mehra et al.’s (1999) work on
the findings of the study of Anju and Banerjee (2011) Cd and Cu for contaminated soils. These results can
on soils of a lead and zinc mining area, India and appear to justify the use of ‘total’ metal contents as a
McGrath (1996)’s on Irish soils, where EDTA useful preliminary indicator of areas where the risks of
extractability followed the sequence metal excess or deficiency are high.
Table 2. EDTA extractable concentrations (mg kg-1) and percentages of total Cd, Pb and Zn in New and Old surface tailings
Cd Pb Zn
Sample ID
EDTA-Extractable Total % Extracted EDTA-Extractable Total % Extracted EDTA-Extractable Total % Extracted
NTD1 3.85 6.98 55.16 735 768 95.70 355 1227 28.93
NTD2 7.06 12.96 54.48 979 987 99.19 597 1990 30.00
NTD3 9.81 19.94 49.20 1379 1525 90.43 754 3069 24.57
NTD4 10.41 16.95 61.42 1186 1246 95.18 727 1758 41.35
NTD5 7.74 12.96 59.72 992 971 102.16 613 1498 40.92
OTD1 3.33 13.46 24.74 747 1584 47.16 956 3538 27.02
OTD2 13.81 18.44 74.89 799 1691 47.25 1686 4276 39.43
OTD3 14.19 20.44 69.42 1070 1845 57.99 1785 4588 38.91
OTD4 30.99 39.38 78.69 1727 2493 69.27 3161 7991 39.56
Table 3. Relative mobility of Cd, Pb and Zn in New and Old tailings as estimated by single extraction
Table 4. Correlation coefficients between amount of Cd, Pb and Zn extracted by EDTA and their “Total” content
EDTA-extractable vs ‘total’
Element
( n =9)
Cd r =0.965 **
Pb r = 0.638
Zn r = 0.976**
** All correlations are significant at the 0.01 level (2-tailed)
1641
Anju/Environmental Engineering and Management Journal 17 (2018), 7, 1635-1644
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1645-1656
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
This paper presents decentralized and centralized decision-making conditions based on consumer carbon sensitivity and carbon tax
policy in a supplier-driven two echelons supply chain. The analysis shows that: 1) the optimal emission reduction amount under
centralized decision-making is more than that under decentralized decision-making; 2) the carbon tax should be levied properly
because the carbon emission reduction will decrease as the carbon tax is higher than a critical value; 3) the consumer carbon
sensitivity is positively correlated with carbon emission reduction, but it may cause total mission rised in certain condition. Then
an extensive numerical analysis is conducted to enrich the discussion and to draw some managerial insights on how to reduce
carbon emission in the supply chain.
Key words: carbon emission reduction, consumer carbon sensitivity, carbon tax policy, Stackelberg game, supply chain
Received: January, 2018; Revised final: May, 2018; Accepted: June, 2018; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: tobailan@foxmail.com; Phone: +8617713288335; Fax: +86312 7528673
Bai et al./Environmental Engineering and Management Journal 17 (2018), 7, 1645-1656
in the manufacturing process. Therefore, how the low carbon in an emission sensitive supply chain or
government levies the carbon tax and how they market, both the channel profit and the emission
produce a reasonable preventive solution is a problem reduction increase in the consumers’ preference to
influenced both government and companies. Thus, low-carbon consumption simultaneously in particular
questions about how the carbon tax and the consumer cases (Du et al., 2015). Liu et al. (2012) analyzed the
carbon sensitivity affect the carbon emission reduction decision-making and profit-making of retailers and
decisions of companies, how the government manufacturers in the supply chain, putting the
formulates the optimal carbon tax considering emphasis on consumer environmental preferences. Ji
consumer carbon sensitivity have become urgent et al. (2017) compared two emission reduction
problems to be solved. strategies, including single manufacturer's emission
In this paper, research focuses on the carbon reduction in production strategy and joint emission
tax levied on companies and consumer preferences for reduction strategy. They indicated that when
low-carbon products from the perspective of supply considering consumers' low-carbon preference, the
chain; the relevant literature review is hence done retailer always has motivation to implement low
from two perspectives as following: carbon promotion though without the manufacturer's
incentives. Yilei et al. (2017) focused their research on
1) Carbon tax: three contract models under low carbon preferences of
Carbon tax can induce companies to reduce consumers to analyze the cooperation and profit
their carbon emissions (Bruvoll and Larsen, 2002; reduction in the supply chain. They concluded here
Meng et al., 2013; Bjørner and Jensen, 2002), and that companies constraining the wholesale price can
different carbon tax rates result in different carbon make the supply chain reduce emissions and optimize
emission reductions. In the supply chain, revenues of supply chain coordination. Wang et al. (2016) analyze
companies change under variable decision-making by contracting emission reduction for supply chains
strategy. Tseng and Hung (2014) have established a considering market low-carbon preference. Therefore,
decision-making model for the sustainable we can get that consumer carbon sensitivity affects the
development of garment processing supply chain revenue of the companies and the entire supply chain.
network under the carbon tax policy, and the strategic Under different strategy, the effects are not the same.
decision-making of companies under different carbon To sum up, the papers reviewed make
tax policies. Comas Martí et al. (2015) take demand contribution to the carbon emission reduction to
uncertainty into account and includes decisions on protect the environment, but seldom paper takes both
supply chain responsiveness under different carbon of carbon tax and consumer carbon sensitivity. In this
policies for both functional and innovative products. paper, we present a game theory model to assist
Yue and Shuaihua (2016) have analyzed the companies facing these joint affect items, and analyze
manufacturers and supplier decisions under the carbon the revenue distribution to help them get proper
tax policy when suppliers involved and not involved decision to make the profits maximized for the entire
in carbon emission and the impact of carbon tax on the supply chain. Suggestions of the carbon tax for the
two kinds of decision-making. Yang and Luo (2016) government are given as well. More precisely, we
produce a model expressing both the emission contribute to the literature with a two-echelon supply
reduction decisions of manufacturers within carbon chain game model that simultaneously considers
tax constraints and the stochastic demand of the carbon tax and consumer sensitivity of low-carbon
wholesale price of companies and their revenue products. It also provide managerial implications for
sharing contract and announce that there only existed the companies to maximize revenue and the
an emission reduction rate within two kinds of government to levy carbon at proper amount.
decision-making to maximize the supply chain The structure of this paper is as follows. In
revenue. Section 2, we present the game modal in both
Besides the decision making, revenue decentralized and centralized mode for the carbon
distribution and are also analyzed. Yang et al. (2017) emission reduction and the balance analysis. In
analyzed the revenue sharing and first-run advantage Section 3, we present detailed numerical analyse to
in manufacturers' carbon emission reduction efforts illustrate the influence of the carbon tax and consumer
and firms' profitability in linear demand settings of a carbon sensitivity captured by the model and the type
manufacture-driven supply chain. of managerial insights that it allows to derive. In
These papers show that carbon tax play a Section 4, we conclude and discuss future research
significant role in reducing emissions and useful opportunities.
methods are also given, but joint influence of carbon
tax and other related items such as are not mentioned. 2. Material and methods
1646
Supply chain emission reduction optimization under consumer carbon sensitivity and carbon tax policy
symmetrical. The manufacturer can only order generic reduction cost coefficient of the supplier; that is, c(e )
or low-carbon raw materials from upstream, so the satisfies c' (e ) < 0 , c'' (e ) < 0 . In the actual production
supplier is in the leading position in the supply chain.
Since the supply chain is driven by the supplier, process, the reduction of carbon emission e will lead
which means the supplier is in the dominant position, to increasing marginal costs, indicating that the early
the government charges carbon tax on the supplier is stage emission reduction will be easy to carry on, but
more feasible to get the influence of the entire supply become more and more difficult later.
chain. Consumers who are sensitive to low-carbon Hypothesis 4: When there is some demand
environmental protection also grow in number. for low-carbon products in the market, the supplier
Therefore, the supplier will implement carbon adopts the order-oriented production method with the
reduction technologies to reduce the carbon emissions same market demand without regard to stock-out and
per unit of product. Hence, several situations of the stock-extrusion problems. This article uses the
consumer carbon sensitivity are considered under the symbols and their meanings as shown in Table 1.
carbon tax: decentralized decision-making when
demand is unrelated to emission reduction; centralized 2.2. Methods and models
decision-making when the demand is related or
unrelated to emission reduction; and how the supplier 2.2.1. Decentralized decision when demand unrelated
and the manufacturer will make the decision. The to carbon emission reduction
following assumptions have hence been made for the In this situation, the product demand is
simplification and research convenience of the model: expressed as Q = a - p. When the demand is unrelated
Hypothesis 1: Assuming that upon the occasion with the consumers’ sensitivities of carbon emission
the supplier does not invest in carbon emission reduction, the game is normally a two-echelon game.
reductions, the initial carbon emission reduction per In the game, the supplier first determines the
unit of production is e0. Then the government imposes wholesale price w and the emission reduction rate e ,
a carbon tax on carbon dioxide emissions from the while the manufacturer determines the final retail
supplier at a rate of t yuan/ton CO2. price p according to the wholesale price and the
Hypothesis 2: The wholesale price and emission reduction rate provided by the supplier (w,e )
production cost of the supplier's unit product are w and and the observed market information.
c respectively, as the wholesale price is the supplier's In the model, the government levies carbon tax
decision variable and the manufacturer sell their t of the CO2 , which is generated by the supplier in the
products with the price p per unit. production process. At this point, we can model the
Hypothesis 3: Carbon emission reductions for profit maximization decision function of the supplier
the supplier after carbon reduction investment is e, and the manufacturer as Eqs. (1-2):
0≤ e ≤ e0 and e is the supplier's decision variable. The
emission cost of the supplier after carbon emission π sN = (w − c − te0 )(a − p) − ke 2 / 2 (1)
reduction satisfies c(e ) = ke 2 / 2 , k > 0 (Ma et al., 2013;
Peng et al., 2013), where k is the carbon emission π mN = ( p − w)(a − p) (2)
Variable Meaning
w whole sale price of a unit product
p retail price of a unit of product
Q market demand for products
πs supplier's revenue
πm manufacturer's revenue
πc supply chain’s revenue
* optimal decision-making
t a unit of carbon tax levied by he government
c supplier production costs
N decentralized decision when demand isn’t related to carbon emission reduction
D decentralized decision when demand is related to carbon emission reduction
C centralized decision-making when demand is related to carbon emission reduction
e the amount of carbon emission reduction of the supplier
k cost coefficient for carbon emission reduction
e0 initial discharge of per unit product
E discharge of supply chain
η consumer sensitivity to low carbon products
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Bai et al./Environmental Engineering and Management Journal 17 (2018), 7, 1645-1656
Calculating the first-order partial derivative of 2.2.2. Decentralized decision when demand related to
π rN with respect to the retail price p in Eq.(1) and carbon emission reduction
Since consumers' sensitivity for low-carbon
make ∂π mN / ∂p = 0 , we can obtain the manufacturer's
products will result in lower sales of products of
retail price relative to the wholesale price of the carbon-laden companies, if companies want to sell
supplier as Eq. (1): more products, they will have to take active measures
to deal with carbon emission. Energy-saving and
p = (a + w) / 2 (3) emission reduction technology allows companies to
reduce energy consumption in the process of
Substituting Eq. (3) into Eq. (1) and calculating production, and the manufacturer will invest in
the first-order partial derivative of the wholesale price applying certain technology to achieve the reduction
w and letting ∂π sN / ∂w = 0 , we get the optimal of carbon emissions rather than traditional production,
wholesale price w of the supplier, as Eq. (4): which means the carbon emission of per unit product
will decrease. The demand of consumers will thus
increase because of the carbon sensitivity.
a + c + te0
wN =
*
As long as the carbon emission varies, the
2 (4) carbon tax cost of companies, the increase of market
demand and the revenue of the supply chain
Substituting Eq. (4) into Eq. (3), we could yield companies change. When companies reduce carbon
*
the optimal retail price p N as Eq. (5): emissions, the demand will be expressed as
Q = a − p + ηe within the emission reduction amount
3a + c + te0 e as the decision variable. The revenue functions for
pN =
*
(5)
4 the supplier and manufacturer are constituted by Eqs.
(7-8):
Substitute the optimal decision of the supplier
and the manufacturer into the demand function and π sD = [w − c − t (e0 − e )](a − p + ηe ) − ke 2 / 2 (7)
revenue Eqs. (1-2), and then the market demand, the
optimal revenue for the supplier and the manufacturer
will be as Eq. (6): π mD = ( p − w)(a − p + ηe ) (8)
π sN =
* (a − c − te0 )2 − 4ke 2 determines its own wholesale price and emission
reduction amount according to the maximization of
8 (6) revenue. In the second stage, the manufacturer
determines the retail price according to the emission
π mN =
* (a − c − t 0 )2 reduction amount of the supplier and the wholesale
16 price. Then we can use the inverse inductive method
to solve the problem, while the supplier would offer
According to Eq. (1), we can get that when the optimal wholesale price as Eq. (9):
demand is unrelated to the initial emissions of the
a + c + te0 + (η − t )e
wD =
*
products, the optimal emission reduction of the
supplier is e = 0 . It means that the supplier will not be 2 (9)
willing to reduce the carbon emission because
emissions reduction has no effect on consumers’ The optimal retail price is computed as Eq.
purchase of the product. However, if consumers' (10):
carbon sensitivity is related to the carbon emission of
the product, which means when the manufacturer 3a + c + te0 + (3η − t )e
pD =
*
π sD
*
=
[a − c − te0 + (t + η )e] − 4ke 2
2
(11)
8
1648
Supply chain emission reduction optimization under consumer carbon sensitivity and carbon tax policy
π mD =
* [a − c − t 0 + (t + η )e]2 ∂ 2π C / ∂e 2 ∂ 2π C / ∂p∂e 2ηt − k t + η
H = 2 C =
2
16 ∂ π / ∂p∂e ∂ π / ∂p t + η
2 C
− 2
*
and e N satisfies Eq. (12).
*
eC =
(t + η )(a − c − te0 )
(19)
Substitute the optimal emission reductions into 2k − (t + η )2
Eq. (11), then the demand, the revenue of supplier and
the manufacturer are computed as Eq. (15): * *
Taking P C and e C into demand, we get that
k (a − c − te0 ) the total demand and revenue of the whole supply
QD =
*
k ( a − c − te 0 )
QC =
*
k (a − c − te0 )
2
π sD = 2 k − (t + η )
*
2
[
2 4k − (t + η )
2
] (15)
k ( a − c − te 0 )
2
πC =
*
k 2 (a − c − te0 )
[ ]
2
π mD = 2 2 k − (t + η )
*
2
[4k − (t + η ) ] 2 2
(20)
1649
Bai et al./Environmental Engineering and Management Journal 17 (2018), 7, 1645-1656
wmin =
*
π sD + ke2 / 2 + cQC + t e0 − eC QC
*
*
( *
) *
reduction amount is more than decentralized. It shows
that under the precondition that the government levies
C
Q carbon tax, the emission reduction effect will be more
(22) effective within the cooperation between the supplier
p C Q C − π mD
* * *
and the manufacturer in the supply chain. Thus, when
wmax = the carbon tax policy is levied, the government should
QC
*
w (24) When
{ (
w − c − t e − eC Q c − k eC
) ( ) (1−α )
2
/ 2 −π D*
}
* * *
0 s 2
4e0 4k − ( t + η ) −
2
Then the best solution to the retail price follows 4ke − e ( t + η )2 − ( t + η ) ( a − c − te ) > 0
Eq. (25): 0 0 0
π C*
s = + 3. Results and discussion
2 2 (26)
When the government imposes carbon tax on
π mD π C − π sD
* * *
the supplier, the supplier will consider the cost and
π mC = +
*
1650
Supply chain emission reduction optimization under consumer carbon sensitivity and carbon tax policy
decision to meet the low-carbon needs of both or not, the demand is negatively correlated with the
consumers and government, as well as try to get carbon tax. In addition, consumers have the maximum
maximum revenue. demand when they are carbon-sensitive under
Owing to the complexity of solving the model, centralized decision-making. Meanwhile, demands
to verify the model conclusion and simplify the model under decentralized decision-making only experience
calculation process, we use Matlab (R2016a) as a minor differences in demand both related and
calculation tool to solve each equation in the model. unrelated to carbon emission reduction. In Fig. 2, the
To illustrate the effect of carbon tax and carbon- supply chain revenue are all negatively related to the
sensitive coefficient on emissions reductions, it is carbon tax in the three game models. The revenue
assumed that a = 100 , c = 60 , k = 2 , η = 0.4 , under centralized decision making within carbon-
e0 = 40 , t = 0.1 , then compare companies revenue intensive is the highest, and when the demand is
unrelated to the emission reduction, the supply chain
and total revenue on the supply chain under demand
revenue is the lowest. Therefore, the emission
related/unrelated to carbon emission or not under
reduction effect within supply chain cooperation is
centralized decision-making and decentralized
higher than that within individual emission reduction.
decision-making, as shown in Table 2. This Table
When the government has levied a carbon tax, we
shows that, when consumers' demand is related to
should encourage upstream and downstream
carbon emission reduction, companies have increased
companies in the supply chain to cooperate in
the revenue of both the supplier and the manufacturer
emission reduction.
by investment in emission reduction. At the same
According to Figs 1-2, when the government
time, Nash bargaining constrains the wholesale price
wants to levy carbon tax to protect the environment, it
and the Shapley method to allocate companies revenue
should carefully decide the tax amount. That’s
under centralized decision-making, so that the profits
because if the tax is too heavy, the market will
of all parties under decentralized decision-making
decrease badly and even the supplier and manufacturer
have been improved and the supply chain participates
may quit the market leading to industry decline in the
are coordinated. We then analyze the impact of carbon
long term. It illustrates in Fig. 3 that when the tax rate
tax changing demand, supply chain revenue, emission
is low, while the level of emission reduction of supply
reductions and total emissions, as shown in Figs. (1-
chain rises with the increase of carbon tax. When the
4). We set the consumer preference as η = 0.4 ,
tax rate exceeds a certain threshold, the optimal
while the range of variation of t is 0~1. In Fig. 1, we emission reduction will decrease with the increase in
can get that no matter consumers are carbon-sensitive carbon tax.
Table 2. Revenues of companies and entire supply chain under different decision-making mode
1651
Bai et al./Environmental Engineering and Management Journal 17 (2018), 7, 1645-1656
450
C*
D*
400
N*
350
300
250
200
150
100
50
0
0 0.2 0.4 0.6 0.8 1
t
*
eC
4 D*
e
3
e
*
eN
0
0 0.2 0.4 0.6 0.8 1
t
In Fig. 4, it shows that the total carbon as shown in Fig. (5-8). We set carbon tax as t = 0.5
emissions under the three decision-making modes , η range of 0 ~ 1. In Fig. 5 it is shown that, when
have a negative correlation to the carbon tax. When consumers are carbon-sensitive, if carbon-sensitivity
0 < t < 0.33 , carbon emissions under decentralized increases, the demand increases too, and will reach the
decision-making within carbon-sensitive demand is top under centralized decision-making. Meanwhile,
larger than that within non-carbon-sensitive demand, there is only a little difference of the demand under
which means that when 0 < t < 0.33 , the carbon tax decentralized decision-making no matter the demand
rate is low and so does the carbon emission. When is related or unrelated to emission reduction.
0.33 < t < 1 , since the carbon tax rate rise, Fig. 6 presents that when the demand is related
companies should sell more products to make up for to consumer carbon sensitivity, the supply chain
carbon emission reduction costs and the carbon tax, revenue has a positive correlation to consumers’
while the total carbon emission is largest under carbon sensitivity under both decentralized and
centralized decision making. centralized decision-making, and the revenue of the
Therefore, the government should not make the supply chain is higher under centralized rather than
tax amount too low or too high when levying it decentralized decision-making.
because a high tax rate will decrease the enthusiasm of Therefore, we use Nash bargaining to restrict
companies in emission reduction and a low tax rate the wholesale price and then distribute the revenue
will not achieve the purpose of emission reduction. under the centralized decision-making within the
The government needs to balance between industry Shapley method. Hence, under decentralized decision-
and environment protection. Then we analyze the making, both of the supplier and the manufacturer can
impact of the consumer changes on demand, supply get more profit.
chain revenue, emission reduction and total emissions,
1652
Supply chain emission reduction optimization under consumer carbon sensitivity and carbon tax policy
800 24
N*
E
D*
E
22
700 C*
E
20
600
18
500
16
400
E
14
Q
300 12
10
200
C* D*
Q Q
8 N*
Q
100
6
0
0 0.2 0.4 0.6 0.8 1 4
0 0.2 0.4 0.6 0.8 1
t
Fig. 4. Impact of carbon tax on total emissions Fig. 5. Impact of consumers’ carbon sensitivity differences
on demand
240
220
200
180
160
140
D*
C*
120
N*
100
80
60
0 0.2 0.4 0.6 0.8 1
According to Figs. 5-6, the companies in the emissions amount within demand related to consumer
supply chain should improve the promotion of low- carbon sensitivity is lower than demand unrelated to
carbon products to increase consumer carbon the sensitivity. When η = 1 , the level of emissions
sensitivity, then they can work together within almost achieves zero. Under centralized decision-
centralized decision-making in order to sell more making, when 0 < η < 0.61 , the total carbon
products and get more revenue.
emissions amount within demand related to consumer
In Fig. 7, we find out that with the increasing
carbon sensitivity is lower than demand unrelated to
of consumer carbon sensitivity, the carbon emission
the sensitivity. When 0.61 < η < 1 , the emission is
reduction increases as well under both centralized
decision-making mode and decentralized decision- higher than the demand unrelated to carbon
making mode, which can be concluded that sensitivity, and when η = 1 , the carbon emission
consumers' carbon sensitivity can push companies reaches the maximum value. It means that although
forward to reduce carbon emissions. In Fig. 8, the the emission reduction increases, the increase of the
total carbon emissions under the three decision- consumers’ carbon preference leads to the increase in
making modes are positively correlated with the sales and finally causes more emissions. Therefore,
consumers’ carbon sensitivities. Under decentralized the consumer carbon sensitivity plays a vital role in
decision-making, when 0 < η < 1 , the total carbon carbon emission reduction of the supply chain.
1653
Bai et al./Environmental Engineering and Management Journal 17 (2018), 7, 1645-1656
12
350
10 300
D*
C* E
E N*
250 E
8
200
6
e
E
150
100
*
eN
2
* * 50
eC eD
0
0
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1
Fig. 7. Impact of consumers’ carbon sensitivity differences on Fig. 8. Impact of consumers’ carbon sensitivity differences on
carbon emission reduction carbon emissions
On the basis of encouraging the supplier and (2) When demand is unrelated to carbon
the manufacturer to cooperate on emissions reduction, sensitivities, carbon tax and consumers’ carbon
the government should try to keep the consumer sensitivities will not affect the emission reductions of
carbon sensitivity at 0 < η < 0.61 , in order to get companies. When demand is related to carbon
better environment protection. sensitivities, emission reductions will first increase
and then decrease with the carbon tax increases,
4. Conclusions meaning that emission reductions and consumer
carbon sensitivity are positively correlated;
This paper s presents the game model between (3) When the carbon tax is considered, the total
the supplier and the manufacturer under the carbon tax emission reductions in the supply chain decrease when
policy and consumers' carbon-sensitive differences. 0 < t < 0.33 under decentralized decision-making.
By comparing the demand related or unrelated with Considering the carbon sensitivities of consumers,
the emission reduction under both decentralized and when 0 < η < 0.61 , the total emission reductions of the
centralized modes of decision-making, we have supply chain will increase under centralized decision-
provided optimal emission reduction decisions, profit making. Therefore, the comprehensive consideration
decisions and optimal emissions in the supply chain of the carbon tax and consumer carbon sensitivity is
within different decision-making situations. particularly important for the formulation of emission
Comparing with reviewed paper’s conclusion reduction strategies.
as manufacturer’s optimal carbon emissions per unit This paper is based on recognition of the reality
product the centralized channel, no matter whether the that both the supplier and the manufacturer are risk-
supply chain is coordinated or not, or when neutral and information symmetric. In fact, since the
considering consumers' low-carbon preference, the cost of the supplier's emission reduction investment is
retailer always has motivation to implement low- uncertain and affected by risk aversion, it is very
carbon promotion though without the manufacturer's difficult to realize the complete sharing of information
incentives, we focus on more comprehensive effect by on the supply chain, while uncertainty factors will also
considering both carbon tax and consumer carbon affect the cost and profit distribution between the
sensitivity and finally, we get different conclusions by supplier and the manufacturer. Therefore, considering
calculating the equilibrium solution and numerical the information uncertainty of both parties is one of
analysis as below: the principal research directions to be taken in the
(1) Demand and supply chain revenue are future.
negatively related to carbon tax, but positively related
to consumers’ carbon-sensitivity preferences. Besides, Acknowledgements
the demand and supply chain benefits are highest We thank the support provided by the Project 691249 RUC-
under centralized decision-making under both demand APS (EU H2020-MSCA-RISE-2015), National Natural
and carbon sensitivities; Science Foundation of China: Urban Logistics Management
(71390334).
1654
Supply chain emission reduction optimization under consumer carbon sensitivity and carbon tax policy
54, 313-332.
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Also, in centralized decision-making mode, we can Tseng S.-C., Hung S.-W., (2014), A strategic decision-
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∆E C = E N − E C = e0 Q N − ( e0 − e ) Q C =
*
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Howell B.C., (2011), Customer response to carbon
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0 0 0
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carbon preference, Journal of Cleaner Production, 120, Yang H., Luo J., Wang H., (2017), The role of revenue
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Zhou Z.F., Xiao Y.X., Ziqi D., Liu L.M., Chen X.H., Zeng contract game model for joint emission reduction at
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1656
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1657-1666
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Mingyang Zhang1,4, Kelin Wang1,4∗, Huiyu Liu2, Weijian Luo3, Jing Wang1,4, Yuemin Yue1,4
1KeyLaboratory of Agro-ecological Processes in Subtropical Region, Institute of Subtropical Agriculture,
Chinese Academy of Sciences, Hunan 410125, China
2College of Geography Science, Nanjing Normal University, Nanjing 210046, China
3Central South Forest Inventory and Planning Institute of State Forestry Administration, Changsha 410014, China
4Huanjiang Observation and Research Station for Karst Ecosystems, Chinese Academy of Sciences, Huanjiang, 547100, China
Abstract
The changing characteristics of vegetation carbon patterns in the karst region of northwest Guangxi, China and their impact factors
were analyzed on the basis of vegetation inventory data from 2005 to 2010. A radial basis function network model (RBFN) was
constructed using data from 1377 samples and 13 environmental factors. The results for the 5-year study period were as follows:
(1) The total carbon storage of vegetation had increased with an annual growth rate of 1.84% and the carbon density of vegetation
increased from 29.04 t hm-2 to 29.57 t hm-2. The carbon density in the west (>40 t hm-2) was greater than that in the Middle East
(<25 t hm-2). Hot spot analysis revealed a random distribution of vegetation carbon density in 2005, but a highly aggregated
distribution in 2010. (2) The four most important impact factors on spatial distribution of vegetation carbon density in this area
were land type, forest type, forest category, and vegetation type (significance <50%). The least important factors were location,
slope, aspect, and elevation (significance of 2–11%). Vegetation carbon density increased significantly with the implementation of
rocky desertification control measures. Factors changed by human activities had much greater impacts than topographic factors on
the spatial distribution of vegetation carbon density. Therefore, the Ecological Immigration Program, returning farmland to forests,
and rocky desertification control measures had an important effect on the pattern of vegetation carbon density.
Key words: Guangxi China, impact factors, karst, northwest, pattern characteristic, radial basis function network (RBFN),
vegetation carbon
Received: February, 2014; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: my_1223@163.com; Phone: +86 731 84615208; Fax: +86 731 84612685
Zhang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1657-1666
campaign, 49,133 families (232,705 persons) were characteristics in karst regions. This will permit an
relocated in northwest Guangxi, China. The total area accurate estimation of the carbon storage in karst
of the Green for Grain Program was up to 1,278.67 regions. We used forest resources inventory data
km2 in Baise during 2001–2004 (Zhang et al., 2011). collected in 2005 and 2010 to study vegetation carbon
This included 605.33 km2 of farmland that was density in a typical karst area in northwestern
restored to woodland and 673.33 km2 of reforestation Guangxi, China. In addition, a radial basis function
activities of barren hills. For example, in Duan network (RBFN) model was applied to test the
County, the land area of rocky desertification had been influence of environmental factors on carbon spatial
reduced to 333,356.9 hm2, and 45,333.33 hm2 of land distribution.
were converted from farmland to forest as part of the
Green for Grain program by 2009. The comprehensive 2. Study area and methods
treatment of rocky desertification was expected to
have caused changes in the vegetation carbon pattern. 2.1. Study area
Impact factor analysis could be used to evaluate the
treatment of rocky desertification. The study area was located in northwest
Vegetation carbon in the karst area has been Guangxi, China (104°29´–109°09´E, 23°41´–
studied by many researchers (Liu et al., 2008; Wang 25°37´N) (Fig. 1), which includes 23 counties
et al., 2012; Ye et al., 2010; Luo et al., 2010; Tian, et covering an area of 69,400 km2 and sustaining a
al., 2011). However, most of the studies focused on population of 7.97 million people. The region has a
the micro or local ecological system scale. subtropical wet monsoon climate with an annual
Investigation of the spatial pattern of vegetation temperature 19.5°C and an annual precipitation of
carbon is needed at regional scale. Furthermore, 1,000–1,600 mm. The elevation in this hilly region
factors that affect the formation of vegetation carbon ranges from 100 m to 2,000 m above sea level and the
spatial patterns have been scarcely studied. dominant vegetation communities are mixed
Investigation of the changes in vegetation carbon subtropical evergreen and deciduous forests. The
patterns in a typical karst area, and further analysis of landforms in this region are typical karst landforms,
the main impact factors can provide a scientific including poljes, cockpits, towers, and dolines. The
reference for the evaluation of karst rocky region supports a mountainous agricultural region in
desertification control and basic data for which the cropland areas are generally not very fertile.
understanding the driving mechanisms of carbon
1658
Factors affecting the pattern of vegetation carbon density in a karst region in northwest Guangxi, China
1659
Zhang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1657-1666
N
(2) Identify the winner yw = max (yi), i < n.
F ( x)
= ∑ w G( x − x )
i =1
i i (3) If yw > αT, then change the position of the center
(5)
of the winner using (Eq. 13):
where G (x-xi ) is a Green’s function and x is its center.
The Green’s functions were characterized by a cw( k +1) =cx( k ) + r ( x j − cw( k ) )
(13)
mean vector xj and common variance σ2, as (Eqs. 6-7):
x − xi where α is an arbitrary ratio (α = 2.0 in this case) and
−
G ( x − xi ) =
e
2δ 2j T is the threshold value (T = 10-4).
(6) (4) If yw < T/α, then construct a new hidden node with
center at the point xj and variance equal to δ and
and
increase the number of total hidden nodes n by 1.
−
x − xi The algorithm stops when there are no new
N
F ( x) = ∑ wi e
2δ 2j hidden nodes after testing all points of data set D.
i =1 (7)
2.2.4. Impact factors of vegetation carbon density
where: each equation consists of a linear superposition The following 13 factors were selected for
of multivariate Gaussian basis functions (probability analysis:
bells) with centers xj, located at the data points and (1) Altitude: the range of altitude in the study area
δ j2 was 92–1876 m;
widths . (2) Aspect: divided into 9 aspects; North (338–22°),
The initial number of nodes was set at two. The the Northeast (23–67°), East (68–112°), Southeast
first node was assigned a Gaussian function centered (113–157°), South (158–202°), Southwest (203–
on the center of data set, determined by Eq. (8): 247°), West (248–292°), Northwest (293–337°), and
no slope (<5° slope). Aspects were coded 1, 2, 3, 4, 5,
N
xi
xav = ∑
6, 7, 8 and 9, respectively
i =1 N (8)
(3) Slope position: 6 positions, ridge (mountain
watersheds), above, middle, lower (the downhill), vale
(collection waterline on both sides of the valley), flat
and the second node was assigned a Gaussian function (plain and tableland). Slope positions were coded 1, 2,
centered on the point determined by the vector xp that 3, 4, 5, and 6, respectively;
maximized the function (Eqs. 9-10) (4) Slope angle: the slope of samples in the study
area were between 0 and 80°;
P( x) = ∫ S Q( x)dS (9) (5) Soil thickness: sample thickness was 1–180 cm;
(6) Humic layer: the thickness of humus layer was
where: 0–35 cm;
Q( x) = {1,0, if x∈D
(7) Vegetation coverage: total vegetation coverage
if x∉D in the study area was 10–100%;
(10)
(8) Land type: according to the characteristics of
The variance of Gaussian functions is assumed land cover and utilization, including arbor, shrub,
to be constant and equal to (Eq. 11): farmland, grass, and construction land;
(9) Vegetation type: including coniferous forest,
N m
( j) evergreen broad-leaved forest, deciduous broadleaf
∑∏ ( x
i =1 j =1
( j)
i −x ) forest, bamboo forest, deciduous shrubs, and
δ =r m
evergreen shrub;
N
( j)
∏ ∑ (x
j =1 i =1
( j)
i − x )2 (10) Grade of rocky desertification: the degree of
rocky desertification was defined as in the Forest
(11)
Inventory Check Operating Rules of Guangxi. The
where m is the number of dimensions (number of study area included the following grades: no rocky
nodes in the hidden layer), x-(j) is the mean value for desertification, potential, mild, moderate, and severe
dimension j and r is an arbitrary ratio defining the total rocky desertification;
number of Gaussian functions. (11) Forest species: 23 sub forest species were
The second layer was carried out using a self- categorized as in the forest inventory check operating
organizing algorithm with the following steps: rules of Guangxi. Species were categorized according
(1) Calculate the output of the Gaussian functions for to their potential for such uses as soil and water
all hidden nodes (Eq. 12) conservation, national protection, scenic value,
timber, et al.;
x j − ci
− (12) Forest type: the main two forest types were
yi = e δ2
(12) ecological forest and commercial forest. The
ecological forest was subdivided into national
where i < n (number of nodes). ecological forest and local ecological forest.
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Factors affecting the pattern of vegetation carbon density in a karst region in northwest Guangxi, China
Commercial forest was divided into timber forest, hm-2) (Fang et al., 1996; Wang, 2004; Cao et al., 2002;
firewood forest, and economic forest; Jiao et al., 2005; Huang et al., 2008). The vegetation
(13) Area level: there were 7 categories, according carbon density at the study site was close to that of
to the contiguous area of each vegetation type. Jiangxi (25.38 t hm-2) (Wang and Wei, 2007). The
Categories were <1 hm-2, 1–4.9 hm-2, 5–9.9 hm-2, 10– cover type with the highest vegetation carbon density
19 hm-2, 20–49 hm-2, 50–99 hm-2, and >100 hm-2 and was arbor (34.82 t hm-2 and 35.12 t hm-2 in 2005 and
were coded 1, 2, 3, 4, 5, 6, and 7, respectively. 2010, respectively), followed by bamboo, which
accounted for about 50.82% and 54.62% of total
3. Results and discussion vegetation carbon storage in 2005 and 2010,
respectively.
3.1. Pattern characteristics of vegetation carbon Because the samples were fixed, changes in the
number of samples in each land type classification
3.1.1. Temporal change in vegetation carbon may indicate regional vegetation changes to some
Vegetation carbon density in the study area degree. In the period from 2005 to 2010, the number
increased from 29.04 t hm-2 in 2005 to 29.57 t hm-2 in of samples classified as arbor and shrub increased,
2010 (Table 1). Accordingly, the storage of vegetation whereas samples classified as no stumpage forest,
carbon had increased from 4.19 × 104 t to 4.27 × 104 t unused land, and farmland decreased dramatically
with an increase of 1.84%. The vegetation carbon (Table 1). These changes indicate that the vegetation
density in the study area was lower than the overall coverage in the study area has been improved by rocky
vegetation carbon density of China (38.05 t hm-2), desertification control policies, such as ecological
Fujian Province (32.85 t hm-2) and Hainan Province migration program and the Green for Grain program.
(32.59 t hm-2). Although the greatest vegetation carbon
However, the vegetation carbon density in the density was in provincial and national nature
study area was higher than in northern Hunan protection areas, the other projects also resulted in
Province (18.53 t hm-2) and Sichuan Province (18.47 t dramatic increases in vegetation carbon (Fig. 3).
Table 1. Vegetation carbon density and their changes in Guangxi, China between 2005 and 2010
Vegetation Vegetation
Sample number
Land type carbon density (t.hm-2) carbon storage (* 104 t)
2005 2010 05-10 2005 2010 05-10 2005 2010 05-10
Arbor 612 664 52 34.82 35.12 0.30 2.13 2.33 0.20
Bamboo 10 11 1 29.35 28.52 -0.83 0.03 0.03 0.00
Shrub 231 244 13 24.63 24.53 -0.11 0.57 0.60 0.03
No stumpage forest 134 108 -26 24.66 25.20 0.53 0.33 0.27 -0.06
Farmland 324 308 -16 24.86 24.80 -0.06 0.81 0.76 -0.04
Grassland 18 10 -8 24.90 25.31 0.40 0.04 0.03 -0.02
Water area 14 19 5 24.55 24.41 -0.15 0.03 0.05 0.01
Unused land 70 45 -25 24.41 24.55 0.14 0.17 0.11 -0.06
Construction land 31 35 4 25.11 25.61 0.50 0.08 0.09 0.01
Total 1444 1444 - 29.04 29.57 0.53 4.19 4.27 0.08
Pearl River
Water
Protection Forest conservation
50 forest
40
40 35
30
No forestry 30 Land conversion 25
engineering projects 20
20 15 Protected
Fruit trees 10
10 national forests
5
0 0
2005 2005
Provincial Nature
Reserve 2010
2010
(a) (b)
Fig. 3. Vegetation carbon density of areas influenced by (a) different conservation projects
and (b) different vegetation species (t.hm-2)
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Zhang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1657-1666
The vegetation carbon density of water Vegetation carbon density had improved in this
conservation forest and special use forest was study region as the result of recent implementations of
relatively high (more than 30 t hm-2) (Fig. 3). This control measures for dealing with rocky
could be attributed to the implementation of rocky desertification. Results of previous researches showed
desertification control measures. that the ecosystem service has improved since 2005 in
typical karst regions (Zhang et al., 2011).
3.1.2. Spatial distribution of vegetation carbon
Vegetation carbon density tended to be greater 3.1.3. Distribution pattern of vegetation carbon
in the western part of the study area than in the eastern In order to evaluate the pattern of vegetation
part of the study area (Fig. 4). Whereas vegetation carbon distribution in the study area, we used hot spot
carbon density was 28–35 t hm-2 in the western part, it analysis (spatial statistics, Getis-Ord General G). The
was 25–30 t hm-2 in the eastern part of the study area. resultant Z scores indicated whether features were
The distribution of vegetation carbon density was tightly clustered or widely scattered. This method
similar to that of vegetation net primary productivity works by examining each feature within the context of
(NPP) and vegetation coverage. The Previous research neighboring features. A feature with high vegetation
showed that mean vegetation coverage was more than carbon density was interesting but may not be a
60% and mean NPP was more than 1000 g m-2 in the statistically significant hot spot.
west, and vegetation coverage was less than 30% and To be a statistically significant hot spot, a
NPP was 100 g m-2 in the east in 2005 (Zhang et al., feature must have a high value and be surrounded by
2011). The rocky desertification land in Guangxi other features with high values as well. The local sum
China was the third largest region of rocky for vegetation carbon density and its neighbors is
desertification in China and was mainly distributed in compared proportionally to the sum of all features;
the counties of Pingguo, Dahua, Duan, Masan, when the local sum is much different from the
Donglan, Bama, and Fengshan (Yang, 2003). These expected local sum, and that difference is too large to
counties were mainly located in the eastern or middle be the result of random chance, a statistically
part of the study area. significant Z score was generated. The G statistic
The spatial variation of vegetation carbon returned in the dataset is a Z score.
density differed from the spatial distribution of Hot spot analysis of vegetation carbon density
vegetation carbon density. The vegetation carbon indicated a random pattern of distribution in 2005, but
density generally increased in the study area (Fig. 5). a highly clustered pattern in 2010 (Fig. 6). Large,
Between 2005 and 2010, the vegetation carbon density positive Z scores indicate intense clustering of high
of 16 counties remained at the same level and that of values (hot spot). Small, negative Z scores indicate
7 counties increased, including the counties of Napo, intense clustering of low values (cold spot). The Z
Pingguo, Longlin, Donglan, Leye, Huanjiang, and score was -0.273287 in 2005, but was 2.780397 in
Tiane. According to results of rocky desertification 2010. This indicates that the distribution pattern of
monitoring in 2005, there was 83,366.67 hm2 of rocky vegetation carbon density may have been impacted by
desertification in Pingguo county. In this county, the rocky desertification control measures.
Green for Grain program was carried out in areas .
totaling 45,333.33 hm2.
Fig. 4. Distribution of vegetation carbon density of samples in Guangxi, China in 2005 and 2010
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Factors affecting the pattern of vegetation carbon density in a karst region in northwest Guangxi, China
(a) (b)
Fig. 6. The general G for distribution of vegetation carbon in the study area in 2005 (a)and in 2010 (b)
3.2. Impact factor analysis of vegetation carbon vegetation species > vegetation type > degree of rocky
pattern desertification > humus layer thickness > area level >
vegetation coverage > soil thickness > slope position
3.2.1. The model > slope > aspect > altitude. The top 4 impact factors
The total number of samples was 1377, were land type, forest type, vegetation species, and
excluding non-vegetated samples. The effective vegetation type, and their significances were all above
number of samples was 1297 (80 test samples were 50%. The next 5 factors, rocky desertification degree,
excluded from analysis automatically). We used humus layer thickness, area level, vegetation
74.3% of the effective sample (964) for training and coverage, and soil thickness, had standardization
25.7% of the effective sample (333) to test the model. significances of 15–30%. The least significant impact
There were 13 impact factors in the input layer of the factors for vegetation carbon density were the 4
FRBN model in this study. The output layers were topography factors, and their standardization
vegetation carbon density, significance of impact significances were only 2–11%. This indicated that the
factors, and an error function (Table 2). There were impacts of topography factors on the distribution of
516 hidden layer units in the trained model. The vegetation carbon density were limited, and factors
activation function was softmax and the error function associated with human activities, such as land type,
was the sum of squares. forest type, vegetation species, and vegetation type
had relatively larger impacts on vegetation carbon
3.2.2. Results of impact factors on vegetation carbon density. Therefore, the ecological immigration
The rankings of the significance of the 13 program and the Green for Grain program had
factors that affect the spatial distribution of vegetation important impacts on the spatial distribution of
carbon density were (Fig. 7): land type > forest type > vegetation carbon density.
1663
Zhang et al./Environmental Engineering and Management Journal 17 (2018), 7, 1657-1666
Levels Information
Input layer Factors 1 Altitude
2 Aspect
3 Slope position
4 Slope
5 Soil thickness
6 Humus layer
7 Vegetation coverage
8 Land type
9 Vegetation type
10 Degree of rocky desertification
11 Vegetation species
12 Forest type
13 Area grade
Units 516
Hidden layer Units number 5a
Activation function Softmax
Output layer Dependent variable 1 Total_c (Vegetation carbon density)
Units number 1
Scale dependent variable rescaling method Standardization
Activation function Identical
The error function Quadratic sum
Fig. 7. The significance of impact factors for the distribution of vegetation carbon density
Table 3. The correlations between environmental factors and vegetation carbon density
AL AS SP SL ST HL VC LT VT DR VS FT AG
VC 202** -072** -160** 065* 323** 348** 246** .374** -.089** -205** 305** 236** 155**
VC: Vegetation carbon density, AL: Altitude, AS: Aspect, SP: Slope position, SL: Slope, ST: Soil thickness, HL: Humus layer, VC: Vegetation
coverage, LT: Land type, VT: Vegetation type, DR: Degree of rocky desertification, VS: Vegetation species, FT: Forest type, AG: Area grade. **
Significant at 0.01 level * Significant at 0.05 level
1664
Factors affecting the pattern of vegetation carbon density in a karst region in northwest Guangxi, China
Of the 13 impact factors investigated, 12 were karst areas should take priority over restricting the
significantly correlated with vegetation carbon density uncontrolled reclamation of these areas for economic
at the 0.01 level (Table 3). The remaining impact purposes in future land use practices. Controlling karst
factor (slope) was significant at the 0.05 level. Soil rocky desertification requires the optimization of land
thickness, humus layer, vegetation coverage, forest use structure. Although discontinuing all reclamation
type, vegetation type, altitude, and area level were activities in karst areas might not be possible, future
positively related to vegetation carbon density. The land reclamation projects need to be controlled and
pattern of vegetation carbon density was positively should be implemented after rigorous environmental
affected by these environmental factors. Slope aspect, impact assessment. More detailed studies of the
slope position, and rocky desertification were impacts of karst reclamation projects on ecosystem
negatively correlated to vegetation carbon density. As services provided in the southwest China were
the degree of rocky desertification increased, the necessary.
vegetation carbon density decreased (Hu et al., 2008). The present study has some limitations that
should be addressed in future studies. First, we did not
4. Conclusions consider the soil carbon pool, so the carbon capacity
of the whole forest system was not estimated. Second,
In this study, we used forest inventory data in the degree of uncertainty associated with the BEF
2005 and 2010 and geospatial technology to analyze method of vegetation biomass estimation requires
the spatial pattern of vegetation carbon and factors that further research. Finally, although the main impact
impact it in a typical karst area of northwest Guangxi, factors on the pattern of vegetation carbon density
China. The results showed that vegetation carbon were investigated using RBFN, more comprehensive
density increased from 29.04 t hm2 to 29.57 t hm2 and accurate investigation into the driving
between 2005 and 2010. The storage of vegetation mechanisms of the distribution of vegetation carbon
carbon increased 1.84% during the same period. density in karst regions are needed.
Spatial variation in vegetation carbon density
generally increased in the study area between 2005 Acknowledgements
and 2010. Hot spot analysis indicated a random This study was supported by National Natural Science
distribution in 2005, but a highly clustered distribution Foundation of China (31370484, 31470519, 41471445), he
in 2010. The impacts of factors associated with human National Key Basic Research Program of China
activities had relatively high impacts on the (2015CB452703), the National Key Re- search and
Development Program of China (2016YFC0502400), the
distribution of vegetation carbon density. The results Youth Innovation Team Project of ISA, CAS
indicated that the ecological immigration program and (2017QNCX_ZJ), and the Public Service Technology
Green for Grain program had important impacts on the Center, Institute of Subtropical Agriculture, Chinese
spatial distribution of vegetation carbon density. Academy of Sciences.
The distribution trend of vegetation carbon
density was similar to the distribution of vegetation. References
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1667-1677
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Bottled water (commonly called mineral) makes an important source of minerals for humans. Its consumption has been
systematically rising in the highly industrialized countries, even though not every water type has appropriate health properties. As
a result, drinking bottled water ought to be supported with understanding its qualities and physicochemical content.
The following article presents the results of the research into pH levels, electrical conductivity, selected inorganic anions (F-, Cl-,
NO3-, PO43-, SO42-), cations (Na+, NH4+, K+, Mg2+, Ca2+), metals and metalloids (Co, Ni, Cu, Zn, Cd, Pb, As, Cr, Mn, Ba, Rb, Sr,
Ag, Tl, V, U, Bi, Mo, Sb) of determined for the 48 bottled waters commercially available in Polish supermarkets. The methodology
optimization applied for the selected inorganic anions and cations as well as metals and metalloids helped to determine them on
the ultra-trace levels (<µg L-1). Inorganic ions were analyzed with the ion chromatography method. On the other hand, the ICP-MS
method was applied to analyze metals and metalloids. The validation parameters (limits of detection and quantification, recovery,
regression coefficients and coefficient of variation) were sufficient for the ultra-trace analysis. Due to the comparison of the
obtained results with the data provided by producers, numerous significant differences were observed.
Key words: bottled water, ion chromatography, inorganic ions, metals, trace elements
Received: May, 2013; Revised final: September, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: rajmund.michalski@ipis.zabrze.pl; Phone: +48 32 2716481; Fax: +48 322717470
Michalski et al./Environmental Engineering and Management Journal 17 (2018), 7, 1667-1677
nomenclature concerning the so-called “mineral transmission, blood coagulation and it is contained in
water” is equivocal (Diduch et al., 2011). The water is bones and teeth. Iron is essential for the transportation
usually classified as lowly, medium and highly and storage of oxygen in the organism. Zinc, copper
mineralized water. Curative, spring and table waters and manganese take part in the metabolic processes
are incorrectly included within this category. It is also while chlorides regulate blood pH. On the other hand,
possible to classify water either as carbonated or non- people suffering from the elevated blood pressure and
carbonated. kidney problems should not drink sodium-rich water
Researchers believe that nearly 20 properly as this element increases blood pressure and
concentrated minerals should be present in the human contributes to water retention and edemas. The
body to ensure proper functions of the human occurrence of those substances in water has usually a
organism and to maintain its homeostasis. Selected positive impact on human health. Unfortunately,
ions and metals/metalloids constitute these minerals consumers are not informed on the presence and
(Birke, et al., 2010). Some of them can be found in concentrations of harmful substances that may also
drinking and mineral water. Mineral waters usually occur in water.
contain sodium, potassium, magnesium, calcium, The maximum concentrations of the potentially
chlorides, sulfates, and several trace metals and harmful substances, i.e. those whose presence in water
metalloids. If the mineral contents in the organism are must be controlled in the Polish bottled waters, are
not appropriate, several imbalances may occur. Some listed in Annex 1 of the appropriate Directive
of them may lead to serious negative human effects (Regulation of the Minister of Health of 31 March
(WHO, 2005). When water is saturated with CO2, its 2011). The requirements concerning determination
taste becomes slightly tart, bacteria development is methods of the potentially toxic substances are given
stopped and its expiry date is longer. CO2 improves in Annex 2. Spring water undergoes the same standard
digestion and whets the appetite. As it enhances urine analyses as the natural mineral water. Spring water at
production and helps to detoxify the organism, it is the intake and in bottles must meet specific
advisable to drink after the physical effort. It should microbiological, chemical, chemicophysical and
be drunk in small portions as it is easily absorbed. On organoleptic requirements defined for drinking water.
the other hand, it is not recommended to people on a Bottled table water must meet microbiological
diet and or those who suffer from the peptic ulcer requirements.
disease. It must also be compliant with the regulations
Non-carbonated water is appropriate for people on the permissible levels of chemical components,
suffering from heartburn, flatulence and which are specifically defined for drinking water and
cardiovascular disorders. Depending on its source, whose excess could pose a threat for the public health.
mineral water contains various amounts of macro and Mineral components that can be used in the table water
microelements (e.g. Mg, Na, K, Li, Ca, Sr, Zn, Mn, Fe, production are: calcium chloride, magnesium chloride
Se, Cu, chlorides, sulfates, fluorides, iodides, or sulfate, chlorides, sulfates, or potassium and
bromides, and nitrates) that have a significant impact sodium bicarbonates. Their chemical purity must
on living organisms. Magnesium regulates heart work comply with the regulations for foodstuff. Bottled
and participates in the thermoregulation and nerve water can be admitted for consumption only when the
conduction. Potassium helps to control the water- concentrations of its constituents do not exceed the
mineral balance, decreases blood pressure and standards specified in various legal regulations. Table
regulates nerve and muscle activities. Calcium has 1 provides a list of such standards recommended both
impact on the muscle contractility, nerve impulse by the international and Polish institutions.
Table 1. Regulations and standards for bottled water intended for human consumption
1668
Analysis of commercially available bottled water in Poland
Ammonium - - - -
Antimony 0.005 0.006 0.006 0.005
Arsenic 0.01 0.01 0.01 0.01
Barium - 1 2 1
Beryllium - 0.004 0.004 -
Boron 1 - - 5
Cadmium 0.003 0.005 0.005 0.003
Chloride - 250 250 -
Chromium 0.05 0.05 0.1 0.05
Copper 1 1 1 1
Cyanide 0.07 0.1 0.1 0.07
Fluoride 5 - - 5
Iron - 0.3 0.3 -
Lead 0.01 0.005 0.005 0.01
Manganese 0.5 0.05 0.05 0.5
Mercury 0.001 0.001 0.002 0.001
Molybdenum - - - -
Nickel 0.02 0.1 0.1 0.2
Nitrate 50 50 50 50
Nitrite 0.1 1 1 0.1
Selenium 0.01 0.01 0.05 0.01
Silver - 0.025 0.1 -
Sodium - - - -
Sulfate - 250 250 -
Thallium - 0.002 0.002 -
Uranium - 0.03 0.03 -
Zinc - 5 5 -
Organic chemicals [µg/L)
Acrylamide - - - -
Benzene - 0.001 0.001 -
Pesticides (the sum
- - - -
of)
Phenols - 0.001 0.001 -
The analytical chemists must develop reliable Polish supermarkets. The samples were determined in
and conclusive methods for determinations a wide terms of the electrical conductivity, pH and contents
range of substances present in bottled waters in the of the main inorganic anions (F-, Cl-, NO3-, PO43- and
qualitative and quantitative ways. Determining SO42-), cations (Li+, Na+, NH4+, Mg2+ and Ca2+),
contents of inorganic and organic compounds is selected metals and metalloids (Co, Ni, Cu, Zn, Cd,
difficult, due to: low levels of individual compounds Pb, As, Cr, Mn, Ba, Rb, Sr, Ag, Tl, V, U, Bi, Mo, Sb).
present in samples; complex compositions (high
mineralization degree); interactions between the 2.2. Research methods
constituents present in samples; and possible changes
in the composition during transport and storage Electrical conductivity and pH were measured
resulting from reactions and potential desorption of with the multifunction CX-401 meter (Elmetron,
constituents from the packaging materials (Birke at al., Poland) with the ERH 111 electrode (Hydromet,
2010; Muntean and Mihaiescu, 2016). Therefore, it is Poland) and CD-2 conductivity detector (Hydromet,
necessary to use appropriate, sensitive and selective Poland). Inorganic ions were determined with an ion
methods, such as gas and liquid chromatography chromatograph (Metrohm, Switzerland) equipped
coupled with the mass spectrometry detectors (Jin et with: IC 818 pump, IC 837 eluent degasser, IC 830
al., 2010). The aim of the study was to test 48 mineral interface, IC 820 separation center, Valco injection
waters available in the Polish market to determine the valve, Metrodata 2.3 software, IC 838 automatic
contents of selected inorganic anions and cations, sample feeder and IC 819 conductivity detector. The
several dozens of trace elements, and the pH and Institute of Environmental Engineering of the Polish
electrical conductivity values. Additionally, the data Academy of Sciences in Zabrze, where analyses were
obtained from water producers and the research results carried out, has the laboratory that possesses the ISO
was compared whenever it was possible. 17025 ISO (ISO standard, 2005) accreditation of the
Polish Accreditation Centre (PCA), number 950.
2. Experimental The analytical conditions for the determination
of inorganic ions were:
2.1. Research subject and range − Anions (F-, Cl-, NO3-, PO43-, SO42-);
− Column-Metrohm Metrosep A Supp 3;
A number of 48 types of bottled water (mineral,
− Eluent-1.7 mM Na2CO3 + 1.6 mM NaHCO3;
table, spring and curative ones) were bought in a few
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Michalski et al./Environmental Engineering and Management Journal 17 (2018), 7, 1667-1677
− Eluent flow rate-0.85 mL/min; The ICP-MS spectrometer was optimized daily
− Injection volume-20 µL; with a 10-µg/L solution (Mg, Cu, Rh, Cd, In, Ba, Ce,
Pb, U) in 1% HNO3 Elan 6100 Setup/Stab./Masscal.
− Detection-suppressed conductivity;
Solution (Perkin-Elmer). An application enabling
− Cations (Li+, Na+, NH4+, K+, Mg2+, Ca2+); measurements of 53Cr, 55Mn, 59Co, 60Ni, 65Cu,
− Column-Metrohm Metrosep C3; 66Zn, 69Ga, 75As, 85Rb, 88Sr, 98Sr, 107Ag, 114Cd,
− Eluent-5 mM HNO3; 121Sb, 130Te, 138Ba, 205Tl, 208Pb, 209Bi, 238U
− Eluent flow rate-1.0 mL/min; isotopes was prepared. To determine Pb in a
quantitative way, a correction equation
− Injection volume-100 µL;
(Pb208=Pb208+Pb206+Pb207) was employed. The
− Detection-non-suppressed conductivity. analyses were carried out with the internal standard
The contents of selected metals and metalloids method, which was constituted by 10 µg/L Rh solution
were determined with the ICP-MS technique (ICP-MS introduced on-line with a peristaltic pump. All
Elan 6100 DRC-e Perkin Elmer spectrometer). The solutions and standards were made with the high-
ICP-MS spectrometer analytical parameters are given quality deionized Milli-Q-Gradient Millipore water
in Table 2. (Merck, Germany). 1 g/L single-element standard
solutions of Cd, Pb, Zn, Sb (Merck, Germany) and a
Table 2. ICP-MS spectrometer parameters certified multi-element standard solution were used
Parameter Settings for calibration. It was obtained by diluting 10 mg/L of
RF generator power [W] 1,125 the VI calibration solution (Merck, Germany).
Argon - plasma gas flow [L/min] 15 Calibration was verified with another certified multi-
Argon - nebulizer gas flow [L/min] 0.76-0.82 element standard, i.e. XXI (Merck, Germany). All
Argon - auxiliary gas flow [L/min] 1.15-1.16 standards were prepared daily with weight dilution.
Nebulizer cross-flow The method validation was performed on the basis of
Torch quartz the certified reference material - NIST 1643e Trace
Scanning mode peak hopping Elements In Water.
Dwell time [ms] 250
Sweeps/Reading 1 2.4. Sample preparation
Number of replicates 830
The carbonated water samples were degassed
2.3. Reagents in a sonic bath before the analysis. The examined
water samples were filtered through a 0.2-µm
NaHCO3 and Na2CO3 of analytical purity were nitrocellulose filter. Subsequently, they underwent
used to prepare the eluent for the inorganic anion chromatographic and ICP-MS analyses. Water
determinations. Ultrapure HNO3 (POCh, Gliwice, samples were acidified with the ultra-pure
Poland) was employed to prepare the cation concentrated nitric acid (Merck, Germany) before the
determination eluent. The properly composed and quantitative analysis with ICP-MS spectrometer.
concentrated eluents were prepared by weighing an
appropriate sample mass (or collecting appropriate 2.5. Validation of the applied analytical methods
volume) of a given substance. It was then solved in a
2-L laboratory flask. Standard solutions of specific Taking into consideration the inorganic ion
anions (F-, Cl-, NO3-, PO43- and SO42-) and cations determination methodologies, the calibration was
(Li+, Na+, NH4+, K+, Mg2+, Ca2+) were made with the performed in compliance with the ISO 8466-1 (ISO
Fluka reference materials (Steinheim, Switzerland). Standard, 1990). 7 standard solutions which contained
Their concentrations amounted to 1000 ± 2 mg/L. various concentrations of given ions were prepared to
Water used for standards and eluents preparation came define validation parameters for the methodology of
from the Millipore deionizer (Merck, Germany). Its the inorganic anion determination. Each solution went
electrical conductivity was < 0.05 μS/cm. Calibration through the chromatographic analysis three times. The
solutions were made by diluting appropriate standard obtained peak areas of the specific ions served to
solutions right before their application. All solutions calculate: standard deviation, variation coefficient,
were kept in glass or high-density polyethylene limits of detection and quantification, and correlation
(HDPE) containers at room temperature. coefficient. The results are given in Table 3.
Table 3. Validation parameters for the ion chromatographic method (inorganic ions)
Anions Cations
Parameter
F- Cl- NO3- PO43- SO42- Na+ NH4+ K+ Mg2+ Ca2+
Concentration range [mg/L] 0.2-2.0 1-100 0.2-20 0.2-20 1-100 1-100 0.2-2.0 0.5-50 1-100 1-100
Standard deviation [mg/L] 0.019 0.232 0.079 0.029 0.132 0.098 0.159 0.102 0.081 0.115
Coefficient of variation [%] 2.68 4.57 2.76 4.82 3.17 3.82 4.94 1.84 3.67 3.43
Limit of detection [mg/L] 0.012 0.064 0.048 0.019 0.131 0.091 0.027 0.095 0.17 0.211
Limit of quantification [mg/L] 0.036 0.192 0.144 0.057 0.353 0.273 0.081 0.285 0.51 0.633
Regression coefficient (r2) 0.999 0.999 0.999 0.999 0.999 0.999 0.998 0.999 0.999 0.998
1670
Analysis of commercially available bottled water in Poland
The ICP-MS method validation was performed The qualitative and quantitative ranges of
on the basis of the certified reference material - NIST substances regulated by the International Bottled
1643e Trace Elements in Water. The validation Water Association (IBWA) and U.S. Food and Drug
parameters are given in Table 4. Administration (U.S. FDA) are much greater than the
ranges defined by the European Economic
2. Results and discussion Community and Polish regulations. Fig. 1 presents
conductivity and pH values for the analyzed water
25 non-carbonated, 12 lightly carbonated and samples. The results of the selected inorganic anion (F-
11 carbonated waters constituted the analyzed group , Cl-, NO3-, PO43- and SO42-) and cation (Li+, Na+,
of the 48 water brands. The bottle volume was usually NH4+, Mg2+ and Ca2+) determinations are shown in
0.5 L or 1.5 L, however there were also 0.33-L and Figs. 2 and 3, respectively. The water producer values
2.5-L bottles. As it is apparent from the data in Table given in Figs. 2 and 3 are marked in red, and the black
1, the requirements of various organizations for the color concerns the analysis data.
quality of bottled waters are highly diverse.
Table 4. Validation parameters for metals and metalloids determined with ICP-MS
(a)
(b)
Fig. 1. Conductivity and pH values of the analyzed samples: (a) pH, (b) conductivity
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Michalski et al./Environmental Engineering and Management Journal 17 (2018), 7, 1667-1677
(a) (b)
(c) (d)
Fig. 2. Concentrations of common inorganic anions in the analyzed samples: (a) F-, (b) Cl-, (c) NO3- (d) SO42-
(a) (b)
(c) (d)
Fig. 3. Concentrations of common inorganic cations in the analyzed samples: (a) Na+, (b) K+, (c) Mg2+, (d) Ca2+
Figs. 4-8 present the determination results for Usually, only the content of the main inorganic anions
the selected metal and metalloid concentrations. and cations is given. The graphical comparison of the
Before deliberating over the trace elements, some study results for inorganic ions with the values
major elements should be discussed as they are usually reported by producers on the bottled water labels is
reported on the label. Manufacturers do not give the shown in Fig. 9.
information on the metal and metalloid In some cases, the same water type was
concentrations, which was the subject of this research. analyzed but either the bottles in which it was sold
1672
Analysis of commercially available bottled water in Poland
differed (samples 11 and 29, 28 and 33, 30 and 31) or water, while lower ones were observed for carbonated
the water was saturated with carbon dioxide to a water (Fig. 1). A classic example is sample 4. The non-
different extent (samples 4 and 15, 16 and 40, 34 and carbonated water version had pH of 7.91, but when
48). Most of the examined water types came from saturated with carbon dioxide (sample 43), it was only
Poland but some were produced in the Czech Republic 4.69. There were slighter differences in the case of the
(sample 24) or Lithuania (samples 17, 22, 30 and 31). lightly carbonated sample 34 (pH= 5.29) and
Multinational corporations, such as PepsiCo (samples carbonated sample 48 (pH=5.59). The average value
4, 15 and 43), Coca-Cola (samples 10 and 26) and of electrical conductivity for non-carbonated water
Nestle (samples 8, 11, 29 and 46), produce several was < 1,500 µS/cm. What seems interesting is the fact
popular water types in Poland. The obtained pH values that this value was the same for a few carbonated water
ranged between 4.69 (sample 43) and 8.28 (sample 9). types (Fig. 1). Samples 30 and 31 had definitely higher
Higher pH values were determined for non-carbonated values, which were > 5,000 µS/cm.
(a) (b)
(c) (d)
Fig. 4. Concentrations of V, Cr, Mn and Co in the analyzed samples: (a) V, (b) Cr, (c) Mn, (d) Co
(a) (b)
(c) (d)
Fig. 5. Concentrations of Ni, Cu, Zn and Ga in the analyzed samples: (a) Ni, (b) Cu, (c) Zn, (d) Ga
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Michalski et al./Environmental Engineering and Management Journal 17 (2018), 7, 1667-1677
(a) (b)
(c) (d)
Fig. 6. Concentrations of Rb, Sr, As and Mo in the analyzed samples: (a) Ru, (b) Sr, (c) As, (d) Mo
(a) (b)
(c) (d)
Fig. 7. Concentrations of Ag, Sb, Te and Ba in the analyzed samples: (a) Ag, (b) Sb, (c) Te, (d) Ba
(a) (b)
(c) (d)
Fig. 8. Concentrations of Tl, Bi, Pb and U in the analyzed samples: (a) Tl, (b) Bi, (c) Pb, (d) U
1674
Analysis of commercially available bottled water in Poland
10000
1000
100
Concentration
max
10 min
mediana
1
F- Cl- NO3- SO42- Na+ K+ Mg2+ Ca2+ pH
0,1
0,01
Ions
Fig. 9. Graphical comparison of the study results with the values reported on the bottled water labels. The first line applies
to the results obtained in the laboratory; the second (parallel) line concerns the value declared by the manufacturer
for a given parameter, if it was stated on the bottle label
The average contents of F- ions for most water The highest content of K+ ions (31.68 mg/L)
types did not exceed 0.5 mg/L (Fig. 2). Higher values, was observed for sample 25, even though the producer
close to the limit, were detected for samples 23 and 31. had declared the value of 37.5 mg/L. In most cases,
When comparing the obtained results with the data the K content did not exceed 10 mg/L and was usually
provided by producers, numerous significant the same as the one given in the label (Fig. 2). Calcium
differences were observed. In many cases, the and magnesium make important constituents of the so-
information given by producers (if specified in the called mineral water. Most producers indicated their
label) indicated lower values than those determined in contents but they were often higher than the
the research process. There may be multiple determined ones (Fig. 3). The highest Mg value
explanations of this fact. Nevertheless, the most (131.14 mg/L) was determined in sample 24 but it was
important one seems to be the fact that producers still much lower than the declared one (179 mg/L). A
present information (analyses are performed only similar situation was observed for Ca2+ ions. The
when necessary) which is very convenient as they contents did not exceed 100 mg/L in most water types.
possibly assume that the consumers are not be able to Interestingly, these values were usually lower than the
verify the actual data. The water composition at declared ones. The highest Ca2+ level was found in
intakes may change. It happens not only in emergency samples 33 (238.13 mg/L; producer data - 369 mg/L)
situations. Moreover, the cost of such analyses is high. and 34 (138.57 mg/L; producer data-129 mg/L).
The Directive allows for deviations from the declared Sample 5 is interesting in terms of the Ag
characteristic component contents that are not higher content. Its value reached 0.7 µg/L. The average value
than 20%. The average content of chloride ions did not for the remaining 45 samples was < 0.1 µg/L (Fig. 7).
exceed 20 mg/L (Fig. 2). However, an unusually high Similar deviations were observed for Te (sample 36,
value (over 1.0 g/L) was observed for samples 30 and Fig. 7), Ba (sample 36, Fig. 7), Tl (sample 21, Fig. 8)
31. The analyzed water types did not contain NO2- and Ga (sample 36, Fig. 5). The Pb content did not
ions, whereas the NO3- content ranged between 0.51 exceed 0.2 µg/L in most cases. However, it was higher
mg/L (sample 28) and 11.41 mg/L (sample 39). for samples 20 and 44 (Fig. 8). Bismuth was detected
Unfortunately, only one manufacturer presented the in 9 water types (Fig. 8). The highest Mo content was
declared nitrate ion content in the produced water (Fig. determined in sample 39, while the median value was
2). The PO43- content was not indicated in any label. < 0.5 µg/L (Fig. 6). Interestingly, U was detected in
Their contents varied between 1.28 and 1.56 mg/L and almost all water types (Fig. 8). The highest U value
only three examined water types had PO43- levels (approx. 1.2 µg/L) was observed for samples 3, 7 and
below the detection limit. 39. It did not exceed 0.2 µg/L in most remaining
The determined sulfate ion values did not differ samples.
as much as the Cl- ion contents and ranged between Most water types contained Cr (< 1 µg/L).
1.51 mg/L (sample 1) and 80.85 mg/L (sample 31). In However, its content for samples 44 and 46 was
most cases, the declared values of sulfate ions were approx. 20 µg/L (Fig. 4). A slighter diversification was
consistent with the calculated ones. Fig. 3 shows noticed for Sb. Its average concentrations ranged
results of the selected cation determinations. Lithium between 0.3 and 0.8 µg/L (Fig. 7). Its highest value
and ammonium ions (over the detection limit) were was observed for sample 45. Taking into account the
not present in any sample. The medium concentration quality requirements for bottled water, Table 5
of Na+ ions was lower than 20 mg/L for non- summarizes the number of times when the limit values
carbonated water. In the remaining cases, it varied for all the analyzed waters was exceeded.
between 50 and 270 mg/L (sample 36).
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Michalski et al./Environmental Engineering and Management Journal 17 (2018), 7, 1667-1677
In the literature, there are various examples of noticed that the mineral water composition may
modern analytical techniques (including ion change due to the long-term storage, which could be
chromatography) applied to examine mineral water investigated in the further research.
compositions. The studies concerned Slovenia (Gros
and Gorenc, 1994), South Korea (Jong-Hun, 1997), Abbreviations
Turkey (Guler, 2007; Guler and Alpaslan, 2009), Sri
Lanka (Herath et al., 2012), Italy (Dinelli et al., 2012), FDA-United States Food and Drug Administration
the USA (Saleh, 2008), or Arabic countries (Shomar, IBA-International Bottled Water Association
2012). The Polish mineral water was also investigated IC-Ion Chromatography
(Astel et al., 2014; Ciężkowski et al., 2007; Michalski, ICP-MS-Inductively Coupled Plasma Mass Spectrometry
ISO-International Standardization Organization
2003), but the research range was different from that NIST-National Institute of Standards and Technology
described in the following paper. In conclusion, there PCA-Polish Accreditation Centre
is a steady tendency related to the bottled water WHO-World Health Organization
consumption. Hopefully, the decision whether to drink
it and which one to drink could be facilitated by the References
findings provided in this article.
Astel A., Michalski R., Łyko A., Jabłońska-Czapla
4. Conclusions M., Bigus K., Szopa S., Sarapata A., Kwiecińska
A., (2014), Characterization of bottled mineral
In the following study, 48 various carbonated, waters marketed in Poland Using hierarchical
lightly carbonated and non-carbonated mineral waters cluster analysis, Journal of Geochemical
available in the Polish market were examined. The Exploration, 143, 136-145.
researchers determined the pH and electrical Birke M., Reimann C., Demetriades A., Rauch U., Lorenz
conductivity values, and the concentrations of the H., Harazim B., Glatte W., (2010), Determination of
main inorganic ions, metals and metalloids. major and trace elements in European bottled mineral
Most of the measured parameter values were water - analytical methods, Journal of Geochemical
below the permissible limits defined by the WHO, EU Exploration, 107, 217-226.
and Polish institutions. For the metal and metalloid Ciężkowski W., Chowaniec J., Górecki W., Krawiec A.,
Rajchel L., Zuber A., (2010), Mineral and thermal
contents, some values were exceeded in a few cases waters of Poland, Przegląd Geologiczny, 58, 762-773.
(antimony – 13 waters; barium – 8 waters; manganese Diduch M., Polkowska Ż., Namieśnik J., (2011), Chemical
– 3 waters; and arsenic – 3 waters). No value exceeded quality of bottled waters: A Review, Journal of Food
the permissible limits for the inorganic anions and Science, 76, 178-196.
cations. Nonetheless, it must be stated that the Dinelli E., Lima A., Albanese S., Birke M., Cicchella D.,
qualitative research range embraced a much larger Giaccio L., Valera P., De Vivo B., (2012), Comparative
number of analytes than that to which the regulations study between bottled mineral and tap water in Italy,
on mineral waters apply. Journal of Geochemical Exploration, 112, 368-389.
The comparison of the analysis results with the Gros N., Gorenc B., (1994), Ion chromatographic
determination of alkali and alkaline earth metals in
water label data showed a significant discrepancy mineral waters, Chromatographia, 39, 448-452.
between the declared and measured values (for ions, Guler C., (2007), Evaluation of maximum contaminant
metals and metalloids). Importantly, it should be levels in Turkish bottled drinking waters utilizing
1676
Analysis of commercially available bottled water in Poland
1677
1678
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1679-1683
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Industrial wastewater is of particular importance. In most wastewater treatments, physicochemical parameters are used to determine
the performances which are costly while protozoa can be used as less expensive biological indicators to determine the efficiency
of the treatment plant. The purpose of this study was to investigate the relationship between protozoa and physic-chemical
characteristics of the Abadan wastewater treatment industry.
Samples were collected from wastewater stabilization ponds in the Abadan industrial park. A total of 66 samples for biochemical
and chemical tests and protozoa counts were taken. The sites of sampling were influent of sewage and effluent from maturation
pond. For the parameters from influent, first 300 mL of samples was collected in depths of 0.1, 0.35 and 1 m and then mixed to
provide a composite sample. 300 mL sample was directly taken from the effluent.
The results of this study indicate that there is a positive relationship between the number and population percentage of amoeba and
mastigophora (flagellate) with BOD and COD, whereas is the negative relationship between sticking ciliates with BOD and COD.
Furthermore there is a positive relation between DO, the percentage, number of ciliates and amoeba population and there is a
correlation, with flagellate population. Increase of flagellate numbers is indicative of high effluent Kjeldahl nitrogen. There was
also an increase of input TSS and amoeba population percentage and a reduction of free ciliates numbers.
The type and abundance of protozoa in industrial wastewater treatment following biological methods is an indicator of the system
performance and effluent quality. This study shows the use of biological indicators can be used for monitoring as a much cheaper
alternative resulting in a better economy. It is also a good indicator for the detection of toxic materials entering the plant or refinery
and also its organic load shocks.
Key words: Abadan, amoeba, ciliate, industrial wastewater, mastighophora, monitoring, protozoa,
Received: August, 2013; Revised final: September, 2014; Accepted: September, 2014; Published in final edited form: July, 2018
∗
Author to whom all correspondence should be addressed: e-mail:mahdikargar1@gmail.com; Phone:+9817- 32431602; Fax: +981732431607
Bay et al./Environmental Engineering and Management Journal 17 (2018), 7, 1679-1683
presence of organisms such as protozoa, their Since the use of stabilization pond treatment
abundance and species diversity are associated with system is rapidly increasing specially in the tropical
quality, type of waste and emissions which can be used areas and due to the difficulties and the high cost of
to evaluate the performance of refineries or plants wastewater quality control testing, in this study, we
(Puigagut et al., 2005). In recent decades, regulatory have tried to propose appropriate solutions for
authorities in industrialized regions have also monitoring and evaluation of system's performance by
endeavored to improve water quality by advanced investigating the relationship between protozoan and
wastewater treatment (Eslami et al., 2016; Foley et al., physicochemical indicators.
2010). Therefore, evaluation and monitoring of
industrial wastewater treatment is necessary. The 2. Material and methods
reason that the use of stabilization ponds in
wastewater treatment are growing rapidly around the In this study, samples were collected from
globe and especially in tropical areas is due to their wastewater stabilization ponds in the Abadan
methods of function. industrial park. Abadan is a region with a warm
Since the type and frequency of biological climate in the Iran. The pool was made of concrete and
agents represent the performance of wastewater the average of raw sewage was 800 cubic meters per
treatment plants, therefore the possibility of day.
monitoring refineries performance by measuring The major wastewater productions were from
protozoan is possible. So due to its low cost and high soft drink industry, tuna fish and dairy and food
speed, this technique for monitoring of wastewater industry. The pond design specifications are given in
treatment plants have been recommended Table 1.
(Papadimitriou et al., 2010; Zhou et al., 2006). Variety
of studies such as the following research has reported 2.1. Sampling
the existence of protozoa in sewage in many countries.
Papadimitriou et al. (2010) studied protozoa as In this study the samples were collected within
an indicator of wastewater treatment efficiency in four months (during spring and summer). Eight
wetlands. They also showed there is a significant samples were collected per month through duplicate
relationship between the total coliform and sampling. A total of 66 samples for BOD, COD, TSS,
phosphorus removal rate and by increasing the TKN tests and protozoa counts were taken. DO and
removal of loaded organics, the number and variety of pH parameters were measured daily in place by a Hach
protozoa also increase. Dubber et al. (2011) in Ireland portable. The sites of sampling were influent of
during the study of SBR reactors evaluated the effect sewage and effluent from maturation pound. For the
of anoxic and anaerobic process on protozoa parameters from influent, 300 mL of samples were
population. They measured chemical and biochemical collected in a depth of 0.1, 0.35 and 1 m and mixed
parameters such as BOD, COD, TKN in four different that to provide a composite sample and 300 mL
times of the reactor use and also determined the sample was taken from the effluent directly.
abundance and diversity of protozoan. Their studies
showed that prolonged anoxic and anaerobic 2.2. Determination of physicochemical parameters
processes were reducing the entire population of
protozoa in the reactor. Chen et al. (2005) conducted For measuring BOD, COD and TKN, the
a survey on wastewater sturgeon fish in south of samples were filtered by fiber glass filters. In order to
China. They used protozoa as bio-indicators to deposit determine the amount of TSS the effluent was passed
effluent quality assessment. They found that the through Whatman filter and then dried at 103 to 105°C
protozoa populations are dependent on distribution and the weight difference filter was calculated. All
and pollution rotation period that this property can be physic-chemical parameters were measured according
used as a treatment bio-indicator. They also reported to standard methods (APHA, 2005).
that more than 80 percent of the 216 ciliates species
are omnivorous (Chen et al., 2005). Perez-Uzet al. 2.3. Protozoan population monitoring
(2010) studied the likely assessment of bio-indicators
to determine the performance of treatment in advanced For protozoa counting after stirring the
wastewater treatment systems. sample with distilled water, the sample was prepared
Their results showed that the reduction of diluted in a ratio of 1 to 3. Then 1 mL of the diluted
nitrogen removal efficiency increased ciliates sample was placed on counting slide of Sedgwick-
population or the high existence of Ciliates resulted in Rafter and observed with optical microscope with
low efficiency in system nitrogen removal. Poole 100X enlarging and protozoa were counted.
compared the species of parasites where they operated Field method was used to count protozoa and
activated sludge systems in which nitrification and 10 randomly selected fields and protozoa counts were
operating systems were not performed and indicator performed in four major categories of moving ciliates
organisms were introduced to the system (Poole, (free), sticking ciliates, amoeba and mastigophore
1984). The organic load entering relation to plant and (flagellate). This count for each sample was repeated
protozoa population were studied by Salvador and twice and the results were calculated based on the
Gracia (1993) in Spain. number of mL from Eq. (1) (APHA, 2005).
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Survey of industrial wastewater treatment performance with biological monitoring of protozoa
2.4. Data analysis 3.1. Relationship between BOD and COD with
protozoa
Data were analyzed by using SPSS v.18
software. For data interpretation, the mean and The results of this study indicate that there is a
standard deviation (mean ± SD) were used. Data positive relationship between the number and
normality was evaluated by Shapiro-Wilk test and for population percentage of amoeba and mastigophore
normal data the average. Comparing of input and (flagellate) with BOD and COD whereas is negative
output variables paired T-test was used. The Pearson the relationship between sticking ciliates with BOD
correlation was used to determine the correlation and COD. Furthermore the results demonstrated that
severity and linear regression models to determine the there is a positive relation between DO, the
relationship between variables studied in input and percentage, number of ciliates and amoeba population
output places. P-value of 0.05 was considered as and there is a correlation with flagellate population.
statistical significance for all tests.
Table 2. The important genus or species of protozoa that were found in wastewater treatment plants
Table 3. The quality and statistical indicators of the raw wastewater entering the anaerobic treatment pond in industrial park
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Bay et al./Environmental Engineering and Management Journal 17 (2018), 7, 1679-1683
Table 4. The quality and statistical indicators of the final effluent in established pond of the industrial park of Abadan
Table 5. The quality and biological indicators of the effluent entering the maturation pond of industrial park of Abadan
Table 6. The quality and biological indicators in final effluent of industrial park of Abadan
In other words, with the increase in flagellate research findings were consistent with Puigagut and
population it can be expected that the output effluent colleagues on nitrogen amount and total population of
quality will not be satisfactory and with the increase in ciliates (Puigagut et al. 2005).
number of attached ciliates it can be expected to
achieve satisfactory effluent quality. These findings 3.4. Relationship between TSS and Protozoa
are consistent with Dubber reports on the terms of
ciliates populations. The Relationship between incoming suspended
According to Dubber’s study there is a direct solids and protozoa population showed that there is a
relationship between the reduced amount of BOD and significant relation between this parameter and the
organic matter with the total population of protozoa percentage of amoebas population and the numbers of
(Dubber et al.2011). ciliates (P<0.05) which both have direct and inverse
relationship. This means that by increasing input TSS,
3.2. Relationship between DO concentration and the amoeba population percentage and free ciliates
Protozoa numbers were reduced. Moreover the results of input
TSS measurements have a direct correlation with
The results of this study show that there is a flagellate population.
direct relation between DO and the number and
percentage of Ciliates and Amoeba population and 4. Conclusions
also a correlation with flagellate population (P<0.05).
But the highest correlation is related to the association Changes in the abundance of biologic indicator
of DO and attached (sticking) ciliates. The existence species of the microbial community can give advance
of high dissolved oxygen can cause spreading in warning of impending problems in wastewater
attached ciliates population. treatment plant. Changes in operating conditions of
the wastewater treatment plant may cause rapid
3.3. Relationship between Kjeldahl nitrogen and changes in the structure of the communities of
protozoa microscopic organisms, and it is hoped to work
towards an understanding of how to regulate the
Since Kjeldahl nitrogen amounts in sequential operating conditions to maintain an ideal balanced
wastewater ponds is decreasing, comparing Kjeldahl community of protozoa.
nitrogen amounts with the number and percentage of The type and abundance of protozoa in
ciliates and also the number of amoeba results in a industrial wastewater treatment working on biological
direct relationship. Whilst, total Kjldal nitrogen in methods are the indicator of system performance and
pond and the final effluent has a significant direct effluent quality. Among protozoa, the presence of
correlation with the number of flagellate (P<0.05). In certain variety of ciliates is considered highly
other words, increasing of flagellate numbers is important compared to other species. This study
indicative of high effluent Kjeldahl nitrogen. The shows increase in the ciliates population reduced
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Survey of industrial wastewater treatment performance with biological monitoring of protozoa
concentrations of BOD, COD, TSS and nitrogen in Eslami A., Moradi M., Ghanbari F., Vatanpour V., (2016),
output wastewater effluent and leads to satisfactory Electrochemical catalytic degradation and
quality of wastewater. Whereas the increasing in the biodegradability enhancement of real textile
number of amoeba and flagellates indicates the wastewater by anodic and cathodic reactions,
Environmental Engineering and Management Journal,
sewage treatment is incomplete. It is also 15, 2319-2326.
demonstrated that there is susceptibility between DO Foley J., Haas D., Hartley K., Lant P., (2010),
concentration and flagellate population in which by Comprehensive life cycle inventories of alternative
increasing dissolved oxygen, the number of flagellate wastewater treatment systems, Water Research,44,
decreases. 1654-166.
Thus, it can be deduced from the findings of Luna-Pabello V.M., Mayen R., Olevera-Viascan V.,
this study that low cost biological indicators can be Saavedra J., Duran de Bazua C., (1990), Ciliated
used for monitoring and hence result in a better Protozoa as Indicators of a Wastewater Treatment
economy especially in tropical area. Furthermore it is System Performance, Biological Wastes,32 , 81-90.
Madoni P., (1994), Estimated of ciliated protozoa biomass
also a good indicator for the detection of toxic in activated sludge and biofilm, Bioresource
materials entering the plant or refinery and also its Technology,48, 245-249.
organic load shocks. Especially in industrial Papadimitriou C.A., Papatheodoulou A., Takavakoglou V.,
wastewater because of the cost of testing is expensive, Zdragas A., Samaras P., Sakellaropoulos G.P.,
also in developing countries and technical problems of Lazaridou M., Zalidis G., (2010), Investigation of
the analysis, the use of bio-indicators for operating protozoa as indicators of wastewater treatment
plant can be very helpful. efficiency in constructed wetlands, Desalination,250,
378-382.
Perez-Uz B., Arregui L., Calvo P., Salvado H., Fernandez
Acknowledgments
N., Rodrıguez E., Zornoza A., Serrano S., (2010),
Special thanks to the head of environmental health research
Assessment of plausible bio indicators for plant
center and company officials of industrial park in Khuzestan
province as well as Dr. Bijan Bina and Dr. Jafarzadeh for performance in advanced wastewater treatment
their efforts in providing research facilities and their systems, Water Research,44, 5059-5069.
Popescu M., Koncsag C.I., Birladeanu A.I., (2009),
guidance.
Monitoring of PAHs in refinery effluents,
Environmental Engineering and Management Journal,
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Poole J.E.P., (1984). A study of the relationship between the
APHA., AWWA., WEF., (2005), Standard Methods for the mixed liquor fauna and plant performance for a variety
Examination of Water and Waste Waters, 21st Edition, of activated sludge sewage treatment works, Water
USA, American Public Health Association. Research,18, 281-287.
Chen Q., Xu R., Tam N., Cheung S., Shin P., (2008), Use of Puigagut J., Salvado H., Garcia J., (2005), Short-term
ciliates (protozoa: Ciliophora) as bioindicator to assess harmful effects of ammonia nitrogen on activated
sediment quality of two constructed mangrove sewage sludge microfauna, Water Research,39, 4397-4404.
treatment belts in Southern China, Marine Pollution Salvado H., Gracia M.P., (1993), Determination of organic
Bulletin, 57, 689–694. loading rate of activated sludge plants based on
Dubber D., Gray N.F., (2011), The effect of anoxia and protozoan analysis, Water Research, 27, 891-895.
anaerobia on ciliate community in biological nutrient Zhou K., Xu M., Dai J., Cao H., (2006), The microfauna
removal systems using laboratory-scale sequencing communities and operational monitoring of an
batch reactors (SBRs), Water Research, 45, 2213-2226. activated sludge plant in China, European Journal of
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1683
1684
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1685-1692
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
The reuse of sewage sludge will be increasing in the future, with expansion of sewerage works and advanced sewage treatments.
During anaerobic digestion of sewage sludge from wastewater treatment plants the humification of organic matter will have an
important effect on the physico-chemical forms of heavy metals. The aim of our paper was to investigate mobility of zinc from
dried anaerobic sludge (DANS) from municipal wastewater treatment plant (WWTP) via single step (simultaneous) extraction
protocols. We tried to optimize extraction process as a function of amount of sludge biomass, concentration of extracting agent and
reaction time. The three parameters namely 0.55 g of anaerobic sludge, 50.5 mmol/dm3 HCl as extracting agent and 3 hour of
reaction time were chosen as center points. The experimental data on extractable Zn concentration (cZn) from DANS were obtained
by stripping chronopotentiometry and fitted into a quadratic polynomial model using multiple regression analysis. The optimal
extraction parameters were studied using experimental Box-Behnken design under response surface methodology (RSM). Results
showed that interaction effect of reaction time and amount of biomass to Zn extraction is minimal, but in combination with the
concentration of HCl significant increase of extractable zinc from DANS was detected. The maximum metal solubilization was
obtained at 0.55 g of DANS, 100 mmol/dm3 HCl and 5 hour of reaction time. Correlation among to predicted and experimental
data showed ability to reducing the number of total experiments from 39 to 17.
Received: August, 2013; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: fristak.vladimir.jr@gmail.com; Phone: +421335921459; Fax: +421335921403
Frišták et al./Environmental Engineering and Management Journal 17 (2018), 7, 1685-1692
component from sewage sludge into environment. The main aim of paper was to describe the
Sludge as an organic matter rich material with low effect of amount of sludge biomass, concentration of
toxic metals concentration can be utilized as fertilizer extracting agent and reaction time on zinc extraction
and soil conditioner in agriculture (Frišták et al., from DANS. Therefore, three level three factor (33)
2013). The benefit of biosolids application to land is quadratic polynomial model under Box-Behnken
to supply and recycle organic matter and nutrients design (BBD) was developed to predict the
(Martinez et al., 2003). The ecological and relationship between the experimental variables on the
toxicological effect of potentially toxic metals from total of zinc extracted (response variable) from
sewage sludge on agro-ecosystem is directly related to DANS. Obtained results are useful for application of
their partitioning between mobile and complexed anaerobic sludge as a soil amendment and conditioner.
species in the highly heterogeneous soil system
(Merrington et al., 1997). Many factors influence this 2. Material and methods
partitioning of toxic metals in soil amended with
sludge including the soil and sludge characteristics. 2.1. Preparation of sludge sample
The extraction of toxic metals from the sewage
sludge, before land application, is therefore a Municipal anaerobic sludge was obtained from
necessary step for reducing the adverse effects of mechanical-biological WWTP in Zeleneč (Slovak
biosolids application (McBride, 2003). For extraction Republic). After repeated washing in deionised water,
of heavy metals from sewage sludge a variety of single sludge biomass was oven dried at 105°C for 48 h,
and sequential extraction techniques can be used. In ground, sieved and stored in closed bottles at 22°C.
recent years there has been a great interest for the For extraction experiments fraction < 2 mm was used.
methods of toxic metals removing from sewage sludge
(Babel and Dacera, 2006; Frišták et al., 2012a; 2012b; 2.2. Extraction experiments
Marchioretto et al., 2002). These methods can be
clasified as a: chemical extraction, using inorganic Leachable and bioavailable fractions of zinc
acids (Marchioretto et al., 2002), organic acids from dried anaerobic sludge (DANS) were obtained
(Veeken and Hamelers, 1999), alkaline reagents after one-step extractions with HCl of variable
(Hsiau and Lo, 1997), chelators (Lo and Chen, 1990), concentrations. HCl as extraction agent with highest
bioloeaching (Pathak et al., 2009), electroreclamation extraction efficiency for Zn and anaerobic sludge was
(Wang et al., 2005) and advanced biosolids treatment used (Frišták et al. 2012b).
methods (Dewil et al., 2006). Chemical extractions as Extraction experiments were carried out by
a tool for Zn removal from sewage sludge were suspending of DANS (10 g/dm3 d.w.) in 10 cm3 of
extensively descripted in work Shiro and Tahei extraction agent. Flasks were agitated on a reciprocal
(2000). Zhang and Zhang (2012) showed the shaker (150 rpm) at 22°C. After centrifugation (5 min,
application of [S, S]-EDDS as extracting agent for Zn 5000 rpm) the supernatant was obtained and
extraction from sewage sludge. Zn extraction by concentration of zinc was determined by
organic acids provides some disadvantages (Babel and electrochemical analysator. All experiments were
Dacera, 2006). Our previous paper (Frišták et al., carried out in triplicates. Amounts of DANS,
2012b) found out, that inorganic extractants such as concentrations of HCl and reaction time were set
hydrochloric or nitric acid solutions remove the Zn according to experimental design methodology.
from sludge structures with highest efficiency. For
differences in biosolids structures, extracting 2.3. Experimental design and optimization of zinc
parameters and using only limited number of chemical extraction
extractants, it is difficult to perform comparison
among experimental data and find out the optimal Variable number of factors such as reaction
conditions of extraction protocols. time, amount of DANS and concentration of HCl as
In the paper, we tried to optimize chemical extracting agent can significantly affect the total zinc
extraction efficiency of zinc from dried anaerobic extraction efficiency. Therefore, Box-Behnken design
sludge (DANS) of municipal wastewater treatment (BBD) under RSM was used to identify the
plant (WWTP) via single step (simultaneous) relationship between the response variable (total
extraction protocols using stripping extracted zinc concentration) and the experimental
chronopotenciometry. The optimal extraction variable (amount of sludge biomass, concentration of
parameters were studied using experimental Box- extracting agent and reaction time).
Behnken design under response surface methodology The statistical software Statgraphics Centurion
(RSM). RSM is a collection of mathematical and XV (StatPoint Inc., USA) was used for the
statistical techniques useful for analyzing the effects experimental design, data analysis, quadratic model
of several independent variables on the response (Box building, graph plotting (three-dimensional response
and Draper, 1987). The methodology is more practical surface and contour plots) and to estimate the
as it arises from experimental methodology which responses of amount of sludge biomass, concentration
includes interactive effects of the variables and, of extracting agent and reaction time. The range of
eventually, it depicts the overall effects of the experimental variables and their units and notation are
parameters on the process (Bas and Boyaci, 2007). indicated in Table 1.
1686
Application of response surface methodology (RSM) for optimization of zinc extraction from anaerobic sewage sludge
Coded levels
Independent variables Symbols Unit
-1 0 +1
mDANS A mg 100 50 1000
cHCl B mmol/dm3 1 50.5 100
T C h 1 3 5
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Frišták et al./Environmental Engineering and Management Journal 17 (2018), 7, 1685-1692
3.2. Optimization of zinc extraction protocol – RSM model, suggests the statistical significance of the
application model equation, as it is evident from the Fisher`s F-
value (86.19) with a low probability value (p-value
Generally, sewage sludge as an organic matter- <0.0001).
rich material contains larger concentration of heavy
metals than the background values found in soil. c Zn = +5.49265 + 4.06566.10 −3 × m DANS − 0.13619 ×
Application of sludge as soil conditioner can gradually c HCl − 2.42866 × t + 1.01010.10 − 4 ×
raise the total toxic metal concentration of soil (Smith, (2)
et al., 2009). Although, metals present in compost m DANS × 4 + 8.33333.10 − 4 × m DANS × t + 0.032828 ×
exist in relatively resistant forms, these are more labile c HCl × t − 5.55556.10 −6 × m DANS 2 +
in the environment of soil matrix. Zinc is the element
1.17335.10 −3 × c HCl 2 + 0.21875 × t 2
which the largest increase in labile forms is reported
when sewage sludge is applied to soil, particularly
under acidic soil conditions (Planquart et al., 1999). A large F-value indicates that most of the
Eneji et al. (2003) found that Zn availability increased variation can be explained by a regression equation
during anaerobic digestion of organic wastes. One of whereas a low p-value indicates that the model is
the main approaches to study the behaviour of toxic considered to be statistically significant (Myers and
metals in sewage sludge has been to use chemical Montgomery, 2002). The goodness of fit was also
extraction protocol to remove metals bound in evaluated by the correlation coefficient (R2) between
different defined phases (He et al., 1992). Parameters the model predicted and experimental values.
of extraction protocols are variable and it is difficult to Coefficient R2 indicates the statistically signification
find out the optimal conditions. For that reason, a Box- of model used. Both values R2 and adjusted R2 are
Behnken design under RSM was used to analyze closed to 1 and indicate a high correlation between the
interactive effect of the amount of sludge biomass, observed and the predicted values (Garg et al., 2008).
concentration of extracting agent and reaction time on On the basis of this investigation, the
total extractable zinc concentration from DANS. The relationship between the independent variables
advantage of the RSM method is the minimization of (amount of sludge biomass, concentration of
the number of experiments and time needed. A total of extracting agent and reaction time) and the response
17 runs were used to optimize the extraction process (total extractable zinc concentration from DANS) can
parameters (Table 2). Each of experiment was be explained according to the regression model. cZn is
performed in triplicate. attributed to the independent variables and only about
Using multiple regression analysis, the second 1.90 % of the total variation cannot be explained by
order polynomial model which characterizes the the model. Regression analysis (Table 3) shows that
relationship between total extractable zinc the square as well as the interaction effects of the
concentration cZn from DANS and actual studied independent experimental variables were significant
variables can be written as given by (Eq. 2). The (p<0.0001). The adequacy of quadratic model was
analysis of variance (Table 3), which is a statistical tested also through the correlation between calculated
technique that subdivides the total variation in a set of and experimental values for total extractable zinc
data into components associated with specific sources concentration from DANS, which is shown in
of variation to test hypotheses on the parameters of the scattered plot (Fig. 1).
Table 3. BBD matrix, the experimental and predicted values of total extractable Zn concentration cZn from DANS for three
independent variables (A: mDANS (mg); B: cHCl (mmol/dm3); C: t (h))
1688
Application of response surface methodology (RSM) for optimization of zinc extraction from anaerobic sewage sludge
p-value
Source Sum of squares DF F value
Prob>F
Model 554.06 9 86.19 <0.0001
A 50.00 1 70.00 <0.0001
B 364.50 1 510.30 <0.0001
C 32.00 1 44.80 0.0003
AB 20.25 1 28.35 0.0011
AC 2.25 1 3.15 0.1192
BC 42.25 1 59.15 0.0001
A2 5.33 1 7.46 0.0293
B2 34.80 1 48.72 0.0002
C2 3.22 1 4.51 0.0713
Lack of fit 5.00 3 0.00
Pure Error 0.000 4 0.00
Total 559.06 16
R2 0.9754 R2adj 0.98
From correlation between predicted cZn pred and not confirmed the statistical significance. For
experimental cZn exp values of zinc extraction from interpretation of the interaction coefficients can be
DANS is evident that the regression model can used three-dimensional plots of regression model.
represent the experimental extraction data well. On the Such three-dimensional surfaces can provide useful
basis of the evaluation of ANOVA outputs, the information about the behaviour of the extraction
statistical significance of a quadratic model for the system within the experimental design, facilitate an
response was confirmed and it can be concluded that examination of the effects of the experimental factors
the model can be used for further analysis of effect of on the responses and contour plots between the factors
process variables (Frišták et al., 2012a; Remenárová (Ahmad and Hameed, 2010).
et al., 2012). Fig. 2 shows that the extraction process of zinc
is strongly influenced by the amount of biomass and
concentration of exracting agent. Effect of sludge
amount in combination with reaction time was less
significant. According to identified relations and
predicted values we found out that the extraction
process of zinc from DANS has highest efficiency at
following parameters: the amount of sludge biomass
550 mg, the concentration of extracting agent (HCl)
100 mmol/dm3 and contact time 5 h. Correlation
among to predicted and experimental data showed
ability to reducing the number of total experiments
from 39 to 17. Mannan et al. (2007) showed the
usefulness of RSM methods and Box-Behnken design
for the optimization of process parameters of
bioconversion of activated sludge by Penicillium
corylophilum.
Fig. 1. Correlation between predicted cpred and Response surface method (RSM) appears to be
experimental cexp values of zinc extraction from DANS a better tool for the evaluation of difficult studies of
multi-component systems than the simple
As was already mentioned above, the aim of extrapolation from single-component systems in
this paper was to optimize the parameters of zinc sorption process of heavy metals by dried activated
extraction protocol, namely: the amount of sludge sludge (Remenárová et al., 2012). Zhang and Zhang
biomass, concentration of extracting agent and (2012) showed the application of [S,S]-EDDS as
reaction time. The statistical significance of each extraction agent of Zn from mixed sludge with
coefficient was determined by p-values shown in effectivity more than 65%. Authors described equally
Table 3. Lower p-value indicates a higher significance the possibility of Zn extraction from this type of
of the parameter. sewage sludge by EDTA with high efficiency.
Our results demonstrate the statistical However extraction of Zn from sewage sludge
significance of linear quadratic coefficients: A (F = requires optimization of reaction conditions (Babel
70.00, p <0.0001), B (F = 510.30, p <0.0001) and C and Dacera, 2006). Our paper showed the RSM as
(F = 44.80, p = 0.0003), and quadratic coefficients A2 useful statistical tool for optimization of Zn extraction
(F = 7.46, p = 0.0293), B2 (F = 48.72, p = 0.0002). process by HCl with comparable removing effect such
Other quadratic form C2 (F = 0.37, p = 0.0713), as well as extraction by H3PO4 published in paper Zhang and
as interaction coefficient AC (F = 3.15, p = 0.1192) Zhang (2012).
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Frišták et al./Environmental Engineering and Management Journal 17 (2018), 7, 1685-1692
Fig. 2 Three-dimensional surface plots of the combined effect of (A) reaction time (t) and amount of DANS (m); (B)
concentration of extracting agent (cZn) and amount of DANS (m); (C) reaction time (t) and concentration of extracting agent (cHCl)
on total extractable zinc concentration (cZn) from DANS (VHCl = 10 cm3, 22°C, 150 rpm)
1690
Application of response surface methodology (RSM) for optimization of zinc extraction from anaerobic sewage sludge
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Frišták et al./Environmental Engineering and Management Journal 17 (2018), 7, 1685-1692
design study, Journal of the Taiwan Institute of Veeken A.H.M., Hamelers H.V.M., (1999), Removal of
Chemical Engineers, 43, 433-443. heavy metals from sewage sludge by extraction with
Shiro Y., Tahei T., (2000), Principle and process of heavy organic acids, Water Science & Technology, 40, 129-
metal removal from sewage sludge, Environmental 136.
Science &Technology, 25, 113-118. Wang C., Hu X., Chen M.L., Wu Y.H., (2005), Total
Shrivastava R., Upreti R.K., Chaturvedi U.C., (2003), concentration and fractions of Cd, Cr, Pb, Cu, Ni and
Various cells of the immune system and intestine differ Zn in sewage sludge from municipal and industrial
in their capacity to reduce hexavalent chromium, FEMS wastewater treatment plants, Journal of Hazardous
Immunology &Medical Microbiology, 38, 65-70. Materials, 119, 245-249.
Smith K.M., Fowler D.G., Pullket S., Graham N.J.D., Zhang L., Zhang H., (2012), Zinc extraction from sewage
(2009), Sewage sludge-based adsorbents: A review of sludge with [S,S]-EDDS, Journal of Central South
their production, properties and use in water treatment University, 19, 3546-3550.
applications, Water Research, 43, 2569-2594.
1692
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1693-1700
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Atmospheric concentrations of PM2.5 and PM10 were measured in Beirut, Lebanon, for a period of 12 months. The daily average
concentrations of PM10 and PM2.5 were found to be 51.3 ± 33.1 and 30.3 ± 9.4 µg.m−3, respectively, with corresponding maximum
values of 359.7 and 208.6 µg.m−3. The annual average concentrations of PM10 and PM2.5 exceeded the World Health Organization’s
standards by 150% and 200%, respectively. The mean concentration of coarse particles (PM10–2.5) was found to be 41% of the
average PM10, suggesting that the site was also influenced by re-suspended surface dust and soil. The mean PM2.5/PM10 ratio for
the entire study period was 0.61 ± 0.12. This indicates that in Beirut, PM2.5 accounts for about 61% of PM10. Such a large fraction
of fine particles could have considerable effect on health; thus, it is necessary to quantify its impact. Daily concentrations of PM10
and PM2.5 exceeded the upper threshold limit on 133 and 129 days, respectively, representing 39% and 38% of the entire sample,
respectively. These findings indicate the important role dust events play within this area. Concentrations of PM2.5 were highly
correlated with NO2, whereas concentrations of PM10 and PM10–2.5 were not associated with any gaseous pollutant. Regression
analysis showed that 93% of PM2.5 and 43% of PM10 particle mass concentrations were derived from road traffic exhaust in Beirut.
Key words: air quality, dust event, health effect, particulate matter, regression analysis
Received: October, 2013; Revised final: September, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: wehbeh.farah@usj.edu.lb; Phone: +96 1142 1374; Fax: +96 1453 2657
Farah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1693-1700
Since the early 1990s, thousands of studies admissions to all hospitals in New Haven
have reported associations between airborne particles (Connecticut) and Tacoma (Washington) for persons
and a range of respiratory and cardiovascular diseases aged 65 years and older with respiratory diseases
and even death. For example, Schwartz (1994) (ICD-9 460-519). The results showed significant
reported an association between concentrations of association between the three studied pollutants (SO2,
daily total suspended particles and the risk of mortality PM10, and O3) and admissions to hospitals of the older
in Ohio, whereas Dockery et al. (1993) associated persons with respiratory problems; however, the
premature death in six eastern US cities with fine strongest evidence of an independent association was
atmospheric particulates (inhalable particles). for PM10. These significant relationships are also
Similar results have been reported in found for children, another group vulnerable to the
association with fine particles, but this time with effects of air pollution and fine particles in particular
regard to hospital admissions. In Birmingham (UK), a (Brauer et al., 2002; Braun-Fahrlander et al., 1997;
study in 1997 showed that following every 10 μg.m−3 Penard-Morand et al., 2005).
increase in concentration of PM10, respiratory and These findings underline the importance of
cerebrovascular hospital admissions increased by ambient PM and for need to monitor PM10 and the
2.4% and 2.1%, respectively (Wordley et al., 1997). associated fraction of PM2.5. In this paper, we explore
Another study revealed an association between the the annual and daily average concentrations of PM10
short-term increase in hospital admission rates and and PM2.5 and compare them with the corresponding
PM2.5 for all health problems except injuries WHO standards to estimate their effects on health. We
(Dominici et al., 2006). The largest association also determine the relative contributions of fine,
regarded heart failure, which had a 1.28% (95% PM2.5, and PM10–2.5 to total inhalable particles (PM10),
confidence interval; 0.78–1.78) increase in risk per 10 and discuss the relationship between levels of PM and
μg.m−3 increase in same-day PM2.5 concentration. concentrations of other gaseous pollutants.
Dominici et al. (2006) concluded that short-term
exposure to PM2.5 increased the risk of hospital 2. Material and methods
admission of people with cardiovascular and
respiratory diseases. 2.1. Study area
Other studies have also found relationships
between low levels of fine particles and hospital Beirut, Lebanon’s capital, is located on the
admissions of people suffering respiratory symptoms. eastern coast of the Mediterranean Sea (Fig. 1),
In Vancouver, Canada, where pollutant levels are covering an area of 20.8 km2 and it has a population
relatively low, Chen et al. (2004) confirmed a positive of about 361,366 inhabitants (CAS, 2007). Beirut is
relationship between PM10, PM2.5, and PM10–2.5 and characterized by two hills that lie to the north and west
emergency hospitalizations for Chronic Obstructive of the city, separated by a thalweg. Each hill rises
Pulmonary Disease in people aged over 65 years. about 100 m above sea level and overlooks the
Schwartz (1995) constructed daily counts of Mediterranean Sea.
Fig. 1. Locations of Lebanon on the Mediterranean Sea and of the HUV and CPF sites
1694
Analysis of the continuous measurements of PM10 and PM2.5 concentrations in Beirut, Lebanon
The typical unplanned urban morphology, high divided into 12 equal periods. Once a cycle has
population density, and high concentration of human completed, the supply reels rotate and a new cycle
activities of the developing world, together with the begins.
Mediterranean climate and topography of the capital, The MP101M has a built-in reference gauge for
are major factors that contribute to the degradation of calibration and the procedure of calibration is repeated
air quality. The main sources of air pollution are every 6 months. This equipment is manufactured
vehicular traffic and dust storms, because industrial according to ISO 10473 standards, certified equivalent
activity does not exist within the study area. The to the US EPA-approved reference methods Nos.
number of registered vehicles in Lebanon exceeds one EQPM-0404-151 and EN 12341.
million, and the average age of the vehicle fleet is over Measurements of the trace gases were taken by
10 years (El-Zein et al., 2007). The government an atmospheric monitoring system for O3 and
exercises little effective control over the quality of NO/NO2 (Environnement SA, 2013), the instruments
fuel, which is imported (El-Zein et al., 2007). of which were installed within a shelter in Beirut,
However, in 2002, a law was introduced banning the Lebanon. Ambient air was sampled through ¼-in
use of diesel fuel for light- and medium-duty engines. Teflon sampling tubing and all the recording
The main thermal power station of the country is instruments were connected to an XR workstation data
located 13 km northeast of Beirut, and the airport is logger, which was used to store their outputs.
located 7 km to the southwest. Pollution data were The AC32M monitor for NO2 is based on
collected from only one station even though there are chemiluminescence (EN 14211) and the O342M
several stations within Beirut for the measurement of monitor is based on the absorption of ultraviolet
air quality. However, we chose the most suitable site, radiation (EN 14625). A gas dilutor (LNI Schmidlin
which we monitored consistently throughout the study SA, Model SONIMIX 3012) was used to calibrate the
period. Wordley et al. (1997) confirmed that instruments using zero and standard gases. The zero
significant variation in pollutant levels could exist air generator (LNI Shmidlin SA, Model SONIMIX
between different stations, but that data obtained from 3052) provided high-purity zero air, while the
one station could be used as proxies for the levels of standard gas consisted of 29 ppm NO balanced with
air pollution required for time series studies. high-purity N2. The ozone analyzer calibration was
conducted using a standard ozone generator regulated
2.2. Instrumentation and sampling procedure by ultraviolet light and integrated in the SONIMIX
dilutor.
The concentrations of PM10 and PM2.5 were The daily average concentrations of
measured using an MP101M (Environnement SA, atmospheric PM10, PM2.5, and other pollutants were
2013) atmospheric monitoring system. The MP101M obtained between January and December 2012. In
is an ambient air-suspended particulate analyzer that addition to the continuous measurements of the
uses a beta gauge. A beta gauge consists of a Carbon- pollutant levels, measurements of wind direction and
14 radioactive source with very low activity, and a speed, and temperature and humidity were routinely
Geiger–Müller tube receives the emitted beta monitored at this site to understand the influence of
radioactive radiations. The detector is fixed below the meteorological parameters on pollutant levels. A
glass fiber filter tape and it collects air-suspended quality control procedure was established such that the
particulates. Sampling is performed using a vacuum average calculations were accepted if 75% of the
pump attached to a sampling head that is connected to quarter-hourly data were valid for any given hour and
the top of the analyzer. The measurement cycle can be 75% of the hourly data valid for any given day.
described as follows: Relationships between PM10, PM2.5, and PM10–
• Stage 1: The tape is blank. The radioactive 2.5 and other pollutant concentrations were
source is placed in front of the Geiger–Müller investigated. This was accomplished either by
detector. At this stage, a specified quantity of beta estimating correlations between the different variables
radiation is absorbed by both the filter and the (Pearson correlation coefficients) or by conducting
compressed air located between the radioactive source regression analysis.
and the detector.
• Stage 2: The sample is absorbed by the 3. Results and discussions
sampling head and collected on the filter tape. Beta
radiation emitted by the source is absorbed by the 3.1. PM10, PM2.5, and PM10–2.5 concentrations
filter, the compressed air, and the fixed particulates.
The particulate concentration is calculated The concentrations of PM10 and PM2.5 were
based on the difference between the radiation count at measured on 343 days, out of the 365 days, from
the beginning of the cycle when the tape is blank, and January through December 2012. These
at the end of the cycle when particulates have adhered measurements produced 8232 data points for
to the tape. This difference in count is directly assessment of the concentration of each pollutant.
proportional to the mass of particulates collected on Statistics for the daily concentrations of PM10, PM2.5,
the tape. The duration of each cycle is 24 h, which is and PM10–2.5 are shown in Table 1. The coarse particle
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Farah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1693-1700
HUV-PM10 vs CPF-PM10
400
Regression line
300
HUV-PM10 (µg.m-3)
200
100
0
0 100 200 300 400
CPF-PM10 (µg.m-3)
Fig. 2. Comparison between PM10 concentration measurements at HUV and CPF sites
1696
Analysis of the continuous measurements of PM10 and PM2.5 concentrations in Beirut, Lebanon
PM10
350
PM2.5
300
200
150
100
50
0
1/1/2012
2/1/2012
3/1/2012
4/1/2012
5/1/2012
6/1/2012
7/1/2012
8/1/2012
9/1/2012
10/1/2012
11/1/2012
12/1/2012
1/1/2013
Fig. 3. Temporal trends of daily average PM10 and PM2.5 concentrations over the study period in Beirut.
Inset shows the correlation between PM10 and PM2.5 concentrations
This Figure shows that the mean values of both study periods. However, the average PM2.5/PM10 ratios
PM10 and PM2.5 reached peaks in February–July, when observed by Khodeir et al. (2012), Shahsavania et al.
wind speeds were also the highest, which is consistent (2012), and Saliba et al. (2010) are much lower than
with Draxler et al. (2001) and also identified by other those found in the present study.
investigators (Badarinatha et al., 2010; Querol et al., The primary reason for this difference is that,
2009). unlike our study, the pollutants in these other studies
Being an enclosed area, the Middle East is were not measured continuously. Thus, the
easily affected by dust storms from two sources: the PM2.5/PM10 ratios calculated for the entire year
Sahara desert in Africa and the Arabian Desert in Asia. include spring and summer. During these seasons, the
In Lebanon, dust events that carry great quantities of fine fraction of PM (i.e., PM2.5) is highest because
sand and dust from the deserts, usually occur in March various sources release fine particulates primarily
and April, but occasionally, they can occur into July. during these seasons; therefore, this produces an
The relationship between PM10 and PM2.5 increase in the PM2.5/PM10 ratio.
concentrations was analyzed in terms of linear
regression and the result revealed that the coefficient
of determination (r2) was relatively high (r2=0.83), as
shown in the inset of Fig. 3. This is expected, because
both fine and coarse particles are associated with local
traffic.
3.4. PM ratios
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Farah et al./Environmental Engineering and Management Journal 17 (2018), 7, 1693-1700
exceeding these standards for PM10 and PM2.5 during emissions, domestic heating during the cold season,
the different months of the study period. For PM10, the and industrial activities. To establish the association
greatest number of exceedance days (25 days) between PM and traffic-related gaseous pollutants,
occurred in July (25 days) followed by August (19 data from the HUV site were considered.
days) and April (16 days). There were 133 days during Simultaneous measurements of NO2 and O3 were
the observation period on which daily concentrations conducted at the same monitoring site to achieve this
of PM10 exceeded the upper threshold limit, which objective, and Fig. 6 summarizes the monthly average
represents 39% of the sampling period (133 out of concentrations of all the gaseous species obtained
343). For PM2.5, the greatest number of exceedance during the study period. The main source of the high
days occurred in April (19 days) followed by May, concentration of NO2 is largely the high volumes of
March, and June (all 16 days). There were 129 days vehicular traffic in Beirut (Afif et al., 2009).
during the observation period on which daily Concentrations of PM10, PM2.5, and PM10–2.5
concentrations of PM2.5 exceeded the upper threshold were correlated with NO2 and O3 measured at the same
limit, which represents 38% of the sampling period monitoring site. The most significant correlation was
(129 out of 343). The highest daily averages of the found for PM2.5 with NO2 (r = 0.7), whereas PM10 and
PM10 and PM2.5 concentration were observed during PM10–2.5 were found not to be associated with any
spring and summer (March to July). These findings gaseous pollutant. Strong associations between fine
indicate the role played by dust events within this area particle mass concentrations and primary gaseous
(Kutiel and Furman, 2003). pollutants have been reported previously reported
following air-quality surveys in Birmingham, UK,
3.6. Relationships between PM and other pollutants suggesting the importance of road traffic-related
emissions (Harrison et al., 1997). The contribution to
Studies have shown that PM causes greater levels of PM10 and PM2.5 from vehicular exhausts was
adverse effects when associated with SO2, NO2, CO, estimated using regression analysis (Table 2). NO2
and O3 (e.g., Cheng et al., 1998; Dockery et al., 1993). was used as a vehicular emission tracer because it is
Gaseous pollutants (except ozone) are associated assumed that NO2 is almost entirely attributable to
mostly with local sources, including exhaust emissions from road traffic.
Dec. Jan.
PM2.5 6%
8%
Feb.
Nov.
12%
12%
Oct.
1%
Sep.
2% Mar.
July 12%
7%
June
12% Apr.
15%
May
14%
(a) (b)
Fig. 5. Percentage of exceedance days for PM10 and PM2.5 concentrations during the different months of the study period: (a); (b)
Fig. 6. Monthly average concentrations of O3 and NO2 during the study period at the HUV site
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Analysis of the continuous measurements of PM10 and PM2.5 concentrations in Beirut, Lebanon
Regression relationship r
PM10 [PM10] = 29 + 0.28 [NO2] 0.39
PM2.5 [PM2.5] = 2.2 + 0.23 [NO2] 0.70
PM10-2.5 [PM10-2.5] = 11.5 + 0.16 [NO2] 0.24
For PM2.5, a very small value of the intercept governmental organization arcenciel, and the CEDRE
was found (2.2 µg.m−3) for the background together project (Ministry of Foreign Affairs in France and the
with 28.1 µg.m−3 (mean–intercept) of vehicular- Ministry of Higher Education and Research in France and
derived material, whereas for PM10, the background Lebanon) for supporting this research financially.
concentration was 29 µg.m−3 with a value of 22.3
µg.m−3 representing the traffic-derived material. References
These results suggest that, on average, 93% of PM2.5
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corresponding maximum values of 359.7 and 208.6 and Planet Change, 72, 164-181.
µg.m−3. The mean concentration of coarse particles Brauer M., Hoek G., Van Vliet P., Meliesfste K., Fisher P.
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± 0.12, indicating that in Beirut, about 61% of PM10 Respiratory health and long-term exposure to air
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1701-1709
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Jing Wei, Xiaoyan Liu ∗, Chuanhua Wang, Xueping Chen, Xia Liang, Qian Wang
Abstract
Though Scirpus triqueter plays an important role in protecting the ecological functions of Yangtze River estuary wetland which is
frequently contaminated by petroleum, knowledge is limited about the mechanisms involved. In this study, comparative analysis
of soil properties, microbial community structure and soil enzymes in the rhizosphere of S. triqueter and bulk soil was conducted
throughout one year to provide an insight into the phytoremediation mechanism in the field. The total petroleum hydrocarbon
content and soil pH in the rhizosphere were averagely 0.06 g kg-1 and 0.1 lower, respectively, than in the bulk soil. Analysis of
phospholipid fatty acids shew the microbial community structure was quite different from that in the bulk soil with much higher
activity and diversity. The relative abundance of Gram-positive to Gram-negative bacteria was 0.12 lower in the rhizosphere, while
the relative abundance of aerobes to anaerobes was 0.74 higher, than in the bulk soil. Positively correlated with the relative
abundance of fungi to bacteria and microbial diversity, the activities of dehydrogenase, catalase, polyphenol oxidase were
significantly lower (P < 0.05) in the bulk soil than in the rhizosphere. Redundancy analysis and Pearson correlation shew that soil
organic matter, total nitrogen, total phosphorus, as well as temperature were crucial factors influencing soil microbial communities
and enzymes which were responsible for the degradation of petroleum hydrocarbons. These results would improve our
understanding of the phytoremediation processes in fragile contaminated wetland and supply valuable information for its
application in the restoration of damaged ecosystems.
Key words: microbial community structure, petroleum pollution, phytoremediation, Scirpus triqueter, soil enzymes
Received: February, 2013; Revised final: August, 2014; Accepted: September, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: lxy999@shu.edu.cn; Phone: +86 21 66137767; Fax: +86 21 66137761
Wei et al./Environmental Engineering and Management Journal 17 (2018), 7, 1701-1709
Soil microorganisms play an important role in Sampling sites were set in the HYRE wetland,
the degradation of organic contaminants (Ciancio et the north of Shanghai, China. Characterized by the
al., 2016; Gerhardt et al., 2009). Liu et al. (2010a) north semi-tropical monsoon climate, the annual
found that 58.2% of the petroleum hydrocarbons were precipitation is 1022 mm and approximately 70
degraded by indigenous microbes after one year of percent falls between May and September. The annual
bioremediation in a pot experiment. It is thought that mean temperature is around 15.3ºC according to
plants can enhance the pollutant-removal ability of Shanghai Meteorological Center. Almost 80 percent
soil microbes through the so called rhizosphere effect of the mesolittoral zone in HYRE wetland is colonized
(Liu et al., 2010a; Mihalache et al., 2016). Sun et al. by S. triqueter, a kind of perennial herb, whose
(2010) proved that root-exudates enhanced the growing period is from April to November.
biodegradation of phenanthrene and pyrene by 15.5% In this study, rhizosphere and bulk soil samples
and 21.3%, respectively, in a low organic matter soil. were collected every month from March, 2011 to
Meng and Zhu (2010) found that components from February, 2012. Rhizosphere soil samples (SS) were
celery roots increased the removal of pyrene by randomly collected from the root surface of S.
around 22% in an industry soil, and lipophilic triqueter at the depth of 0-20 cm and bulk soil samples
components enhanced the relative abundances of (BS) were collected at the same depth, but at least 1 m
pyrene-degraders. In addition, the influences of plants away from the nearest plants (Toyama et al., 2011).
on soil microorganisms are plant-dependent (Yao and All soil samples were processed within 6 h according
Wu, 2010), which may lead to discrepant to previous studies with some modifications (Nie et
phytoremediation efficiencies (Wei et al., 2013). As a al., 2009). Plant roots and stones were hand-picked
culture-independent approach to explore the out. Soils were freeze-dried, then passed through 1
fingerprints of soil microbes, phospholipid fatty acid mm mesh to get homogenized. All the samples were
(PLFA) model is a preferable method to monitor the divided into two parts: one was stored at 4ºC for the
complex soil microbial community structure (Cowie analysis of soil properties and soil enzymes as
et al., 2010; Frostegård et al., 2011). Therefore, PLFA mentioned previously (Wei et al., 2013); the other part
model was used to analyze the relative abundance of was stored at -80ºC to avoid the degradation of PLFAs
certain microflora, including bacteria (B), fungi (F), and used for soil microorganism analysis.
Gram-positive bacteria (GP) and Gram-negative
bacteria (GN), aerobes (AE) and anaerobes (AN), in 2.2. Soil properties
this study.
Soil enzymes, deriving primarily from soil Total petroleum hydrocarbon (TPH) was
microorganisms, plant roots, plant and animal ultrasonically extracted from 5 g of treated soil
residuals, are sensitive indicators for the soil function samples with dichloromethane, then the content was
and environmental strain in affected ecosystems determined through gravimetric analysis as described
(Zhou et al., 2011). Their activities vary widely in previous studies (Liu et al., 2011; Mishra et al.,
depending on the enzyme species, soil types, 2001; Zhang et al., 2013). Values of pH and total
environmental factors, plants, as well as pollutants dissolved solid (TDS) were determined by HI255 pH-
(Wang et al., 2009). Wyszkowska and Wyszkowski TDS-conductivity-salinity meter after mixing the soil
(2010) found that petroleum contamination inhibited with deionized water (1:10, w/w); total nitrogen (TN)
the activities of soil dehydrogenases and urease to a content was analyzed by Kjeldahl apparatus (Buchi
large degree in spring rape and oat soils. Considering Distillation Unit B-324); soil temperature-moisture
that soil enzymes can serve to measure the health and meter (LZB-I) was used for the measurement of the
sustainability of disturbed ecosystems (Boerner et al., soil temperature (T); total phosphorus (TP) and
2005), activities of important soil oxidoreductases and organic matter (OM) were determined by colorimetric
hydrolases, as well as the relationship between soil and volumetry method, respectively (Rukun, 1999).
microbial communities and enzymes, were measured
to probe into the influences of S. triqueter on the soil 2.3. Soil microbial communities
function in this study.
This study was carried out in HYRE wetland The activity of fluorescein diacetate hydrolase
with the objectives: (1) to explore the differences of (FDA), expressed in A490 g-1 dry soil 2 h-1, was used to
soil properties, microbial community structure and reflect the total activity of soil microorganisms (Green
soil enzymes in the rhizosphere and bulk soil; (2) to et al., 2006; Wei et al., 2013). To measure the FDA
monitor seasonal fluctuation of microbial activity, 1 g of treated soil was mixed with 30 mL of
communities and soil enzymes throughout one year; phosphate buffer (pH 7.6) and 1 mL of fluorescein
(3) to investigate the interactions between soil diacetate solution (2 g mL-1, dissolved in acetone),
properties, soil microbial communities and soil then the mixture was incubated in the dark at 30ºC for
enzymes during phytoremediation of petroleum 2 h. After centrifugal separation, the absorbance at 490
polluted wetland. nm was detected.
Microbial community structure was analyzed
2. Materials and methods using PLFA method. In general, crude fatty acids were
extracted from 3 g of soil by a mixture of citrate buffer,
2.1. Field sampling methanol, and chloroform (Frostegård et al., 1993; Li
1702
Contrastive soil properties, microbial structure and soil enzymes in the rhizosphere
et al., 2010). Then the crude fatty acids were passed 1). TPH content in the rhizosphere was significantly
through silica gel columns with methanol as the eluent lower (P < 0.05) than in the bulk soil, indicating that
to obtain phospholipids. After that, phospholipids S. triqueter can greatly enhance the degradation of
were methylated and quantified using GC-MS (Li et petroleum hydrocarbons. In addition, the pH value
al., 2010). PLFAs were named according to the (7.3 ± 0.1) in the bulk soil was significantly higher
nomenclature described in previous study (Cao et al., than that (7.2 ± 0.0) in the rhizosphere (P < 0.001),
2012). Shannon index H was used to evaluate the while the OM content of 75.03 ± 18.21 g kg-1 in the
diversity of microbial communities and calculated by rhizosphere of S. triqueter was slightly higher than
Eq. (1): that of 61.28 ± 17.07 g kg-1 in unplanted soil. By
contrast, differences of soil temperature, TN, TP and
R
H = −∑ pi ln pi (1) TDS contents, between the two types of soil were less
i =1
remarkable.
Organic acids released by plants, including
where H represented the value of Shannon index, pi citric acid, malic acid, oxalic acid and so on, may
was the relative abundance of each detected PLFA, R contribute to the decrease of soil pH. It is thought that
was the total number of detected PLFAs (Yao and Wu, petroleum hydrocarbons can affect increase soil pH,
2010; Zornoza et al., 2009) deteriorate soil function and decrease soil
permeability.
2.4. Soil enzymes On the other hand, plants can improve soil
properties through releasing ample carbon sources and
Activities of three oxidoreductases
mineral nutrients into the soil in the form of root
[dehydrogenase (DHA, EC 1.1), catalase (CAT, EC
exudate, mucilage, colloidal and so on (Bertin et al.,
1.11.1.6) and polyphenoloxidase (PPO, EC 1.10.3.1)]
2003; Hinsinger, 2001; Richardson et al., 2009).
and three hydrolases [sucrase (SUC, EC 3.2.1.26),
Therefore different soil properties between the
urease (URE, EC 3.5.1.5) and alkaline phosphatase
rhizosphere and bulk soil were the combined results
(PHOS, EC 3.1.3.1)] were measured.
by petroleum hydrocarbons and plants.
URE activity, expressed as mg NH4-N g-1 soil
-1
24 h , was measured according to the hydrolysis rate 3.2. Soil microbial communities
of carbamide. SUC activity, expressed as mg glucose
g-1 soil 24 h-1, was determined by incubating treated A total of 23 PLFAs were detected, most of
soil with sucrose solution (Schinner and Mersi, 1990). which had 15-18 carbon in their molecules. PLFAs
PHOS (mg phenol g-1 soil 3 h-1), DHA (mg TF g -1 soil i12:0, a13:0, 13:0, i14:0, i15:0, 15:0, a15:0, i16:0,
48 h-1) and PPO (mg purpurogallin g-1 soil 2 h-1) were 16:1ω7c, 16:1ω7t, i17:0, a17:0, 17:0, 18:0, cy17:0,
measured following the methods previously described 18:1ω7c and cy19:0 were used to indicate bacterial
(Guan, 1986; Tang et al., 2010; Wyszkowska and biomass; 16:1ω5t, 18:1ω9t, 18:1ω9c, 18:2ω6,9c were
Wyszkowski, 2010). Hydrogen peroxide was used as used as fungal biomarkers; 16:1ω7c, 16:1ω7t,
the substrate for CAT determination, and the unit of 18:1ω7c, cy17:0, cy19:0 were chosen to represent GN;
its activity was mL 0.1 M KMnO4 g-1 soil 30 min-1 branched saturated fatty acids i14:0, i15:0, i16:0,
(Johnson and Temple, 1964). i17:0, a15:0 and a17:0 indicated GP; 14:0 and 16:0
were common PLFAs in most microorganisms
2.5. Statistical analysis
(Frostegård et al., 1993; Velasco et al., 2010; Zhang et
Each data was the mean value (±SD) of three al., 2010). The ratio of monounsaturated fatty acids to
replicates. SPSS 17.0 was used for paired t test to branched saturated fatty acids was used to indicate the
examine the differences of rhizosphere and bulk soils relative abundance of aerobic to anaerobic microbes
in data sets of soil properties, soil microorganisms and (AE/AN) (Li et al., 2010; Su and Yang, 2009).
soil enzymes. Principal component analysis (PCA) PCA plot was used to compare the microbial
was used to compare microbial community structure community structure in the rhizosphere and bulk soil
in the rhizosphere and bulk soil. Redundancy analysis (Fig.1). The first principal component accounted for
(RDA) performed by Canoco for windows 4.5 was 75.4% of the total variance and the second explained
used to analyze the microbial characteristics across 17.3%. Samples in the rhizosphere were completely
soil property gradients, as well as soil enzymes across separated with those in the bulk soil as illustrated in
microbial population gradients. Pearson correlation the PCA plot, therefore their microbial structures were
matrix was used to assess the covariance between soil quite different from each other. Microbial
properties, microbial communities and enzyme communities in the rhizosphere were characterized by
activities. monounsaturated fatty acids, such as 18:1ω7c,
16:1ω5t, 16:1ω7t and 16:1ω7c, with higher diversity
3. Results and discussion and activity. By contrast, the relative abundances of
saturated fatty acids were much higher in the bulk soil,
3.1. Soil properties resulting in the higher GP/GN.
Paired t-test analysis was used to compare the
Paired t-test was conducted to compare the soil microbial community structure in the bulk and
characteristics in the rhizosphere and bulk soil (Table rhizosphere soil (Table 2).
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Wei et al./Environmental Engineering and Management Journal 17 (2018), 7, 1701-1709
.
Table 1. Comparison of soil properties in the bulk and rhizosphere soil through paired t-test
Fig. 1. PCA plot of microbial communities in the rhizosphere and bulk soil (FDA, fluorescein diacetate hydrolase; AE/AN, the
relative abundance of aerobes to anaerobes; GP/GN, the relative abundance of Gram-positive bacteria to Gram-negative bacteria;
F/B, the relative abundance of fungi to bacteria; H, Shannon index. BS, bulk soil; SS, soil in the rhizosphere of S. triqueter,
digitals reflect the sampling month)
Table 2. Comparison of soil microbial structure in the bulk and rhizosphere soil by paired t-test
Bulk Rhizosphere Difference t P
FDA (abs g-1) 0.22 ± 0.10 0.29 ± 0.14 0.45 ± 0.32 -2.352 0.038
AE/AN 1.89 ± 0.43 2.63 ± 0.33 0.07 ± 0.10 -4.996 0.000
GP/GN 0.62 ± 0.18 0.50 ± 0.14 0.74 ± 0.51 4.017 0.002
F/B 0.03 ± 0.03 0.12 ± 0.09 0.12 ± 0.10 -4.267 0.001
H 1.94 ± 0.20 2.10 ± 0.25 0.16 ± 0.13 -4.203 0.001
FDA, fluorescein diacetate hydrolase; AE/ AN, the relative abundance of aerobes to anaerobes; GP/GN, the relative abundance of Gram-positive
bacteria to Gram-negative bacteria; F/B, the relative abundance of fungi to bacteria; H, Shannon index
FDA activity was significantly higher (P < vegetative period of S. Triqueter (Fig.2C). In addition,
0.05) in the rhizosphere (0.29 ± 0.14 abs g-1) than that the average value of H was 2.10 ± 0.25 in the
in bulk soil (0.22 ± 0.10 abs g-1), which indicated the rhizosphere, while 1.94 ± 0.20 in the bulk soil,
soil microbes were more active in the rhizosphere than reflecting that soil microbes in the rhizosphere were
in the bulk soil. The activity of soil microorganisms more diverse during the whole year (Table 2, Fig.2D).
was thought to be largely related with petroleum The lower TPH content and moderate pH
biodegradation (Kirk et al., 2005; Liu et al., 2011). (Table 1) in the rhizosphere, as well as various organic
The relative abundance of AE to AN was carbons released by plant roots, provided a better
distinctly higher (P < 0.001) in the rhizosphere than in habitat for soil microbes and accounted for the higher
bulk soil (Table 2), and this disparity reached to the activity and diversity of microbial communities in the
summit in August (Fig.2A). Similarly, the relative rhizosphere (Table 2). It was believed that the
abundance of fungi to bacteria in the rhizosphere was microbial community structure was plant-dependent
3-4 times higher than in the bulk soil (Table 2), and in the rhizosphere (Smalla et al., 2001). For example,
the biggest difference appeared in October (Fig.2B). soil microbial populations were dominated by cy17:0,
However, the relative abundance of GP to GN 16:1ω5c and 18:1ω5c in the rhizosphere of V. tricolor,
decreased by about 20% in the rhizosphere compared while by 18:1ω7c, 18:0 and 10Me18:0 in the
with that in bulk soil (Table 2) during the whole rhizosphere of C. comosum (Wei et al., 2013).
1704
Contrastive soil properties, microbial structure and soil enzymes in the rhizosphere
Fig. 2. Soil microbial community structure in the rhizosphere and bulk soil throughout one year
AE/AN, the relative abundance of aerobes to anaerobes; GP/GN, the relative abundance of Gram-positive bacteria to Gram-
negative bacteria; F/B, the relative abundance of fungi to bacteria; H, Shannon index. BS, bulk soil; SS,
soil in the rhizosphere of S. triqueter
The relative abundances of effective Rhizosphere samples were located on the left
petroleum-degrading microorganisms (AE and GN) of Axis1, while bulk samples on the right. With the
were much higher in the rhizosphere of S. triqueter, greatest arrow lengths among all the environmental
which can explain the reason why S. triqueter had a factors, pH and TPH concentration were two main
good ability to enhance the degradation of petroleum determinants of the soil microbial community
hydrocarbons in the HYRE wetland (Wei et al., 2014; structure. By contrast, TDS affected the soil microbial
Zhang et al., 2011). RDA was used to explore the communities slightly. The completely contrary
effect of soil properties on microbial communities. tendencies of TPH and AE/AN revealed that TPH
The first two axes explained 69.4% and 25.4% of the concentration made a negative influence on the
total variance respectively (Fig.3). relative abundance of AE/AN. However, OM, TP and
TN influenced soil microbial structure by increasing
microbial diversity and activity. In addition, soil
microbial structure appeared to be similar in the same
season, for example, rhizosphere samples in March,
April and May located adjacently in the ordination
diagram of RDA.
As an important indicator for the soil microbial
ecology, the ratio of F/B has been used to indicate the
shift of soil microbial community structure under
environmental stress (Kaur et al., 2005; Yao and Wu,
2010). It has been reported that F/B ratio was
positively correlated with soil fertility quality, but
negatively with pollution level (Liu and Herbert,
2002; Zhang et al., 2012). Therefore, the higher
relative abundance of fungi in the rhizosphere might
Fig. 3. RDA plot based on microbial communities and soil result from the lighter pollution level to some extent.
properties in the rhizosphere and bulk soils throughout one pH deviation could impose great stress on soil
year (FDA, fluorescein diacetate hydrolase; AE/AN, the microorganisms by changing the integrity and
relative abundance of aerobes to anaerobes; GP/GN, the function of cellular membranes or altering the
relative abundance of Gram-positive bacteria to Gram- bioavailability of nutrients and contaminants (Baath
negative bacteria; F/B, the relative abundance of fungi to and Anderson, 2003; Fierer and Jackson, 2006; Wick
bacteria; H, Shannon index. T, soil temperature; TN, total
et al., 2010), therefore it was one of the main factors
nitrogen; TP, total phosphorus; OM, organic matter; TPH,
total petroleum hydrocarbon; TDS, total dissolved solid. determining microbial community structure (Fig.3).
BS, bulk soil; SS, soil in the rhizosphere of S. triqueter, Pearson correlation coefficients between soil
digitals reflect the sampling month) properties and microbial characteristics were listed in
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Wei et al./Environmental Engineering and Management Journal 17 (2018), 7, 1701-1709
Table 3. Coefficients of Pearson correlation between soil properties and microbial characteristics
T TN TP OM pH TPH TDS
Bulk
FDA 0.374 0.444 0.394 -0.358 -0.279 0.317 -0.280
AE/AN -0.423 -0.632* -0.091 0.007 -0.154 0.204 0.667*
GP/GN 0.284 0.656* 0.604* -0.298 -0.568 0.223 -0.455
F/B 0.711** 0.546 0.320 0.447 0.215 0.133 -0.178
H 0.781** 0.799** 0.495 0.278 -0.055 -0.182 -0.296
Rhizosphere
FDA 0.080 0.341 0.709** 0.690* 0.501 0.688* 0.578*
AE/AN 0.271 0.117 0.112 -0.252 0.456 -0.465 -0.168
GP/GN 0.020 0.156 0.276 0.617* -0.082 0.626* 0.078
F/B 0.825** 0.663* 0.225 0.637* 0.391 0.137 -0.121
H 0.823** 0.801** 0.549 0.812** 0.563 0.387 -0.108
Asterisks mark different levels of significance: *P < 0.05, **P < 0.01. FDA, fluorescein diacetate hydrolase; AE/AN, the relative abundance of
aerobes to anaerobes; GP/GN, the relative abundance of Gram-positive bacteria to Gram-negative bacteria; F/B, the relative abundance of fungi
to bacteria; H, Shannon index, represents the microbial diversity. T, soil temperature; TN, total nitrogen; TP, total phosphorus; OM, organic matter;
TPH, total petroleum hydrocarbon; TDS, total dissolved solid
Table 4. Comparison of soil enzymes in bulk and rhizosphere soil by paired t-test
1706
Contrastive soil properties, microbial structure and soil enzymes in the rhizosphere
5
A BS 2.8 D BS
4 SS SS
CAT
2.1
DHA
3 1.4
2 0.7
1 0.0
0.4 B BS
SS 1.0 E
BS
SS
URE
SUC
0.2 0.5
0.0 0.0
C 0.18
0.4 BS F BS
SS SS
PPO
0.12
PHOS
0.2
0.06
0.0 0.00
Apr. 2011
Mar. 2011
Mar. 2011
May 2011
Aug. 2011
May 2011
Apr. 2011
Jun. 2011
Jul. 2011
Sep. 2011
Dec. 2011
Jul. 2011
Sep. 2011
Jun. 2011
Aug. 2011
Oct. 2011
Jan. 2012
Nov. 2011
Dec. 2011
Nov. 2011
Oct. 2011
Feb. 2012
Feb. 2012
Jan. 2012
Date
Fig. 4. Variations of soil enzyme activities in the rhizosphere and bulk soil throughout one year
(DHA, dehydrogenase, mg TF g -1 soil 48 h-1; CAT, catalase, mL 0.1M KMnO4 g-1 soil 30min-1; PPO, polyphenoloxidase, mg
purpurogallin g-1 soil 2 h-1; SUC, sucrase, mg glucose g-1 soil 24 h-1; URE, urease, mg NH4-N g-1 soil 24 h-1; PHOS, alkaline
phosphatase, mg phenol g-1 soil 3 h-1. BS, bulk soil; SS, soil in the rhizosphere of S. triqueter)
Therefore, soil microbes can indirectly In this study, rhizosphere effects on soil
influence the degradation of petroleum by regulating properties, microbial community structure and soil
activities of soil enzymes. Coefficients of Pearson's enzymes, as well as their interactions, were explored
correlation between soil characteristics and enzymes at the HYRE wetland for the first time. Characterized
were listed in Table 5. In both types of soil, CAT, PPO with higher microbial activity and diversity, the
and SUC were positively related with soil microbial community structure in the rhizosphere was
temperature. PHOS was positively correlated with soil quite different from that in the bulk soil.
1707
Wei et al./Environmental Engineering and Management Journal 17 (2018), 7, 1701-1709
T TN TP OM pH TPH TDS
Bulk
CAT 0.782** 0.369 0.249 0.366 0.378 -0.378 -0.093
PPO 0.855** 0.486 0.407 0.674* 0.382 -0.409 0.097
SUC 0.589* -0.193 0.166 0.675* 0.531 -0.313 0.563
URE -0.023 0.133 0.035 -0.074 0.270 0.247 -0.218
PHOS 0.643* 0.843** 0.404 0.031 -0.264 0.135 -0.585*
DHA 0.638* 0.590* 0.480 -0.157 -0.137 -0.030 -0.293
Rhizosphere
CAT 0.743** 0.636* 0.244 0.290 0.772** -0.240 0.033
PPO 0.893** 0.894** 0.446 0.618* 0.652* -0.013 0.084
SUC 0.662* 0.416 0.255 0.206 0.677* -0.425 0.174
URE 0.486 0.365 0.351 0.230 0.502 0.103 -0.041
PHOS 0.452 0.462 0.266 0.696* 0.044 0.479 -0.180
DHA 0.499 0.435 0.205 0.419 0.551 0.142 0.199
Asterisks mark different levels of significance: *P<0.05, **P<0.01. DHA, dehydrogenase; CAT, catalase; PPO, polyphenoloxidase; SUC, sucrase;
URE, urease; PHOS, alkaline phosphatase. T, soil temprature; TN, total nitrogen; TP, total phosphorus; OM, organic matter; TPH, total petroleum
hydrocarbon; TDS, total dissolved solid
Positively correlated with H and the relative Frostegård Å., Tunlid A., Bååth E., (1993), Phospholipid
abundance of F/B, activities of DHA, CAT, PPO in the fatty acid composition, biomass, and activity of
bulk soil were significantly lower (P < 0.05) than in microbial communities from two soil types
the rhizosphere. The microbial structure and activities experimentally exposed to different heavy metals,
Applied and Environmental Microbiology, 59, 3605-
of soil enzymes were greatly affected by OM, TN, TP 3617.
and pH. Frostegård Å., Tunlid A., Bååth E., (2011), Use and misuse
of PLFA measurements in soils, Soil Biology and
Acknowledgements Biochemistry, 43, 1621-1625.
The work was funded by the National Natural Science Gerhardt, K.E., Huang, X.D., Glick, B.R., et al., (2009),
Foundation of China (Nos.41373097, 41073072, 41101230, Phytoremediation and rhizoremediation of organic soil
41203051), China Postdoctoral Science Foundation funded contaminants: Potential and challenges, Plant Science,
project (No.2013M541506), Program for Innovative 176, 20-30.
Research Team in University (No.IRT13078). Green V.S., Stott D.E., Diack M., (2006), Assay for
fluorescein diacetate hydrolytic activity: Optimization
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1710
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1711-1719
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Petru Spataru1, Igor Povar1, Tudor Lupascu1∗, Alfredo Carlos Alder2, Elena Mosanu1
1Institute of Chemistry, Academy of Sciences of Moldova, 3 Academiei str., Chisinau, MD2028, Republic of Moldova
2Eawag, Environmental Chemistry, Eawag, Environmental Chemistry, 133 Uberlandstrasse str., P.O. Box 611,
Dubendorf, CH-8600, Switzerland
Abstract
The presence of nitrogen in its reduced forms serves as an indicator of natural aquatic system degradation. The excessive
concentrations of nitrogen in reduced forms (NH4+, NO2-) found in the sections of the the Shireutsi (of the Prut River) and the
Olaneshti (of the Nistru River) prove that these sites are areas to focus efforts on improving water quality. Laboratory simulations
indicate a good environmental buffer action of natural waters to potential pollution in Sculeni and Ungheni sections of the Prut
River and downstream of Naslavcea and Tiraspol (Nistru River), as well as in sites most affected by pollution with wastewater
from Frasineshti (of the Prut River) along with Lencautsi, Cosautsi and downstream of Bender (the Nistru River). Overcoming the
maximum allowable concentration (MAC) level for the nitrate ion in water from wells is an index of pollution of the land areas
where pollutants can leach into and pollute groundwater. Of the 12 wells from which water samples were collected over three years
(2010-2012), only two wells, in the Cuhneshti and Cobani villages showed MAC level compatible with drinking water quality.
Key words: Moldovan rivers, nitrogen forms, organic compounds, oxidation, seasonal dynamics
Received: January, 2013; Revised final: October, 2014; Accepted: October, 2014; Published in final edited form: July, 2018
∗
Author to whom all correspondence should be addressed: e-mail: lupascut@gmail.com; Phone: +37322739736; Fax: +37322739736
Spataru et al./Environmental Engineering and Management Journal 17 (2018), 7, 1711-1719
was between 85-100%. The absence of waste disposal the same intermediate product - nitrite ion (Philips et
systems as well as basic measures of water sources al., 2002). The nitrite ion concentration, as an
protection are the main causes of water quality indicator of oxidation processes generated by the
worsening in wells. The ratio of wells that exceeded enzymatic catalysis, is higher than the MAC value in
the sanitary-chemical parameters constituted 84.2% in the abovementioned samples, as well as in such
2010 (80.7% in 2009) (NRSERM, 2011). localities near the Prut River, as the town of Leova and
The rivers Nistru and Prut are the largest in the the city of Cahul. In the composed sample from the
Republic of Moldova and their basins comprise the Valea Mare section, this concentration is higher than
entire territory of the country, form and store the most the average value from the same section and period of
significant amounts of water. The waters of Nistru and time, which denotes its authenticity due to
Prut rivers meet the regulatory requirements for biochemical processes.
"Drinking Water" main mineral parameters and Consequently, the main goal of this paper was
represent the greatest source of water for water to study the nitrogen-containing species in function of
treatment plants. The quality of water in these rivers is seasons as well as kinetics of nitrification and de-
guaranteed mainly by self-purification processes that nitrification in the Prut and Nistru waters.
take place in water ecosystems.
Nitrogen, being one of the basic elements in the 2. Methods
formation of organic substances, is among the most
sensitive elements to change in the natural water due Within the Scientific Co-oPeration between
to eutrophication and pollution. The drinking water Eastern Europe and Switzerland (SCOPES) project
MAC level is for NH4+ 0.39 mg/L and NO2- - 0.02 (see Acknowledgments), during the 2010-2012 years,
mg/L (CD, 1998; State Register, 2007). The study of a large amount of aquatic samples were taken from
nitrogen mineral forms highlights the sustainability, as different sections of the Prut and Nistru rivers (see the
well as the vulnerability of the aquatic environment. map, Fig.1), and analytical tests were carried out.
Studies of the hydrochemistry and quality of the water Sampling on the Prut River was started from the
of these rivers have been published in national border between the Republic of Moldova and Ukraine,
specialized journals (Gladchi et al., 2008; Zubcov et above the lake dam (Criva and Shireuti, placed after
al., 2011). Findings show that, for a wide range of the administrative centre Lipcani) and almost
bacteria, in contrast to the situation in animal immediately after the lake (Branishte). The next
(Martinelle et al., 1993) and plant cells (Britto et al., sections were Sculeni and upstream Ungheni (32.5),
2001, Britto et al., 2002), ammonia is not toxic, even before wastewater treatment plant (WWTP), which
in molar concentrations. This happens because most are less affected by human activity. Valea Mare is a
bacteria prefer ammonia as a nitrogen source; some section after the WWTP Ungheni. The Frasinesti
species even produce ammonium ion – for example, section is downstream of the confluence with Jijia
N2-fixing Rhizobia Cyanobacteria and Proteolytic crossing the urban centres Dorohoi (24.3) and Vladeni
Clostridia create ammonia through the fermentation and bringing through the Bahlui River polluted waters
of amino acids. Resistance to ammonia is a common from Iassy (321.6). Cotul Morii is a less affected area,
property in terms of bacteria (Müller et al., 2006). with reduced population. The Leova and Cahul cities
However, nitrites are highly toxic to humans, flora and have respectively 11.4 and 40.9 thousands inhabitants.
fauna, being an important concern regarding water The section Giurgiulesti is influenced by the Danube
quality. They implicate also in the pathology of gastric waters due to frequent changes of its water level. In
cancer (Brunning-Fann et al., 1993, Weng et al., 1992) this segment the Prut water is mixed with that of
and are a possible cause of migraines (Bradberry et al., Danube. The sampling sites of the Nistru River were
1994); they as well compromise the binding capacity mostly chosen close to the towns and cities, as Soroca
of oxygen in the blood and may result in respiratory (28.6), Camenca (23.2), Ribnita (73.6) and Rezina
deficiencies of aquatic animals and humans (Blackall, (10.2) on its middle and Dubasari (35.2), Bender
2000, Van Leeuwen, 2000). Understanding the (99.3), Tiraspol (146.6) and Chisinau (804) on its
toxicity of reduced forms of nitrogen requires the bottom part.
identification of methods of enhancing the oxidation The oxygen fixing and laboratory simulation
of nitrification processes. Furthermore, the pollutants initiating were started along with sampling processes.
are frequently associated into ionogenic groups, Under real conditions many investigations are
becoming less active, and their toxicity decreases and impossible or extremely difficult to accomplish. At the
the rate of oxidation/assimilation processes increase, same time, laboratory simulations offer the
respectively. Otherwise, if pollutants are not opportunity to study the process at the desired stage
associated, their toxicity is higher and the processes of and analyze the degree of influence of a series of
self-purification are blocked (Lewis, 1992). chemical and physicochemical parameters, as the
It is well-known that in the case of nitrification concentration of different components, redox
and denitrification the nitrite ion is an intermediate potential, temperature etc. Preliminary tests were
product. Both processes, oxidation of ammonia (first made for the main mineral parameters: (Ca2+, Mg2+,
stage of nitrification) and denitrification are generated NH4+, NO2-, NO3-, SO42+, HCO3-, Cl-), pH and
by specific enzymes, which cause the production of dissolved oxygen, BOD5, COO-Cr.
1712
Study of nitrogen forms in seasonal dynamics and kinetics of nitrification and denitrification in Prut and Nistru river waters
The natural water tests were carried out For instance, the ammonium ion concentration
according to ISO methods (ISO 7150-1, 2001; SR ISO in the spring water samples of the Camenca River
7890-3, 1988; ISO 8466-1, 1990; SR ISO 7890-3, (near the Balatina village) exceeded 2 MAC; for the
2000; SR EN 26777, 2006; Sandu et al., 1989). Lapusna River (in the summer period) exceeded 1.1
Laboratory simultations were carried out respecting MAC; for the Prut River (the Sculeni village) in
the minimum recommended of water amount for the summer, the Valea Mare village in summer and in the
tested sample in glass bottles (Matveeva et al., (1988). Leova town in fall overcome the MAC by 1.5, 1.4 and
In each sample a solution of NH4Cl was added in 1.2 times respectively.
order to obtain an initial concentration of 2 mg/L of The obtained results were compared with data
ammonium. The tested water samples were kept in obtained by the State Hydrometeorological Service,
natural light conditions and spared from direct rays. HydroMeteo (MB, 2011). The samples were collected
Composed samples over a period of 20 days were also monthly, so in total for each section in two years 24
taken and studied. Test methods were carried out using samples were collected. The comparative analysis of
HACH Company spectrophotometer (2004). data obtained by HydroMeteo and our laboratory
simulations reveals the strength of natural waters to
3. Results and discussion return to the required standard levels for drinking
water and provides a deeper understanding about
3.1. Analysis of experimental data for the Prut River changes in the aquatic environment. The data on
In the first year of our studies (2010) exceeded MAC values for ammonium and nitrite in
ammonium ion concentrations that exceeded the MAC the period of 2011-2012 yrs denote the changes that
("Drinking Water") were detected in some sampling take place in considered cases in the course of the
sections. Ammonium produced by the decomposition middle and bottom of the Prut River (Fig.2), that were
of organic substances affects mostly small rivers. It reported by the State Hydrometeorological Service
also has an evident impact on the larger rivers. (MB, 2011).
1713
Spataru et al./Environmental Engineering and Management Journal 17 (2018), 7, 1711-1719
[NO2-]
Giurgiulesti [NH4+]
Cahul
Leova
Cotul Morii
Valea Mare
Ungheni
Branesti
Siriuti
Criva
0 1 2 3 4 5 6
Number of exceeded MAC
Fig. 2. The number of samples in which the concentrations of NH4+ and NO2- overcome the MAC values
in the middle and bottom sections of the Prut River
Table 1. The concentrations of NH4+, NO2- and NO3- in samples taken from the middle and lower sections
of the Prut River in 2011
Table 2. The concentrations of NH4+, NO2-, NO3-, O2 and BOD5 in samples taken from the middle and lower sections
of the Prut River in 2012
The dynamics of the accident cases (that water"), especially in the Branza village, which
exceeded the MAC values for NH4+ and NO2-) overran the MAC for the ammonium ion concentration
demonstrates an evident influence of anthropic impact in 2011, as well as for the nitrite ion in 2011 and 2012
on the aquatic environment, at the border with Ukraine yrs (Tables 1 and 2).
in the North (up to Lake Costesti-Stanca) and the The most significant decompositions and
Branishte section, which is downstream of this oxidation of organic material in waters are more
reservoir. In the South (the Giurgiuleshti section), the evident in the Prut River, especially in the Branza
water quality of the River Prut is impacted by the section downstream of the Cahul city.
Danube River (Teodoru et al., 2007). The processes of
assimilation and oxidation of organic matter are 3.2. Laboratory kinetic simulation for the Prut waters
significantly more intense upstream of Lake Costesti -
Stanca (the Criva and Shireuti sections) as well as in Using the laboratory simulations, the water
the Leova section; while in the Giurgiuleshti section samples were studied from the following Prut River
they are less obvious. In other words, the more sections: the Sculeni village, the Ungheni city
polluted is area, the less intense are the processes of (downstream of WWTP), the Valea Mare village
assimilation and oxidation of organic matter. (downstream of the Jijia River), downstream of the
The study of the nitrogen-containing species in Leova town and the Branza village. During a period of
waters of the Prut River in the years 2011-2012 8 to 13 days, the ammonia oxidation reached a level of
highlights the values that exceed the MAC ("drinking about 2 mg/L (Fig. 3).
1714
Study of nitrogen forms in seasonal dynamics and kinetics of nitrification and denitrification in Prut and Nistru river waters
a
3,0
Prut, Sculeni
Prut, Sculeni b
[NH4+],mg/L
[NO2-], mg/L
4.0
Prut, after Leova Prut, Branza
2,0 Prut, Branza 3.5
3.0
1,5 2.5
2.0
1,0
1.5
1.0
0,5
0.5
0,0 0.0
0 2 4 6 8 10 12 14 0 5 10 15 20 25 30
Days Days
Fig. 3. The kinetics of the NH4+ (a) and NO2- (b) oxidation for the samples from the following Prut River sections: 1 – the Sculeni
village, 2 – the Ungheni city (downstream of WWTP), 3 –the Valea Mare village (downstream of the Jijia River), 4 - downstream
of the Leova town and 5 –the Branza village
The obtained data of inorganic forms of (ammonium, nitrites) were recorded in the North,
nitrogen are comparable to those of the Yangtze River which was caused by the Novodnestrovsc Dam Lake,
in which there is a noticeable human impact (Muller where the processes of sedimentation and sewage
et al., 2008) and are overcome by the eutrophic water causing an "inertia" of indicators took place, at the
of the Haihe River, from a semi-arid zone of China same time as the Dam Lake Stanca-Costesti gave a
(Pernet-Coudrier et al., 2012). In sections of water stability of the nitrogen forms in the water of the Prut
downstream of Leova and Branza, the ammonia River. The water quality of the Nistru River is affected
oxidation, assimilation of organic compounds, as well especially at the Olaneshti section, and to a lesser
as undergoing transformations under the influence of extent in the sections of Soroca, Dubasari, Vadul-lui-
natural enzymes produced by micro-organisms, Voda and Bender. In the Bik River (tributary of
proceeded very fast. Dniester), downstream of Chisinau, the ammonium
It is known that the numeric rising of concentration is found to be about 10-40 mg/L while
heterotrophic populations in natural water (Daum et at the confluence with the River Nistru ammonia
al., 1998) is coupled with the increase of nitrite exceeds 50mg/L. Formation of ammonium in
concentration (Spataru, 2011; Lin et al., 2010). The wastewaters is mainly supposed to be due to the
samples least prepared for pollution are from the decomposition of organic matter from foodborne/
Sculeni and Ungheni sections. The full process of digestion products containing proteins and urea.
assimilation /oxidation of the reduced nitrogen and
carbon forms for Frasineshti, however, is the longest,
that according to the BOD5 index and the
concentration of nitrites in the destructible sample in
the dark, demonstrates that water sample from the Prut
- Valea Mare, along with the highest content of
organic substance, containts xenobionts, that break the
oxidation of carbon and reduced nitrogen forms. The
complex compounds, which are the ammonia
associated with a wide range of organic substances
(humic complexes), can reduce the toxic effect of
ammonia (for example, in the Leova and Branza
samples). In the case of the water sample from the Prut
– (Valea Mare section), the toxic effect of ammonia is
diminished. Instead, a large amount of organic matter
(in comparison with the rest of the samples) along with Fig. 4. The number of samples in which the concentrations
the presence of toxic pollutants causes a delay of of NH4+ and NO2- exceeded the MAC values in waters of
purification processes (Philips et al., 2002). the Nistru River
3.3. Analysis of experimental data for the Nistru River As one can see from Fig. 4, the anthropogenic
accumulations lead to the increase of the exceeded
Fig. 4 illustrates that for the Nistru River the MAC cases, that is a curve with peaks, which
lowest values of these parameters for accidental cases amplitude is growing to inferior sections, culminating
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Spataru et al./Environmental Engineering and Management Journal 17 (2018), 7, 1711-1719
in the Olaneshti one, and then returns to the normal (Prokopkin, 2010). The change of the hydrochemical
shape up to the Palanca section. regime is also a phenomenon with an important impact
A special case is the pollution of the Dubasari (Mengis et al., 1997).
section. Upstream of this is the Rezina section (Fig. 4), In the Lencauti and Cosauti sections the
where a minimum frequency of prevailing MAC was oxidation takes place more slowly, which shows
found for both ammonia and nitrites. Up to the considerable biochemical diminishes compared to the
Dubasari section, where many cases of the MAC Naslavcea village. It can be assumed that this area is
overruns for nitrites have been found, there are not one of the more vulnerable in the case of the pollution
urban centers which would so strongly influence the treatment. In the upstream section of the Bac,
aquatic environment. It appears that the impact on this downstream of the Bender city, the BOD5 values are
segment is from the secondary pollution of lake larger and growing compared to the sample from the
sediments. The secondary pollution is called the Cosauti village, however the loads of organic matter
pollution that takes place at the interface “water- are much higher. This fact leads to the equalization of
sediment”, caused by underwater deposits, as the oxidation time of ammonia in these samples which
pesticides and heavy metals (Linnik and Zubenko, are different as regards the composition of organic
2000; Zubcov et al., 2010). The Lake Stanca-Costeshti matter and the nitrogen mineral forms from water.
is younger than Lake Dubasari, resulting in a lack of As one can see from Fig. 4, the anthropogenic
evident impact of the secondary pollution in the accumulations lead to the increase of the exceeded
accumulation lake of the Prut River. Therefore, in this MAC cases, that is a curve with peaks, which
case the secondary pollution is a major factor that amplitude is growing to inferior sections, culminating
leads to the decrease of sustainability of the water in the Olaneshti one, and then returns to the normal
treatment system on a segment of the Nistru River. shape up to the Palanca section.
A special case is the pollution of the Dubasari
3.4. Laboratory kinetic simulations for the Prut waters section. Upstream of this is the Rezina section (Fig. 4)
where a minimum frequency of prevailing MAC was
The laboratory kinetic simulation from 2011 found for both ammonia and nitrites. Up to the
demonstrates that in the sample, taken from the Dubasari section, where many cases of the MAC
Naslavcea section, the oxidation process occurred overruns for nitrites have been found, there are not
most quickly (8 days). In the previous publication urban centers which would so strongly influence the
(Spataru, 2011) there were presented data on solved aquatic environment. It appears that the impact on this
oxygen in this section that was lower than in the segment is from the secondary pollution of lake
downstream sections, while the value of BOD5 was sediments. The Lake Stanca-Costeshti is younger than
higher in comparison with the same sections. Lake Dubasari, resulting in a lack of evident impact of
So, it is found that increasing the oxygen the secondary pollution in the accumulation lake of the
concentration has an opposite effect. This result can be Prut River. This fact demonstrates the decrease of
explained by the following evidence. The value of sustainability of the water treatment system on a
BOD5 in the Naslavcea village is higher in comparison segment of the the Nistru River.
with the values of this parameter in the downstream The laboratory kinetic simulation from 2011
sections, since enzyme activity is greater. The proves that in the sample taken from the Naslavcea
oxidation of ammonia, nitrates and organic substances section, the oxidation process occurred most quickly
is related to the fact that the water spilled out of the (8 days). In the previous publication (Spataru, 2011)
lake dam comes from the depth zone of thermocline, there were presented data on solved oxygen in this
where the activity of micro-organisms and section that was lower than in the downstream
biochemical activity is maximum, compared to the sections, while the value of BOD5 is higher in
epilimnion and hypolimnion layers of bulk water comparison with the same sections.
a b
2.5
Nistru, Naslavcea 2.5
Nistru upstream of debus. Bac r.
[NO2-], mg/L
[NO2-], mg/L
1.5
1.5
1.0
1.0
0.5
0.5
0.0
0.0
0 2 4 6 8 10 12 0 2 4 6 8 10 12 14 16 18
Days Days
Fig. 5. The kinetics of the NH4+ ion oxidation in the samples from the Nistru River: (a) represents the sections upstream of the
Bac River; (b) represents the sections downstream of the Tiraspol city
1716
Study of nitrogen forms in seasonal dynamics and kinetics of nitrification and denitrification in Prut and Nistru river waters
a b
7
Nistru upstream of debus. Bac r.
[NO2-], mg/L 8 Nistru downstream Bender sit.
6
[NO2-], mg/L
Nistru, Naslavcea Nistru downstream Tiraspol sit.
7
Nistru, Lencauti
5 Nistru, Cosauti 6
4 5
4
3
3
2 2
1 1
0
0
0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20
Days Days
Fig. 6. The kinetics of oxidation of NO2- -ions in water samples taken from the Nistru River: (a) represents the sections upstream
of the Bac River; (b) represents the sections downstream of the Tiraspol city
As one can see from Fig. 5a, 5b and 6a, 6b the processes of oxidation and destruction, especially in
oxidation of nitrites is more rapidly, although the the sections with an increased concentration of
ammonia oxidation is almost the same as in the nitrites. The study of the samples of water from wells
samples from the Nistru River in the sections upstream on the left side of the Prut River showed an obvious
of the Bac River, downstream of the Tiraspol city, pollution with the nitrate ion (Table 3). Of 12 wells
compared with the Lencauti and Cosauti sections. This from which the water samples were collected within
process keeps its high speed, even if in the lower three years (2010-2012), in only two wells (in the
sections of the Nistru River the organic load is greater. Cuhnesti and Cobani villages) the water corresponds
This fact confirms our earlier finding that the time of to the MAC level (for drinking water). Three of these
oxidation of all reduced nitrogen species depends contain nitrates over MAC, two contain nitrates over
proportionally on the organic matter amounts in 2 MAC, and 5 of these contain over 3 and up to 13
natural waters (Spataru, 2011). MAC of nitrites. In dry seasons many wells remain
The diagram on Fig. 7, with all the accidental without water, leaving the population of villages
cases, demonstrates that the impact of the pollution is without any water supply sources.
more evident in the winter and summer periods. The
climate change mitigation the impact occurred in the 4. Conclusions
spring, compared with the winter and summer. Due to
the pollution of both wastewater and washing of land Most of the main mineral parameters of the
by the pluvial waters the River Prut becomes more rivers Prut and Nistru waters, except ammonia and
affected. These situations can cause low dissolved nitrates, correspond to the European statutory norms
oxygen concentrations due to the intensification of of "Drinking Water".
0
Winter Spring Summer Autumn
Seasons
Fig. 7. The dynamics of the number of accidental cases (the exceeded MAC values) in the 2010-2012 yrs
in the Prut and Nistru rivers (recorded by the State Hydrometeorological Service (MB, 2011))
1717
Spataru et al./Environmental Engineering and Management Journal 17 (2018), 7, 1711-1719
The dynamics of nitrogen mineral forms shows Cazac V., Ceres V., Gherghelegiu V., (2014), Water
the impact of urban activities, where the stations for Resources in the Territory of the Republic of Moldavia,
wastewater treatment do not work satisfactorily. It is L.P. Estetini, Kishinev.
necessary to improve the environmental management CD, (1998), Council Directive 98/83/EC on the quality of
water intended for human consumption Official Journal
upstream of the border with the Ukraine for the Prut of the European Communities, L330, 32-43.
River and upstream of the Olaneshti section in the case Daum M., Zimmer W., Papen H., Kloos K., Nawrath K,
of the Nistru River. Also the secondary pollution Bothe H., (1998), Physiological and molecular
caused by sediments of the Lake dam Dubasari should biological characterization of ammonia oxidation of the
be taken into account. heterotrophic nitrifier Pseudomonas putida, Current
The water in the wells on the east side of the Microbiology, 37, 281-288.
Prut River is polluted with nitrates and disappears in Gladchi V., Goreaceva N., Duca G., Bunduchi E., Borodaev
the most wells in dry periods. It is compulsory to run R., Mardari I., Romanciuc L., (2008), Chemical
a series of projects, in order to fill the lack of drinking composition and redox state of water from the medial
Nistru River, Environment (Mediul Ambiant), 39, 20-
water in the abovementioned villages. 28.
ISO 8466-1, (1990), Water quality - Calibration and
Acknowledgments evaluation of analytical methods and estimation of
This work has been supported by the international program performance characteristics. Part 1: Statistical
SCOPES 2009–2012 Swiss National Science Foundation evaluation of the linear calibration function, On line at:
Joint Research Project “Xenobiotic Input to the Prut River https://www.iso.org/standard/15664.html.
(XENOPRUT)”. Lewis M.A., (1992), The effects of mixtures and other
environmental modifying factors on the toicities of
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1721-1728
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
Novel systems based on modified azo-polysiloxanes and gelatin with potential biological applications were prepared and
characterized. Simultaneous rheological and UV irradiation studies allowed evidencing structural modification inside the gelatin
matrix. For all analyzed samples a shift in the temperature corresponding to the physical network destructuration, from 30˚C
(corresponding to gelatin) to 40˚C (for the composite) was noticed. The experimental results proved the existence of interactions
between gelatin and polysiloxanes intensified after UV irradiation. The increase in the values of G’ and G” is a consequence of
system restructuration leading to more arranged architectures able to release the included active principle. As a function of the azo-
polysiloxane structure, the destructuration temperature of the composite can be tuned in the domain 30- 40°C.
Received: January, 2014; Revised final: October, 2014; Accepted: October, 2014; Published in final edited form: July, 2018
*
Author to whom all correspondence should be addressed: email: ibanescu@ch.tuiasi.ro
Epure et al./Environmental Engineering and Management Journal 17 (2018), 7, 1721-1728
from collagen contained in animal tissues by hot water The ((chloromethyl) phenylethyl)
extraction following an acid or alkaline pre-treatment methyldichlorosilane was purchased from ABCR
and has distinctive sol-gel behavior forming 100% GmbH & Co. KG, Karlsruhe, Germany and also used
thermo-reversible gels. From more than 25 collagen without supplementary purification. The azo-
types, only three can be used to prepare gelatin methacrylate monomer was obtained through Sterlich
(collagen type I, II and III) (Schrieber and Gareis, esterification of acryloyl chloride with 4-
2007). Function of the preparation method, gelatin is phenylazophenol in the presence of 4-N,N-
characterized by different physical properties and dimethylaminopyrydine and
isoelectric points. The ability of tuning the electric dicyclohexylcarbodiimide (Neises and Sterlich,
properties of gelatin has contributed to the 1978). The compound was purified by thin layer
understanding of the concept of sustained release of chromatography technique on silica gel using a
proteins from polymer matrices (Young et al., 2005). mixture of 20/1 dichloromethane and ethyl acetate as
Because the physical network of gelatin hydrogel is eluent. Type A gelatin (G2500) was acquired from
destroyed around 30°C, crosslinking agents are Aldrich, Steinheim, Germany and used as received.
necessary for 3D-system stabilization. There are three The linear polysiloxane was prepared in
important methods to prepare gelatin carriers: gelatin agreement with ref. (Kazmierski et al., 2004). A two-
microspheres, gelatin block hydrogels and porous step reaction was employed for the modification of
gelatin block hydrogels (Hosaka et al., 2004; Kang et azo-polysiloxanes with nucleobases, starting from a
al., 1999; Yamamoto et al., 2000). Two types of polysiloxane containing chlorobenzyl groups in the
crosslinking agents can be used: non-zero length and side-chain (Fig. 1). In the first reaction step, the
zero-length (Kuijpers et al., 2000). A major problem polysiloxane was modified with sodium salt of 4-
arising when chemical crosslinking agents are used is hydroxyazobenzene (50–60% substitution degree)
the total elimination of the unreacted products. and, in the second step, the unreacted chlorobenzyl
Here in we propose a new system based on groups were substituted with adenine (Sample 1) or
gelatin and different polysiloxanes containing azo- thymine (Sample 2). The polymers were characterized
benzene groups in the side-chains, with potential by 1H-NMR, details concerning polymer synthesis and
applications as drug release systems. Due to the characterization being previously reported (Hurduc et
presence of azo-polysiloxanes sequences the al., 2007). The 1H-NMR spectra were recorded on a
modification of the diffusion rate inside the gelatin Bruker 400 MHz apparatus. SET-LRP (single electron
matrix under UV light irradiation is expected. The transfer - living radical polymerization) technique
azo-benzene groups undergo a specific behavior as a (Fig. 1) was used to obtain the graft azo-polysiloxanes
consequence of the azo-benzene groups’ trans-cis (Rusu, 2012a; 2012b; 2013). In a typical reaction 0.09
isomerization capacity under UV/VIS irradiation g bipyridyl were added to 0.1 g cyclic polysiloxane
(Moleavin et al., 2011; Rau, 2003). The geometrical macroinitiator previously dissolved in 1.5 mL DMSO.
modifications of the azo-groups are accomplished by The reaction mixture was introduced in a 25 mL flask
strong alteration of the dipole-moment (in the case of where monomers (0.1 g of azo-methacrylate
unsubstituted azobenzene from 0.1 D to 3.5 D) that (AZOMA), 0.5 g of N,N-dimethyl acrylamide
will also influence the diffusion process inside the (DAM), 0.5 g of butyl acrylate (BA)), and Cu wire
material. (0.25 g) were added. The system was degassed by five
Two different azo-polymers structures mixed freeze–pump–thaw cycles. The flask was heated at the
with gelatin were investigated: azo-polysiloxane reaction temperature (80 °C) and the synthesis was
modified with adenine or thymine and azo- performed under nitrogen atmosphere and stirring, for
polysiloxanes grafted with poly(dimethyl acrylamide) 8 h. At the end of the reaction, the mixture was diluted
and poly(butyl acrylate) segments. A rheological with CHCl3 and the catalyst was removed by passing
method was used to evaluate the composites behavior the solution through a basic alumina column. The
under UV light irradiation. Following the UV purified solution was then precipitated in diethyl ether,
irradiation a shift in the temperature corresponding to washed three times with the same solvent, and dried
the gel network destructuration, from 30°C under vacuum (Sample 3).
(corresponding to gelatin) to 40 °C (for gelatin-
polymer composite) was evidenced. 2.2. Methods
1722
Physical networks based on gelatin and azo-polysiloxanes
Fig. 1. Synthesis of azo-polysiloxanes modified with nucleobases (A) and of graft polysiloxanes (B)
Afterwards, the mixture was cooled at 35 °C (Vanier, QC, Canada), using a 100 W lamp able to
and introduced between the plates of the rheometer deliver UV light of 365 nm using a Mercury bulb.
measuring system. The rheological properties were The UV/Vis kinetic studies in THF solution
investigated using an Anton Paar Physica MCR 501 were carried out using a Shimadzu spectrophotometer
rheometer equipped with a Peltier system for the (Shimadzu UV 1700 Pharma Spy, Kyoto, Japan). The
temperature control. The temperature can be adjusted azo-polymer solutions were irradiated using a UV
between -40 and 200 °C. Measurements were carried lamp (50 W) equipped with 365 nm filter. The
out using parallel-plate geometry (Danu et al., 2012). isomerization kinetics of azobenzene can be
Firstly, a strain sweep was performed to establish the investigated due to the strong absorption peaking at
limits of the linear viscoelastic range (LVE) and then 350 nm, attributed to the π-π* transition of the
temperature tests were carried out at constant azobenzene chromophore. During UV irradiation at
oscillation amplitude (γ = 0.5% situated in linear 365 nm the absorbance corresponding to the π-π*
viscoelastic range) and frequency (f = 1Hz). The transition strongly decreases, permitting to calculate
temperature had been varied between 10 and 100 °C the trans (respectively cis) content of the azo-groups.
with a heating rate of 0.5 °C /min. Simultaneous UV
irradiation and rheological studies could be performed 3. Results and discussion
using an advanced UV system, under a Peltier
controlled P-PTD-UV chamber on Physica MCR 501 The main characteristics of the synthesized
rheometer. As measuring system a 43 mm parallel modified azo-polysiloxanes are presented in Table 1.
glass plate fixture was used. The UV source was the The polymers’ molecular weights (Mn) were
Omnicure Series 1000 manufactured by EXFO calculated using 1H-NMR spectra.
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Epure et al./Environmental Engineering and Management Journal 17 (2018), 7, 1721-1728
The chemical structure of the obtained It was also noticed that the trans-cis
polymers was confirmed by NMR spectroscopy using conversion rate of the azo-groups is influenced by the
CDCl3 as a solvent, at room temperature. If we refer substituted molecule. Likely due to the smaller size of
to Sample 3 in a typical 1H-NMR spectrum we can thymine comparing with the adenine, the structures of
identify: the signal corresponding to the methyl groups Sample 2 are possibly more compact than Sample 1.
(CH3-Si-) from polysiloxane (reference signal for The 60% conversion rate of sample containing
polysiloxane structural unit) at 0.1 ppm, the thymine may be due to the steric hindrance caused by
characteristic signal for the methyl groups (-CH3) the network density (Resmerita et al., 2010). The
corresponding to the poly (butyl acrylate, BA) evaluation of the rheological properties as a function
segment at 0.9 ppm, the signal for (-CH2-CH2-) groups of temperature evidenced the existence of interactions
at 1.5 ppm and (-CH2-O-CO-) signal present at 4 ppm between gelatin and azo-polysiloxanes, the addition of
. The signal corresponding to the methyl groups of modified polymers having significant influence on the
dimethyl acrylamide (DAM) is present at 2.9 ppm. network formation and stability. A 5% gelatin solution
The signals corresponding to the azo-groups are found in water was used as reference for the temperature
in the domain 7.5 - 8.0 ppm. sweep tests. From Fig. 3a the destructuration process
Firstly, the photochromic behavior of the of the physical network corresponding to gelatin (5%
azo-polymers under UV irradiation was investigated. in water) can be evidenced at 30°C, in agreement with
Fig. 2 presents the kinetic curves of the irradiation literature data (Benton et al., 2009). For temperatures
process. Evidently, the polymers response in solution under 30°C, a stable gel structure is developed with
is very fast, less than 2 minutes of UV irradiation the storage modulus G’ higher than the loss modulus,
being necessary to obtain the maximum value of cis- G”. Increasing temperature, the physical bonds
group. In these circumstances 5 minutes of UV between chains are broken and the system turns liquid
exposure were selected for the rheological with G’<G”.
experiments.
Fig. 2. Polymer response after UV irradiation: (a) Sample 1; (b) Sample 2; (c) Sample 3
1724
Physical networks based on gelatin and azo-polysiloxanes
This particular behavior of gelatin networks flexibility and stability of the resulted system is
turning from solid-like to liquid-like behavior by increased (Fig. 3d).
changing temperature can be exploited for the The non-covalent interactions type π-π staking
controlled release of active principles, but the and hydrogen bonding (Mignon et al., 2005) are
characteristic temperature of phase transition is too responsible for the different behaviors of the samples
low. The idea is to bring this temperature closer to the containing nuceobases moieties when geometrical
physiological temperature. conditions are accomplished. Different factors
The polymer addition into gelatin network does (nucleobases type, main chain conformation, network
not significantly modifies the destructuration density) lead to the development of physical
temperature, but in the case of Sample 1 considerable interactions makeing this mechanism more
differences in curves profile were evidenced (Fig. 3b): complicated than in case of solitary nucleobases. The
an increase in both dynamic moduli can be observed possibility of thymine dimers formation (Li et al.,
starting with 40°C, followed by a stabilization of the 2008; Goodsell, 2001) explains the higher stability of
values, two orders of magnitude lower as compared Sample 2 as compared with Sample 1.
with the initial one. Over 60°C some kind of stable The next step was to investigate the influence
week gel structure is formed. The purine structure of of the trans-cis isomerisation of included modified
adenine may be responsible for the complex azo-polysiloxanes on the rheological properties of the
rheological behavior of Sample 1. gelatin networks. The samples were irradiated for 5
In the case of Sample 2 added into gelatin minutes before running the temperature sweep tests,
network (Fig. 3c) more stable and flexible structure at enough time for the complete isomerization of the azo-
higher temperatures can be observed. The rheological groups, according to the kinetic curves of the
behavior of the gelatin network incorporating a irradiation process. As expected a shift towards higher
polysiloxane grafted with thermo-sensitive segments values in the specific phase transition temperatures
(Sample 3) is very similar to pure gelatin, but the was noticed for all samples (Fig. 4).
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Epure et al./Environmental Engineering and Management Journal 17 (2018), 7, 1721-1728
Fig. 4. The influence of UV irradiation on rheological properties of gelatin network incorporating modified azo-polysiloxanes;
(a) 5% gelatin in water with Sample 1, (b) 5% gelatin in water with Sample 2, (c) 5% gelatin in water with Sample 3
1726
Physical networks based on gelatin and azo-polysiloxanes
temperature dependent behavior. Moreover, the UV Ferruti P., Marchisio A., Duncan R., (2002), Poly(amido-
irradiation of the modified systems allows the increase amine)s: Biomedical Applications, Macromolecular
of the phase transition temperature bringing it closer Rapid Communications, 23, 332-55.
to the physiological temperature. In this way the Garcia-Amorós J., Sanchez-Ferrer A., Massad W.A, Nonell
S., Velasco D., (2010), Kinetic study of the fast thermal
systems become suited for the use as drug release cis-to-trans isomerization of para -, ortho - and
systems and the entities included in the azo-polymers polyhydroxyazobenzenes, Physical Chemistry
can determine specific behaviors. Chemical Physics, 12, 13238–42
Goodsell D.S., (2001), The Molecular Perspective:
4. Conclusions Ultraviolet Light and Pyrimidine Dimers, The
Oncologist, 6, 298-9.
New systems based on gelatin and three Gupta S., Tyagi R., Parmar V.S., Sharma S.K., Haag R.,
different polysiloxanes containing azo-benzene (2012), Polyether based amphiphiles for delivery of
groups in the side-chain with potential application as active components, Polymer, 53, 3053-78.
Hosaka A., Koyama H., Kushibiki T., Tabata Y., Nishiyama
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methods combined with UV irradiation. (2004), Gelatin hydrogel microspheres enable pinpoint
The experimental results proved the existence delivery of basic fibroblast growth factor for the
of interactions between gelatin and polysiloxanes development of functional collateral vessels,
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between molecules are generated. Moreover, after the Nguyen A.V., (2007), Nucleobases modified azo-
UV irradiation of the azo-molecules, dipol-dipol polysiloxanes, materials with potential application in
interactions are changing the physical proprieties of biomolecules nanomanipulation, Journal of Polymer
gelatin network. The increase in the values of G’ and Science Part A: Polymer Chemistry, 45, 4240-8.
G” is a consequence of system restructuration leading Janes K.A., Calvo P., Alonso M.J., (2001), Polysaccharide
to more organized architectures able to release the colloidal particles as delivery systems for
macromolecules, Advanced Drug Delivery Reviews, 47,
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polysiloxane structure, the destructuration Kang H.W., Tabata Y., Ikada Y., (1999), Fabrication of
temperature of the composite can be tuned in the porous gelatin scaffolds for tissue engineering,
domain 30-40 °C. Biomaterials, 20, 1339-44.
Kazmierski K., Hurduc N., Sauvet G., Chojnowski J.,
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1728
Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1729-1741
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Tiberiu Rusu1∗, Ciprian Cristea2, Tudor Rusu1, Ileana-Codruţa Groze3, Laurenţiu Stoica4
1TechnicalUniversity of Cluj-Napoca, Department of Environmental Engineering and Sustainable Development
Entrepreneurship, 103-105 Muncii Ave, Cluj-Napoca, Romania
2Technical University of Cluj-Napoca, Department of Electrical Machines and Drives, 26-28 G. Bariţiu Street,
Cluj-Napoca-, Romania
3Babeş-Bolyai University, Faculty of Environmental Science and Engineering, 30 Fântânele Street, Cluj-Napoca, Romania
4Technical University of Cluj-Napoca, Department of Manufacturing Engineering, 103-105 Muncii Ave, Cluj-Napoca, Romania
Abstract
A judicious use of energy is a fundamental factor to achieve sustainable development. The limited character of energetic fossil
resources and the pollution generated by burning fossil fuels for electricity production generate the need to replace them with other
sources of energy. Despite the fact that fossil fuels would continue to play a prevailing role in the energy supply for decades to
come, renewable energy resources have the potential of contributing to the increasing global energy demands, while simultaneously
emerge the most efficient solutions for clean and sustainable energy development in the world. In this framework, the main scope
of the present study is to provide an analysis of the current state of world natural resources used to produce energy and energy
consumption degree across different regions of the world. At the same time, this paper aims to compare the environmental impacts
in water, air, soil and ecosystem produced by a range of conventional and renewable energy sources, which is necessary to be
reduced for building a genuine low-carbon society.
Received: August, 2014; Revised final: September, 2014; Accepted: November, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: tiberiu.rusu@sim.utcluj.ro
Rusu et al./Environmental Engineering and Management Journal 17 (2018), 7, 1729-1741
energy (wind energy, solar energy, geothermal energy, synthesis clearly and meticulously gathered from the
hydroelectric energy) (Axinte et al., 2015; Boyle et al., sources mentioned above is proposed by the authors,
2003; Casper, 2010; Grübler and Fisk, 2012; Tong, along with a pertinent analysis of results.
2010; Zaharia, 2004). There are many definitions of
sustainable development, including the following 2. Urban-industrial systems
common one: “development that meets the needs of
the present without compromising the ability of future Urbanization and economic growth are
generations to meet their own needs” (Bruntland, inextricably linked. Globally, there is no country that
1987). has reached middle-income status without a
Due to the rapid development of the global substantial population shift into cities (Hughes and
economy, energy demand has grown quickly, Cain, 2003). Studies have revealed that the simple
particularly in emergent countries, which tend to have correlation coefficient across countries based on the
a greater part of their economies in manufacturing percentage of urban residents in a country and gross
industries. Fossil fuels supply the majority of energy domestic product (GDP) per capita is of about 0.85
needs worldwide, with 86.7 percent of global energy (Henderson, 2003), fact that leads to the conclusion
consumption in 2013 (BP, 2014). A recent World that urbanization is an inevitable part of a modern
Energy Council study found that without any change society. Cities generate about 80 percent of world’s
in our current practice, the world energy demand in GDP (Grubler and Fisk, 2012). The world’s GDP is
2050 would be 50 percent higher than 2013 level, at expected to rise by an average of 3.6 percent per year
least 80 percent of this increase is anticipated to come from 2010 to 2040, particularly in emerging, non-
from developing countries (WEC, 2013). Because the OECD regions, where it increases by 4.7 percent per
fossil fuel resources required for the generation of year. This increase drives the sustained growth in
energy are expected to dominate the global future energy consumption, based mostly on fossil
consumption of energy resources in the coming years, fuels, which in turn plays a key role in the upward
as well as because these are becoming scarce, trend in CO2 emissions (EIA, 2013). However,
alternatives that would be viable and regenerative to relatively high levels of urbanization do not always
attain sustainability have to be explored (Shamsuddin assure high levels of economic welfare in developing
et al., 2014). In this regard, renewable energy countries. This is most evident in Latin America where
resources represent one of the most efficient solutions the urbanization levels are above 80%, yet with real
to environmental problems that are faced today by per capita incomes and GDP about a third that of
humanity. developed nations (UNEP, 2012).
The renewable energy technologies are In the present era of rapidly growing
recording significant worldwide growth due to development, urban sustainability is threatened by
declining costs of generation, increasing electricity complex global uncertainty and change which have
demand and the environmental concerns, especially broad range, and threaten multiple sectors – such as
those concerning climate change. According to water, energy, transport and waste – that are critical
Bloomberg New Energy Finance (BNEF, 2014), for urban sustainability (MGI, 2011). The urban
global investment in clean energy was $254 billion in population growth rate is superior to that of the total
2013, almost five times the total of $54 billion in 2004. population. As can be noticed in Table 1 not all
Natural resources exploitation represents a key factor regions around the world have reached the same level
of economic growth and development, but is of urbanization (United Nations, 2014).
important to consider the consequences of potential Rosenthal and Strange (2004) show that
irreversible changes that may occur to the doubling city size increases productivity across
environment (Bond et al., 2003; Zaharia, 2004). industries in the United States by roughly 5 percent.
Sustainable development and natural resources are Similar work for Europe finds the impact of density to
indissoluble related with the social, economic, be comparable (4.5 percent).
technological development, and environmental
protection. The economic competitiveness and Table 1. Percentage of urban areas around world’s major
ecological sustainability are complementary aspects of regions (United Nations, 2014)
current society’s common goal (ASCE, 2010). In this Region 1950 1970 2014 2050
context, the main scope of this paper is to analyze and Africa 14.1 23.5 40 56
compare the current state of natural resources used Asia 17.5 23.7 48 64
worldwide to produce energy, in terms of their Europe 51.3 62.8 73 82
potential of contributing to climate change mitigation Latin America 41.4 57.1 80 86
and sustainable development, as well as to review the North America 63.9 73.8 81 87
environmental impact assessment for water, air, soil Oceania 62.4 71.2 71 74
and ecosystem for a range of conventional and
renewable energy sources. Currently, urban areas generate 60-80 percent
This paper is based on data sources including of all greenhouse gas emissions and consume 75
peer-reviewed papers, state and agency reports, non- percent of natural resources (UNEP, 2012). Therefore,
governmental organizations’ reports, and recent it can be asserted that urbanization has enormous
statistical data and reviews. A unitary manner of data environmental consequences, putting pressure on
1730
Energy sources analysis from the perspective of sustainable development
energy and water resources; thus it can be stated that energy, a recent statistic (United Nations, 2014)
sustainable cities are going to be vital for the future, as regarding world energy consumption in 2011 per
urbanization expands. world’s regions is presented in Table 3. It can be
noticed that world's largest energy consumer is Asia
3. Fundamental natural resources Pacific region, accounting for 40.5 percent of the
global energy consumption and over 70 percent of the
Natural resources are regarded as “fixed global coal consumption. Asia Pacific was also an
endowments”, being used to fuel industrial undisputed leader in oil and hydroelectric
economies. Environmental pollution became an consumption. Europe and Eurasia is the leading region
important global concern because of the rapid growth for nuclear power consumption, natural gas and
of industrialization and urbanization. The intensive renewable energy (BP, 2014). Table 3 shows a
exploitation of fundamental natural resources (water, significant disparity between the highest per capita
air, land, ecosystems) contributed in disturbing the energy consumption region and the lowest, reflecting
ecological balance and the environmental quality disparities of development between various regions in
(Fulekar, 2010). In this section the main energy the world.
sources are being discussed. According to IEA (2011), in the last three
decades the per capita energy consumption increased
3.1. Energy production sources – generalities about 10 percent while world population increased 27
percent. Middle East recorded the most significant
Smalley (2004) stated that the growing energy growth of energy consumption per capita, with 170
demand of the world is going to need a new sustainable percent. By 2035 in industrialized regions, such as
energy source. The risk of catastrophic climate disruption North America, the energy use per capita is estimated
increases due to anthropogenic impact on the environment, to decline at an annual average of 0.5 percent per year
especially the changes of the Earth atmosphere because the population rate growth is going to be
composition (the concentration of CO2, N2O, CH4). higher than the energy use rate. In developing regions
Several studies report that CO2 is the primary such as East and South-East Asia, by 2035, the energy
greenhouse gas emitted due to human activities. Fossil use per capita is estimated to rise at an annual average
fuels combustion in the electricity generation process is of 3 percent per year (IEA, 2011).
the largest source of CO2 emissions in the world (IEA, According to Observ’ER (2013), the structure
2011). Globally, the atmospheric CO2 concentration for of electricity production from renewable sources in
July 2014 was 399 ppm far above the maximum CO2 2012, was as following: the main source was
concentration of about 280 ppm registered before the hydroelectricity with a 78% share; wind power
Industrial Revolution in the 19th century; today’s rate of reclaimed the second place summing 11.4% of the
increase is more than hundred times faster than the renewable total. It is essential to mention that in 2002
increase that took place when the last ice age ended wind power generated was 52.5 TWh and in 2012 the
(Scripps Institution of Oceanography, 2014). same source generated 543.3 TWh, an increase of over
Nonetheless, globally, the energy systems are ten times. These were followed by biomass power
at different stages of development and also at different (6.9%), solar power (2.2%), geothermal power (1.5%)
stages of achieving sustainability. According to the and marine energies (0.01%).
World Energy Council (WEC) the energy
sustainability is based on three core dimensions: 3.2. Energy production sources analysis
energy security, social equity and environmental
impact mitigation (WEC, 2012). During the last In 2012 (Observ’ER, 2013) world energy
century, the world energy consumption has increased production summed 22613 TWh, from which the
significantly. Table 2 shows the world energy renewable electricity production weighted in with
consumption during the last four decades in relation 4699.2 TWh, representing 20.8% of 2012 yearly total.
with the world’s population. Also, presented are data Fossil fuels generated 15394.3 TWh, representing
regarding the world carbon dioxide emissions due to about 68% of global electricity production. The other
oil, gas and coal consumption and the main energy conventional source, the nuclear fission generated
carriers. In order to highlight the importance of about 11% of electricity production.
Table 2. Global energy consumption [tons oil equivalent] and CO2 Emissions (BP, 2011)
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Rusu et al./Environmental Engineering and Management Journal 17 (2018), 7, 1729-1741
Table 3. World energy consumption at the end of 2013 (BP, 2014; United Nations, 2014)
Source of energy
C [t oil
Region Natural Nuclear Hydro-
Oil Coal Renewable * Total equivalent/capita]
gas energy electricity
Europe and Eurasia 878.6 958.3 508.7 263 201.3 115.5 2925.3 3.33
North America 1024.2 838.6 488.4 213.7 156.3 65.4 2786.7 5.78
Africa 170.9 111 95.6 3.1 25.7 1.7 408.1 0.36
Latin America 311.6 151.8 29.2 4.7 158.1 18.3 673.5 1.34
Middle East 384.8 385.5 8.2 0.9 5.7 0.2 785.3 3.38
Asia Pacific 1415 575.2 2696.5 77.8 308.7 78.2 5151.5 1.28
Total 4185.1 3020.4 3826.7 563.2 855.8 279.3 12730.4 1.76
Consumption by
32.87 23.73 30.06 4.42 6.72 2.19 100 -
fuel [%]
*
includes wind, geothermal, solar, tidal energy etc.
Fig. 1 presents in points A, B, C and D, the 2013) and is expected to increase by close to 18
global cumulative installed wind power, geothermal, million barrels/day over the period 2014-2035,
solar and nuclear capacity. reaching almost 107.3 million barrels/day by 2035
(OPEC, 2012). Coal is currently the second largest
3.2.1. Fossil fuel energy source of primary energy worldwide. Likewise, coal is
Currently, fossil fuels represent the cornerstone powering the largest growing economies because it is
of global electricity production with more than two- widely distributed across the globe, abundant,
thirds of the total. Fossil fuels grew between 2002 and accessible and it is also the least subsidized of all fuel
2012 from a 64.99 percent share to a 68.08 percent sources (WEC, 2013). Natural gas is expected to play
share (Observ’ER, 2013). The main fossil fuel an increasingly important role in meeting the energy
reserves are unevenly distributed on Earth due to the demand in the world. At the moment there is an
geologic history of the areas. This is presented in important potential for shale gas, but are considerable
Table 4. The global oil demand was estimated to uncertainties about the size of the resources and the
average 89.7 million barrels/day in 2013 (OPEC, economics of developments (OPEC, 2012).
66,000
282,587
50,583
Direct uses capacity [MWth]
198,001
CAPACITY [MW]
CAPACITY [MW]
120,624
27,825
73,938
15,200
47,620
11,224
10,906
8,664
31,100
8,064
8,933
7,072
7,972
17,400
6,833
5,834
10,200
4,794
1,950
1,300
2,110
6,100
3,490
2,510
1,180
1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 1975 1980 1985 1990 1995 2000 2005 2010 2012
YEAR YEAR
(a) (b)
328,000
340,000
349,000
368,000
375,000
364,000
196
172
135,000
147 152
128
98.4 111 102
71,000
69.7
47.6 55.2
16,000
40
4,800
23.2
9.4 15.8
830
Year YEAR
(c) (d)
Fig. 1. Global cumulative installed wind power, geothermal, solar and nuclear capacity (modified after GWEC, 2014; GEA, 2013;
IEA, 2011-2013; EPIA, 2014; IAEA, 1960-2012): (a) Global cumulative installed wind power capacity; (b) Global geothermal
installed capacity; (c) Global solar installed capacity; (d) World nuclear installed capacity
1732
Energy sources analysis from the perspective of sustainable development
The global natural gas demand is estimated to 2013; wind is meeting 8% of Europe’s electricity
increase by 2.4% per year to reach 3962 billion cubic demand (GWEC, 2014). In 2030 the global
meters in 2018, at a barely slower rate than coal (2.6% cumulative capacity for installed wind power is
per year) but faster than oil (0.7% per year) (IEA, estimated to reach 917798 MW, Asia is expected to be
2013). Despite the shale gas revolution in the United the global leader with a 41% share (GWEC, 2012).
States where over the past years took place a switch
from coal to natural gas in power generation, the use 3.2.4. Geothermal energy
of coal is expected to rise by over 50 percent by 2030, Geothermal resources consist of thermal
especially in developing countries that face major energy from the Earth’s interior stored in both rock
challenges in providing energy to their populations, and trapped steam or liquid water. Resource utilization
and is expected to replace oil as the world’s largest technologies for geothermal energy can be grouped as
source of primary energy (WEC, 2013). types for electrical power generation, for direct use of
the heat, or for mixed heat and power in cogeneration
3.2.2. Hydroelectric energy applications (Goldstein et al., 2011). In Fig. 1b is
Hydropower is a renewable energy source presented the global evolution of geothermal power
based on the natural water cycle. To meet the and geothermal direct use during the last 37 years. A
increasing world electricity demands the electricity significant development is observed. In 2012 the
generation from hydropower produces about 16 installed electric capacity was almost ten times larger
percent of the world electricity. During 2012 an than that of 1975, and the installed capacity of direct-
estimated 30 GW of new hydropower capacity came use geothermal energy in 2012 was 50 times more than
on line, about 51% of it was in China. In 2012 the that of 1975s.
world production of hydroelectricity reached 3748 Asia is the leading market for geothermal
TWh/year, three times more than that of 1970s. Table power having about 44 percent of the global
5 presents the hydropower technical potential in terms geothermal installed capacity (11765 MW) in August
of installed capacity, undeveloped potential for 2012 2013 (GEA, 2013). By 2050 geothermal deployment
and estimated for 2035. is estimated to generate 1180 TWhe/yr for electricity,
Hydropower is the largest current source of representing more than three percent of global
renewable energy in the electricity sector with a electricity demand, and 2100 TWhth/yr for heat
significant potential. It is noticed that the percentage applications, representing about five percent of global
of undeveloped potential range from 18.35% in heat demand (Goldstein et al., 2011). Although the
Europe to 93.28% in Africa, indicating a lot of world’s geothermal resources are immense and
opportunities for hydropower development in the ubiquitous, it is difficult to accurately determine the
world. global geothermal resource potentials, mostly because
the technologies used are continuously evolving (INL,
3.2.3. Wind energy 2006).
Wind energy has been used by humankind for
thousands of years, at the beginning it was used to 3.2.5. Solar energy
provide mechanical energy and currently to provide Solar energy is the most abundant of all energy
electricity. It has been estimated that the available resource on Earth. Annually, the total amount of solar
wind power that can be converted into other forms of radiation falling on Earth is more than 7500 times the
energy is about 1.26x109 MW. Due to the fact that this world’s annual primary energy consumption of 500 EJ
value represents 20 times the rate of the present global (WEC, 2010). The most widely used solar
energy consumption, wind energy could meet the technologies are solar photovoltaic (PV) systems and
entire global needs (Tong, 2010). Fig. 1a shows the solar thermal power plants. In Figure 1c it is shown,
evolution of global cumulative installed capacity of globally, the evolution of solar photovoltaic systems
wind power during the last two decades. A spectacular and solar thermal power plants during the last decade,
increase of the cumulative installed capacity being noticed a substantial development. At the end of
worldwide can be noticed; in 2013 was 126 times 2012, Asia (especially China) was the undisputed
larger than that of 1992. Europe was the global leader global leader in solar thermal energy with a 67 percent
in wind energy technology use. Almost 39% of the share, followed by Europe with 16 percent share (IEA,
world capacity was installed in Europe by the end of 2014).
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Rusu et al./Environmental Engineering and Management Journal 17 (2018), 7, 1729-1741
Table 5. Regional hydropower technical potential and hydroelectricity generation (Kumar et al., 2011; Rajgor, 2013).
Table 6. Technical potential of biomass plantations worldwide (Chum et al., 2011; Fisher et al., 2009)
Total grass- and woodland Unproductive or very low productive Bioenergy area Technical Potential
Region
area [Mha] areas [Mha] [Mha] [EJ/yr]
Europe and Russia 902 618 122 17
North America 659 391 111 19
Africa 1086 386 275 69
Latin America 765 211 160 45
SE Asia 556 335 14 4
Pacific OECD 515 332 97 17
Middle East and N
107 93 1 0.2
Africa
World 4605 2371 780 171
1734
Energy sources analysis from the perspective of sustainable development
The growth stagnated in the 1990s due to (MGI, 2011). Energy and water are intricately
increased concerns about safety following the connected. Electricity generating technologies use
Chernobyl accident, and even more in the 21st century water for different production processes throughout
due to the Fukushima accident (Hernández- Ceballos the entire lifecycle. For assessing the impact regarding
et al., 2012), but also due to a return to lower fossil freshwater use two aspects are analyzed: “withdrawal”
fuels prices. By the year 2030, world nuclear capacity (the water removed from the ground or diverted from
is expected to grow between about 540 GW net in low a water source for use) and “consumption” (the water
demand case and 746 GW net in the high demand case, evaporated, transpired, incorporated into products or
especially in Asia (OECD, 2012). Currently, nuclear crops, or otherwise removed from the immediate
and hydropower are the only low-carbon sources, water environment) (Kenny et al., 2009).
providing significant amounts of energy. Energy The electrical energy necessary for economic
generated from nuclear plants avoids annual CO2 growth requires massive withdrawals of water. Table
emissions of about 2.9 billion tones compared to coal- 7 presents the median lifecycle uses of water for
fired generation (IEA, 2010a, c). Although a generally conventional and renewable electricity generation
high security standard is required as accidents can technologies.
happen with devastating consequences for human
beings and for the ecosystem. Therefore deployment Table 7. The average water footprint for different
of nuclear energy should be preceded by complex electricity generation technologies (adapted upon Fthenakis
comparative analyses of all available options (Vujic et and Kim, 2010; Macknick et al., 2011; Wilson et al., 2012)
al., 2012).
Electric fuel Water footprint [l/MWh]
Coal 63382
4. Energy production and environmental impact
Hydroelectric 1699649
assessment Natural gas 26986
Nuclear 68191
A major objective of sustainable development Geothermal 5823
is to guarantee environmental quality. However, an Solar PV 882
ideal energy production technology that is at the same Wind 234
time environment-friendly, risk-free and cost- Biomass 46984
effective does not exist. Every technology deployment
implies some trade-offs to be made, in order to ensure Wind and PV technologies are by far the most
optimal use of energy resources, while restricting “water-friendly” energy options (their lifecycle
environmental and health impacts (Vujic et al., 2012). median water usage ranging from 234 to 882 l per
The goal of this section is to review the MWh produced) while hydropower, coal and nuclear
environmental impact assessment for water, air, land have the largest water use (ranging from 63382 to
and ecosystem for different types of electricity almost 1.7 million l per MWh).
generation sources. Considering that most of the energy is
generated by conventional technologies that require
4.1. Environmental impact assessment for water in large volume of water flows, energetic efficiency and
case of energy production water conservation programs are essential for
protecting the freshwater resources from the impact of
Currently, worldwide, industry accounts for 20 electricity production. Instead of altering the site’s
percent of all water consumption, compared to 70 hydrology and ecosystems, technologies like solar PV
percent for agriculture and 10 percent for domestic use and wind, which are highly sustainable with respect to
(UNESCO, 2012). water consumption, should be implemented at larger
The global average water footprint related to scale (Wilson et al., 2012).
consumption was 1385 m3∕y per capita over the period
1996–2005 (Hoekstra and Mekonnen, 2012); the 4.2. Environmental impact assessment of air in case of
water footprint is one of the most used indexes when energy production
analyzing the relationship between the total amount of
fresh water that is used to produce the goods and This section reviewed available estimates for
services consumed by the inhabitants of a nation. major air pollutants that are emitted by renewable and
However, freshwater withdrawals have tripled over non-renewable electricity generation sources. These
the last 50 years. Globally, the annual population include CO2 emissions, nitrous oxides (NOx), sulphur
increase of 80 million per year implies an increased dioxide (SO2) and particulate matter (PM) emission.
demand for freshwater of approximately 64 billion All these cause negative impacts on human health and
cubic meters a year. Considering that there would be the ecosystems’ quality.
an additional 1850 cubic kilometers of water Lifecycle greenhouse gas emissions intensity
consumption by 2030, 30 percent higher than today’s in electricity generation depends on the source used. It
level, more sustainable water use programs have to be is necessary to be evaluated not only the emissions
implemented, especially in the regions with rapid exhausted during the generation of electricity, but also
population growth and with growing water stress emissions from upstream processes (fuel exploration,
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Rusu et al./Environmental Engineering and Management Journal 17 (2018), 7, 1729-1741
mining, fuel transport, plant construction), as well as tons of CO2/GWh depending on the combustion
downstream processes (decommissioning, waste efficiency, power rate, type of feed. The majority of
management and disposal), in order to assess the emissions arise during the upstream processes (Chum
impact of the power generation sources (Weisser, et al., 2011). Lifecycle NOX emissions are about 5
2007). Fig. 2 illustrates a comparison of greenhouse g/kWh, SO2 emissions are approximately 2.5 g/kWh
gas emissions, normalized in tones of CO2 equivalent and PM emissions are about 0.5 g/kWh (Bauer, 2008;
per GWh, for different electricity generation sources. Sathaye et al., 2011). For nuclear energy, the majority
of greenhouse gas emissions occur upstream of
operation, depending on the enrichment process. NOX,
SO2 and PM emissions are negligible (Sathaye et al.,
2011). Lifecycle greenhouse gas emissions from
hydropower projects range between 1-34 tones
CO2/GWh, depending on type of the plant (reservoir
or run-off), its size and usage as well as the electricity
mix used for its operations (Weisser, 2007). Lifecycle
NOX, SO2 and PM emissions are negligible (Sathaye
et al., 2011). Wind energy is currently the most
environmental friendly technology with the median of
greenhouse gas emissions at 12 tones CO2/GWh, 83
times less than coal fired power plants (Stacey and
Fig. 2. Lifecycle greenhouse gas emissions from different
Garvin, 2012). Lifecycle NOX, SO2 and PM emissions
electricity generation sources (adapted upon Chum et al., are negligible (Sathaye et al., 2011).
2011; Goldstein et al., 2011; Hsu et al., 2012; Stacey and Hence, for reducing greenhouse gas emission
Garvin, 2012; Weisser, 2007; WNA, 2011) from electric power generation is required a
substantial increasing of the share of total electricity
It is noticed that fossil fuel sources generate the generated from renewable source and improving
highest greenhouse gas emissions on a lifecycle basis, efficiency of existing power plants (Scripps Institution
ranging from 469 tones CO2/GWh (natural gas) to of Oceanography, 2014).
1001 tones CO2/GWh (coal). Most of lifecycle
greenhouse gas emissions for fossil fuels sources are 4.3. Environmental impact assessment for land use in
registered during the operation of the power plant. The case of energy production
emissions throughout downstream activities are
insignificant but during upstream activities may be In order to assess the land use impact of the
released considerable emissions depending on power generation sources, this has to be evaluated not
processes involved in extraction, fuel transportation only the land on which the power plant is situated, but
and fuel preparation (Weisser, 2007). Fossil fuel based also the impact of the full land use life cycle. Land
electricity production can be a major source of air transformation and land occupation are the main
pollution: NOX (lifecycle emissions ranging from 0.4 metrics used in the literature to describe and compare
g/kWh (natural gas) to 4 g/kWh (oil)), SO2 (lifecycle land requirement for different energy production
emissions ranging from 5 g/kWh (natural gas) to 27 sources. The former indicates the area of land altered
g/kWh (coal)), PM (lifecycle emissions ranging from from an original state, while the latter involves the
0.02 g/kWh (natural gas) to 2.3 g/kWh (coal)) (Bauer, duration over which the area of the transformed land
2008; Sathaye et al., 2011). returns to its reference state, measured as a product of
For geothermal plants, the greenhouse gas land area (m2) and time (year) (Koellner and Scholtz,
emissions are less than 50 tones CO2/GWh for flash 2007). Table 8 summarizes the land transformation
steam plants and less than 80 tones CO2/GWh for and land occupation for power production using
projected EGS (Enhanced Geothermal System) plants different conventional and renewable sources
(Goldstein et al., 2011). Lifecycle NOX emissions are (Fthenakis and Kim, 2009).
lower than 0.4 g/kWh. SO2 and PM emissions are It is noticed that land use impacts vary widely
negligible (Sathaye et al., 2011). between and within sources, also depending on
PV systems generate negligible greenhouse gas regional conditions. From Table 8, it is noticed that, as
emissions during the electricity generation. However, concerns the non-renewable sources, coal-fuel cycle
about 70 percent of emissions arise during upstream affects the land transformation pattern the most. The
processes, especially in the system components mining, beneficiation, and electricity-generation
manufacture (Hsu et al., 2012). Solar power stages can involve destruction of existing landscape,
equipment releases 50–1000 times less direct Hg soil erosion, land subsidence, water contamination,
emissions than traditional electricity generation land acidification, removal of vegetative cover and
(Turney and Fthenakis, 2011). In terms of NOx, SO2 topsoil (Fthenakis and Kim, 2009; Miranda et al.,
and PM emissions are negligible (Sathaye et al., 2003; Spath et al., 1999).
2011). As regards renewable sources, hydroelectric
Lifecycle greenhouse gas emissions from power plants affect the pattern of land transformation
bioenergy systems range between about 16 and 74 the most (Fthenakis and Kim, 2009). Nuclear power
1736
Energy sources analysis from the perspective of sustainable development
entails the lowest land transformed per unit of refineries, destroy habitats for animals and plants,
electricity. However, land transformed accidentally by affecting the biodiversity, due to the inability of many
disasters in the nuclear-fuel cycle can have dramatic species to survive in such conditions (Wake, 2005).
consequences. In November 2011, the Japanese Hydrocarbons-based energy sources impact
Science Ministry reported that the destruction of the maritime ecosystems through different ways. Seabird
Fukushima Daiichi nuclear power plant contaminated populations are vulnerable to the effects of oil and gas
more than 30000 square kilometers of land with pollution, especially from the surface oil pollution.
radioactive cesium (Ishizuka, 2011). Fish and shellfish populations, benthic communities
and plankton are vulnerable to impacts from
Table 8. Land transformation and land occupation hydrocarbon pollution, especially from hydrocarbon
for electricity production from different sources spills (BP, 2010; Karacik et al., 2009; Mosbech,
(Fthenakis and Kim, 2009) 2000). Studies have shown that new road building,
pipeline construction and expanding drilling
Energy Land transformation Land occupation operations disrupt migration, habitat, and wintering
source [m2/GWh] [m2/GWh] grounds for many wildlife species (EPA, 2008; Riley
Coal 239-489 1290-25200 et al., 2012). Coal mining causes extensive
Natural degradation to natural ecosystems, reducing the
265 4200
gas number of tree species in the mined areas and
Nuclear 109-124 300000
impairing the plant diversity (Sarma et al., 2010). The
Solar PV 164-552 9900
environmental impacts of coal mining-derived runoff
Wind 1030-3230 2040
Hydro 2350-25000 100000
(e.g., acid drainage) are severe, large scale, and long
Biomass 12550 380000 lasting, especially on aquatic fauna and flora
(Bernhardt and Palmer, 2011; Ochieng et al., 2010).
For non-renewable fuel cycles, such as coal Hazardous air pollutants emitted from fossil fuels-
and nuclear energy, the land occupation is dominated fired power plants deposit into rivers, lakes and oceans
by upstream and downstream processes. The full and are taken up by underwater fauna and flora. These
recovery of coal-mined lands is expected to be several pollutants lead to bioaccumulation of toxic metals,
hundred years (it would take 200–300 years before the environmental acidification, contamination of aquatic
composition of native forest to be reestablished life, can harm plants and the wildlife (EH&E, 2011).
(Burger, 2002). Hydropower, usually, requires the reservoir
As shown in Table 8, bioenergy requires the formation which involves special biotope and habitat
greatest land occupation (380000 m2 year/GWh) loss due to inundation, climate change and can cause
because of the need to cultivate feedstock. It has to be the relocation of communities living nearby the lake
noticed that inadequate land use change due to biofuel (Salvarli, 2006). When the oxygen-poor water from
production can aggravate soil and vegetation the bottom of the lake is released through a dam into
degradation associated with overexploitation of the river, downstream habitat condition change (e.g.,
forests, too intensive crop and forest residue removal it can kill fish that are accustomed to warmer, oxygen-
(Koh and Ghazoul, 2008; Robertson et al., 2008). rich water) (Hamilton, 2013). The construction of
Wind power-plants entail the lowest land occupation onshore wind farms alters ecosystems through the
per unit electricity. Moreover, wind farms can be clearing of vegetation and can lead to habitat loss and
located on low quality lands (e.g., brownfields or other fragmentation, especially on forested ecosystems
contaminated site), and often be used for a variety of (Katsaprakakis, 2012).
other productive purposes, including livestock Wind energy developments cause fatalities of
grazing, agriculture, highways, and hiking trails (Mai birds and bats through collision, being responsible for
et al., 2012; NREL, 2010). The assessment of 0.003 percent of bird mortalities caused by human
environmental impacts of land transformation and activities (EWEA, 2009). The construction of offshore
occupation is complex. Although hydroelectric energy wind farms may disturb benthic communities and
and bioenergy require large amounts of land, the other marine mammals, changing the existing biodiversity
renewable technologies, such as wind energy and solar in the area and creating a new local ecosystem
PV, involve similar or less disturbance of land than (EWEA, 2009). The construction of a geothermal
non-renewable sources (Fthenakis and Kim, 2009). plant and roads alters ecosystems through the clearing
of vegetation. During well testing, due to the noise,
4.4. Environmental impact assessment for the wildlife in the vicinity of the drill rig can be
ecosystem in case of energy production moderately affected (Noorollahi and Yousefi, 2003).
Solar PV may cause disturbance during the
In energy systems around the world changes, installation stage. Also the PV panels cast shadows
which will have implications for ecosystems and and may change the microclimate, causing an
livelihoods take place (Boyle et al., 2003). All energy unstudied effect on vegetation (Turney and Fthenakis,
sources affect the ecosystem. Although renewable 2011). Studies revealed that central concentrator
sources are significantly safer, they can have a power systems could pose a danger to birds
negative impact on the ecosystem. The constructions (OECD/IEA, 1998), and flying insects can also be
of fossil fuel-fired power plants, as well as oil burnt when flying in the vicinity of the reflector’s area,
1737
Rusu et al./Environmental Engineering and Management Journal 17 (2018), 7, 1729-1741
but the loss of the insect population is negligible technologies are not universally considered
(Tsoutsosa et al., 2005). sustainable due to the environmental and health
Diversion of crops into bioenergy production hazards they bring along, as shown from the recent
can influence food commodity prices and food accident in Fukushima Daiichi, which seems to have
security (Headey and Fan, 2008). Growing demand for halted their expansion.
bioenergy put pressure on the degradation and loss of Unlike bioenergy which requires the greatest
more remote habitats and landscapes (Firbank, 2008). land occupation, wind power plants entail the lowest
The insertion of invasive or genetically modified land occupation per unit electricity. Finally, in terms
species causes the decline of biodiversity, especially if of impact on the ecosystem, studies have shown that
forest, peat, grass and wetlands are used for feedstock the renewable technologies are considerably safer than
production and if large monoculture plantations are the conventional ones.
created (CBD, 2008; Sathaye et al., 2011). Regarding
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1743-1752
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Abstract
The aim of this study was to evaluate the content of Zn, Mn, Cu and Ni in the aboveground and underground shouts of Glyceria
maxima and in the bottom sediments of the Słupia River. These studies allow for assessment of the existing and potential hazards
resulting from toxic influence of heavy metals on water environment and human health. The concentration of research elements
was determined by atomic absorption spectrometry (AAS). Results indicate that the concentration of heavy metals in the examined
bottom sediments remained within the limits of the geochemical background for majority of the determined elements. The
concentrations of Zn and Cu, sporadically exceeded the level of the geochemical background at the stations in the central part of
the city, and in the case of Ni in all researched positions. Following the LAWA classification, the bottom sediments within the
Słupsk area were classified in the first class, as slightly contaminated. It was found the G. maxima underground sprouts accumulated
several times more of Zn, Mn, Cu and Ni than their aboveground sprouts. The indices of quality of the tested bottom sediments
and the enrichment factors of the sprouts with heavy metals indicate that the Słupia River is the least contaminated along the
segments of the river with a low or moderate transformation of the river bed and the largest load of Zn, Mn, Cu and Ni is found at
the stations with a high transformation of the river bed. The strong positive correlations between the concentrations of Mn in bottom
sediments and the level this element in aboveground and underground sprouts indicate that the sprouts of Glyceria maxima are
potentially useful in biomonitoring environmental contamination with Mn.
Key words: bottom sediments, heavy metals, indicators of quality of sediments, macrophytes
Received: February, 2014; Revised final: October, 2014; Accepted: November, 2014; Published in final edited form: July 2018
and transported with the suspended matter whose underground sprouts of Glyceria maxima as well as in
deposition leads to origination of bottom sediments in the bottom sediments of the Słupia River, (2)
surface waters, both with fast and slower flow. A part specification of accumulation coefficients of the
of such chemical compounds is deposited at bottom above mentioned heavy metals in sprouts of Glyceria
sediments (Kruopiene, 2007). maxima, and (3) evaluation of the quantity of the
Heavy metals are biologically transformed and bottom sediments within the area of the city of Słupsk
can be maintained in bottom sediments for a long time from the point of view of the concentration of selected
in tens or hundreds of years (Bettinetti et al., 2003; Liu heavy metals in them.
et al., 2009). When accumulated in bottom sediments,
they can constitute secondary sources of pollution 2. Material and methods
which are still harmful to water ecosystems (Yuan et
al., 2004). The quality of sediments is a good indicator 2.1. Research area
of pollution of water environment, as well as the
quantity of emitted pollutants in the river catchment The Słupia River is situated in the central part
(Klavins et al., 2000; Vandecasteel et al., 2004; of Pomerania (Northern Poland). It is a lowland
Wiśniowska-Kielian and Niemiec, 2005). Tests of watercourse 138.6 km in length and with a catchment
benthos revealed that the polluted sediments can cause area of 1620 km2. In the north the Słupia River
acute and chronic toxic effects water organisms, catchment borders the Baltic Sea catchment; in the
especially fish (Obolewski and Glińska-Lewczuk, west, the Wieprza River catchment; in the South, the
2006; Obolewski et al., 2016). Brda River catchment, and from the east, Łeba and
The pollution of bottom sediments has impacts Łupawa. The Słupia River headwater is at the
on the reduction of many species of water fauna which Kashubian Lake District close to Sierakowska Huta at
are important from the point of view of exploitation the height of 178 m a.s.l.
and ecology, such as snails and fish. Heavy metals are The river flows to the Baltic Sea in Ustka. The
biologically accumulated in plant and animal tissues, width of the river bed varies from 7 m in the upper part
so the toxic hazard increases at subsequent levels of of the river to 40 m at its mouth, where the average
the trophic chain (Klink et al., 2013; Kurilenko and flow is 15.5 m³.s-1. The river stream is strongly
Osmolovskaya, 2006; Loska and Wiechuła, 2003). meandered (Piechura et al., 1997). The area of the City
Plants react in various ways to increased concentration of Słupsk covers a 8 km stretch of the Słupia River
of heavy metals in the environment. Absorption and with various levels of transformation of the water bed
bioaccumulation of trace elements by plants is a part (low, moderate or high) (Table 1) (Obolewski and
of the natural cycle. In biological identification of Glińska-Lewczuk, 2006), whose banks are covered
water ecosystems, the plants of coastal zone with numerous macrophytes.
(macrophytes) are used, which, along with
phytoplankton, macrozoobenthos and fish, constitute 2.2. Research methods
basic elements of ecological evaluation of the status of
rivers (Klink et al., 2013, Obolewski and Glińska- The research was done in July 2013 at the area
Lewczuk, 2006; Skorbiłowicz, 2003; Skorbiłowicz of 10 stations situated within the city limits. Samples
and Skorbiłowicz, 2011). Macrophytes reflect the of bottom sediments and aboveground sprouts (leaves,
status of heavy metal pollution of water reservoirs stems) and underground ones (rootstock) of Glyceria
very well (Samecka-Cymerman and Kempers, 1996, maxima, (Fig. 1) were taken at the river bank zone of
Miretzky et al., 2004, Aksoy et al., 2005). the Słupia River where the sedimentation of the
The heavy metals content in aquatic plants may suspended material takes place. The bottom sediments
exceed many times their content in the surrounding were collected with the use of the Eckman sampler
water environment, the wide range of variability is from the depth of 0-15 cm.
caused by biology and ecology of particular species. After their transport to laboratory, the samples
Some aquatic plants are used in environmental were dried at a temperature of 65oC, they were sieved
research (Salt and Kramer 2000, Baldantoni et al., through a 1mm and ground in a mortar. Before
2004, Mishra and Tripathi, 2008). Glyceria maxima analysis, the deposit samples were tested as to the
plays the role of bioindicator of water pollution content of CaCO3 (with 0,1M HCl). In the bottom
(Tanner 1996, Sriyaraj and Shutes 2001, Rabajczyk sediments, the granulometric composition was marked
and Jóźwiak 2009, Teuchies et al., 2013). Control of by means of the gradation test, as well as active acidity
the chemical composition of bottom sediments and (pH, H2O), exchange acidity (pH, KCl), and the
aquatic plants in municipal areas is very important due organic matter content by the method of heat loss in a
to the harmfulness of heavy metals (Dauvalter and muffle furnace at the temperature 550oC. The samples
Rognerud, 2001; Xiangdong et al., 2000). These of Glyceria maxima at the area of each station were
studies allow for specification of the existing and taken for testing from several sprouts creating mixed
potential hazards resulting from toxic influence of samples both from aboveground and underground
heavy metals on water environment and human health. sprouts. After their transport to laboratory, the plant
The research aimed at (1) evaluation of the material was cleaned of mineral parts of the soil and
content of Zn, Mn, Cu and Ni in above-ground and flushed in distilled water.
1744
Heavy metals content in the sprouts of Glyceria maxima (Hartm.) Holmb. and in river sediments (Northern Poland)
The aboveground sprouts (leaves, stems) were coefficients of variation (CV) are presented.
separated from the underground ones (rootstock), Classification of bottom sediments was made in
dried to stable mass at the temperature of 65oC, and according with the classification of LAWA (1998),
then homogenized in a laboratory grinder. The content which divides the sediments on the purity class as the
of Zn, Mn Cu and Ni were determined by AAS method increasing content of heavy metals (Table 2). It is
(Perkin Elmer, Aanalyst 300) in a solution after assumed that the metal content in the dry matter of
mineralization in a mixture of the concentrated HNO3 bottom sediments for classes I and I-II at the level of
and 30% H2O2. The analyses were performed in the the geochemical background, while class II to IV
oxy-acetylene flame according to Ostrowska et al. indicate to the increasing influence of anthropogenic
(1991). The tests were carried out following the pollution of bottom sediments of rivers, and thus of the
original standards (Merck KGaA,1g/1000ml). whole aquatic ecosystem.
For evaluation of the level of contamination of
2.3. Elaboration of results sediments, classification of water sediments in Poland
on a basis of geochemical criteria was used
The results obtained were verified by means of (Bojakowska and Sokołowska, 1998). The indexes
statistic methods using Statistica software (7.1.). The calculated were pollution load index (PLI),
values of minimum, maximum, mean, standard Geoaccumulation index (Igeo) and enrichment factor
deviation, Spearman correlation coefficients and (EF) according to Eqs. (1-4).
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Parzych and Cymer/Environmental Engineering and Management Journal 17 (2018), 7, 1743-1752
Table 2. Classification of LAWA over 50%, and medium grained sand (0.5-0.25 mm) –
over 23%. At the research stations 5, 6, 7 and 9 small
Purity class quantities of gravel (7.9 %) and stone (0.5 %) were
I I-II II II- III III- IV found. At all stations, the lowest contribution had a
III IV fraction of dust (<0.05 mm) – average 1.2 %, (Fig. 2).
Zn ≤ ≤ ≤ ≤ ≤ ≤ >
The tested sediments did not contain CaCO3.
100 200 400 800 1600 3200 3200
Cu ≤ ≤ ≤ ≤ ≤ ≤ >
They were characterized by the a slightly alkaline
20 40 80 160 320 640 640 reaction both in the case of pH (H2O), and pH (KCl),
Ni ≤ ≤ ≤ ≤ ≤ ≤ ≤ (Table 3).
30 60 120 240 480 960 960 The average reaction was from 7.00 to 8.19,
Class I Uncontaminated reflecting variability at the level of 4.6 % within the
Class I-II Uncontaminated / Moderately area of 10 research stations. The content of organic
contaminated matter in the bottom sediments of the Słupia River was
Class II Moderately contaminated substantially diverse with the levels from 0.56 to 7.94
Class II-III Moderately contaminated / Heavily %, and variation coefficient was 117.0 % (Table 3).
contaminated
Class III Heavily contaminated
Class III- Heavily / Very heavily contaminated
IV
Class IV Very heavily contaminated
where:
n – number of analyzed positions;
CF – pollution factor, (Chakravarty and Patgiri, 2009)
Ce
CF = (2)
(Ce )EC
Fig. 2. Granulometric composition sediments of the River
Ce Słupia, point (mean), rectangle (standard deviation),
I geo = (3) whiskers (minimum-maximum)
1.5(Ce )EC
The highest level of organic matter content was
Ce in the samples of sediments from stations 4 and 10,
characterized by strong river meanders which
C Al S
EF = (4) welcomed substantial accumulation. The lowest
Ce quantities of accumulated organic matter (<1%) were
C Al EC
found at the stations 2, 3, 5, 6 and 8, with a prevailing
process of free transport of organic matter down the
river stream.
where:
Zinc content in the bottom sediments of the
(Ce)s - concentration of elements in the sample,
Słupia River varied substantially (CV= 82.2 %) with
(CAl)s – concentration of aluminum in the sample,
levels from 12.4 to 104.7 mg∙kg-1, average 34.1 mg∙kg-
(Ce)EC – geochemical background 1
(Table. 4). In 25 % of tested samples, the zinc content
was between 20 and 25 mg∙kg-1 (Fig. 3). The zinc
3. Results and discussion
concentration in the river sediments within the city
limits of Słupsk in 2013 exceeded the value of
The bottom sediments in the Słupia River were
geochemical background (>48 mg∙kg-1) only at
characterized by diverse granulometric composition.
stations 4 and 9.
Fine sand constituted the largest part (0.25-0.1 mm) –
pH pH Organic
(H2O) (KCl) matter
Average ± SD 7.84 ± 0.36 7.66 ± 0.40 2.14 ± 2.51
Median 7.95 7.79 0.91
Minimum 7.00 6.68 0.56
Maximum 8.19 8.08 7.94
CV, % 4.6 5.2 117.0
1746
Heavy metals content in the sprouts of Glyceria maxima (Hartm.) Holmb. and in river sediments (Northern Poland)
The natural content of Zn in sediments of Table 4. Heavy metals (mg∙kg-1) contents in bottom
surface water (lakes and rivers) in Poland is about 74 sediments of the river Słupia
mg∙kg-1 (Lis and Pasieczna, 1995). As a geochemical
background of zinc in the bottom sediments of the Zn Mn Cu Ni
Vistula River and its tributaries, the value of 110 Average ± 34.1 ± 152.1 ± 8.4 ± 11.9 ±
SD 28.0 111.5 4.4 2.8
mg∙kg-1 (Helios-Rybicka, 1991) was adopted.
Median 22.8 119.0 7.5 11.7
A slightly different type of aquatic ecosystems Minimum 12.4 58.1 2.6 8.5
of rivers and lakes are old river beds. This is Maximum 104.7 376.7 15.1 16.8
particularly evident in the assessment of the CV, % 82.2 73.3 52.8 23.5
concentration of individual metals in bottom
sediments, which is usually more. Concentration of Zn Only at two stations (4, 10) Mn content
in the bottom sediments of old river beds of the Słupia exceeding 300 mg∙kg-1 was discovered (Fig. 3).
River was on average 142.6 mg∙kg-1 and resulted from Obtained manganese contents in bottom sediments of
accumulation and the lack of water outflow the Słupia River did not exceed the level of
(Obolewski and Glińska-Lewczuk, 2013). Zinc is a geochemical background (500 mg∙kg-1). Slightly
metal commonly introduced to surface waters along higher manganese concentrations were found in the
with municipal sewage and surface flow. Burning of old river beds of the Słupia River – 645 mg∙kg-1
coal is a source of zinc in the environment along with (Obolewski and Glińska-Lewczuk, 2006), which
use of zinc covered water pipes. Zn concentration in could have been a result of accumulation connected
bottom sediments of the Słupia River does not have with the lack of outflow of water.
negative impact on living organisms. According to the The Oder River bottom sediments contained
classification Lawa (1998) the Słupia River sediments 770 mg∙kg-1, and the Rhine River deposits even 960
should be classified to the 1st quality class as to the mg∙kg-1Mn (Kucharzewska et al., 1991). Manganese
zinc content – uncontaminated sediments (Table 2). of the bottom sediments is characterized by high
Manganese content was between 58.1 and mobility (Kabata-Pendias and Pendias, 1999), which
376.7 mg∙kg-1, average 152.1 mg∙kg-1. The manganese is especially stimulated by pH~8. The main source of
concentration variability coefficient in the bottom manganese in environment is washing out of rocks and
deposits was 73.3 % (Table. 4). For 50 % of the soils. Anthropogenic sources comprise mainly coal
examined stations Mn content was from 50 to 100 and gasoline.
mg∙kg-1.
(a) (b)
(c) (d)
Fig. 3. Histograms of heavy metals contents in bottom sediments of River Słupia. Black line – values of geochemical background
1747
Parzych and Cymer/Environmental Engineering and Management Journal 17 (2018), 7, 1743-1752
Copper content in bottom sediments of the and Glińska-Lewczuk, 2013), and most probably, it
Słupia River was on average 8.4 mg∙kg-1 with the was an effect of increased accumulation of organic
values ranging from 2.6 to 15.1 mg∙kg-1. Cu matter and the lack of water outflow (Bettinetti et al.,
concentration showed variability at the level of 52,8% 2003; Liu et al., 2009). The natural nickel content in
within the area of research stations (Table 4). The the bottom sediments of the Vistula River was 40
copper content in the sediments was low and was mg∙kg-1 (Helios-Rybicka, 1991), and in the case of
within the limits of the geochemical background (6 other rivers of Poland, about 10 mg∙kg-1 (Lis and
mg∙kg-1) except the stations 4, 5, 6, 7, 9 and 10. The Pasieczna, 1995). Burning of coal and liquid fuels is a
highest content of Cu (15.1 mg∙kg-1) was found at source of nickel in the natural environment. Effluents
station 5, where substantial transformation of the river from the municipal and industrial dump sites
bed took place (concrete covering), (Fig. 3). Slightly constitute additional sources of nickel contamination
higher levels of Cu (34.9 mg∙kg-1) were revealed in of water sediments, as a result of dumping of
bottom sediments of the old river beds of the Słupia accumulators and nickel-cadmium batteries and
River by Obolewski and Glińska-Lewczuk (2006), discharge of waste from galvanizing plants used
which could have resulted from the increased catalysts. A series of statistically significant
accumulation of organic matter caused by the lack of relationships were found among the tested parameters
water outflow (Bettinetti et al., 2003; Liu et al., 2009). (Table 5).
The copper content in the water sediments is Along with the increase of organic matter
connected with the kind of the parent rock and usually content in bottom sediments, decrease of pH was
is several mg∙kg-1. According to Lis and Pasieczna observed (r=-0.78 and r=-0.81, p<0.05, n=30) together
(1995) the natural content of Cu in the river sediments with increase of concentration of Mn, Cu and Ni
usually does not exceed 20 mg∙kg-1. Contamination of (r=0.90, r=0.53 and r=0.91, p<0.05, n=30). Active
environment with copper, including river sediments, acidity and exchange acidity were also significantly
takes place mainly due to mining and processing of related to one another. Increase of acidity had a
copper ore, but can also be a result of applied significant impact on release of ion forms of Mn, Cu
pesticides, additives to fodder in agriculture and a and Ni from bottom sediments. It was also found, that
result of burning fossil fuels. Discharge of untreated with the increase of concentration of Zn and Mn, an
sewage from galvanizing plants and their improper increase of Cu concentration was found. A positive
storage makes ions of copper penetrate the bottom and statistically vital correlation was also found
waters and sediments (Bojakowska and Sokołowska, between Mn and Ni and Cu and Ni (respectively r=
1998). Due to its small content in tested sediments 0.90 and r=0.47, p<0.05, n=30), (Table 5).
(Cu<36 mg∙kg-1), copper has no negative impact on The values of geo-accumulation indexes were
living organisms. between: 0<Igeo<1, which according to a 7-grade
Nickel content in the bottom deposits of the classification of bottom sediments LAWA (1998),
Słupia River was from 8.5 to 16.8 mg∙kg-1, average Eqs. 1, 3 and 4 shows moderate contamination of the
11.9 mg∙kg-1. The concentration variation coefficient bottom sediments of the Słupia River in relation to Zn,
of Ni was the lowest from among tested heavy metals Mn, Cu and Ni. The values of enrichment factors EF,
and was 23,5 % (Table 4). The largest quantity of show the lack of contamination of bottom sediments
nickel (>15 mg∙kg-1) was found at the stations 4 and of the Słupia River in case of Zn and Mn (EF<1) and
10, as well as in the case of manganese (Fig. 3). At all a slight contamination with copper and nickel (Table
stations, the content of Ni exceeded the level of the 6). Enrichment factors (EF>1) in the case of Cu and
geochemical background (>5 mg∙kg-1), but according Ni reveal anthropogenic contamination with these
to classification Lawa (1998) it belonged to the class I elements. Also the indexes of pollution load (PLI)
of the clarity (<30 mg∙kg-1), Table 2. Higher Ni show slight contamination of the Słupia River bottom
content was found in the sediments of the old river sediments with Zn and Mn (PLI<1) and Cu and Ni
beds of the Słupia River – 32.2 mg∙kg-1 (Obolewski (PLI<2.33), (Table 6).
Table 5. The correlation coefficient between the researched parameters (n = 30, p <0.05, rcrit. = 0.30) in the bottom sediments of
Słupia
Organic pH pH Zn Mn Cu Ni
matter H2O KCl
Organic matter -
pH (H2O) -0.78 -
pH (KCl) -0.81 0.98 -
Zn 0.29 -0.28 -0.24 -
Mn 0.90 -0.65 -0.67 0.21 -
Cu 0.53 -0.44 -0.40 0.41 0.43 -
Ni 0.91 -0.76 -0.75 0.10 0.90 0.47 -
rcrit. - critical values of Spearman’s correlation coefficient referred to Ramsey (1989), bold values are statistically significant
1748
Heavy metals content in the sprouts of Glyceria maxima (Hartm.) Holmb. and in river sediments (Northern Poland)
Table 6. Quality indicators of bottom sediments of the Solubility of metals is low as to neutral and
Słupia River alkaline reactions (Table 3), and increases along with
lowering of the value of pH (Smal and Salomons,
Zn Mn Cu Ni 1995). Increase of mobility of Zn and Mn is most
PLI 0.57 0.25 1.21 2.33 effective with pH=6, while Cu and Ni at pH=5.5.
Igeo 0.0099 0.0004 0.1548 0.3167 Manganese, however, is characterized by increased
EF 0.71 0.30 1.39 2.38
solubility also in alkaline environment (pH~8),
(Alloway, 1995, Martinez and Motto, 2000).
The heavy metal content in the tissues of the Cu content in aboveground and underground
water plants and in the bottom sediment of the rivers sprouts of Glyceria maxima was 10.3 mg∙kg-1 and 21.1
reflects the impact of anthropomorphic pressure on mg∙kg-1 respectively and shows variability within the
natural environment. The zinc content was from 17.9 area of 10 stations of 21.9% and 55.7% respectively
to 53.0 mg∙kg-1 in aboveground sprouts and from 15.8 (Table 7). Copper in plants displays low mobility
to 119.5 mg∙kg-1 in underground sprouts of Glyceria (Kabata-Pendias and Pendias, 1999). The
maxima, showing variability at the level of 43.3 % and physiological demand of most plants is below 4-5
56.0 % (Table 7). To cover physiological needs of mg∙kg-1 and is quite variable depending on the part of
most plants, the concentration in leaves at the level of the plant, its development stage, variety and species.
15-30 mg∙kg-1 is sufficient (Kabata-Pendias and Its average content in the aboveground parts of the
Pendias, 1999). The plants absorb Zn in the quantities plants is from 5-20 mg∙kg-1 (Kabata-Pendias and
proportional to its concentration in soil (Kozanecka et Pendias, 1999). The average nickel content was 17.4
al. 2002). An average zinc content in aboveground mg∙kg-1 and 24.9 mg∙kg-1 respectively in aboveground
parts of the plants which are not under the influence of and underground sprouts of Glyceria maxima.
pollution is 10-70 mg∙kg-1 (Kabata-Pendias and Variability coefficients within the area of the research
Pendias, 1999), which shows a permissible level of Zn stations were 25.8% and 18.5% respectively (Table 7).
in aboveground sprouts of Glyceria maxima covering Physiological nickel content in plants at the
the banks of the Słupia River. area which was not under the impact of pollution was
Manganese content in Glyceria maxima was on most often: 0.1-5.0 mg∙kg-1 (Kabata-Pendias and
average 261.7 mg∙kg-1 in aboveground sprouts and Pendias, 1999), and in municipal agglomerations such
441.2 mg∙kg-1 in underground ones. Variation in values can be higher since nickel easily undergoes bio
concentration at 10 stations, at 68.4% and 86.8%, was accumulation especially in water plants which are
much higher than in the case of Zn. According to sensitive bio-indicators of waters (Sarosiek and
Kabata-Pendias and Pendias (1999), the demand of Wożakowska-Natkaniec, 1993). The slightly higher
plants for manganese varies and in most cases 10-25 Ni content than physiological demand in the sprouts
mg∙kg-1 is sufficient. A concentration about 500 of Glyceria maxima therefore indicates some pollution
mg∙kg-1 can be toxic for most of the plants. Increased of bottom sediments with that element. Enrichment
Mn content in the sprouts of Glyceria maxima in factors (EF) of determination of heavy metals in
relation to physiological demand can show a positive aboveground sprouts had the values lower than 1.9,
impact of that macrophyte on purification of water and and in the underground sprouts < 3.3 (Table 7). All of
bottom sediments of the Słupia River. The main factor the determined heavy metals were accumulated much
deciding about the availability of heavy metals for easily in underground sprouts than in the aboveground
plants is the reaction of bottom sediments. ones of Glyceria maxima.
Table 7. Heavy metals (mg∙kg-1) contents, coefficients of variation (%) and the enrichment factor (EF) in the aboveground
and underground sprounts of Glyceria maxima
Zn Mn Cu Ni
Glyceria maxima - aboveground sprouts
Average ± SD 29.9±12.7 261.7±179.1 10.3±2.3 17.4±4.5
Median 23.4 200.9 10.1 17.2
Minimum 17.9 98.2 7.6 11.9
Maximum 53.0 622.7 13.7 24.3
CV, % 43.3 68.4 21.9 25.8
EF 1.2 1.9 1.7 1.5
Glyceria maxima - underground sprouts
Average ± SD 59.3±33.2 441.2±383.1 21.1±11.7 24.9±4.6
Median 57.3 242.7 19.3 25.8
Minimum 15.8 130.3 12.3 17.8
Maximum 119.5 1276.3 51.5 30.3
CV, % 56.0 86.8 55.7 18.5
EF 2.5 3.1 3.3 2.2
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Parzych and Cymer/Environmental Engineering and Management Journal 17 (2018), 7, 1743-1752
1750
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1753-1764
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
Dana Malschi1∗, Liviu Muntean1, Ioan Oprea 1, Carmen Roba1, Gabriela Popiţa1,
Lucrina Ştefănescu1, Bianca Malschi Florian2, Elena Rînba3
1Babeş-Bolyai University, Faculty of Environmental Sciences and Engineering,
30 Fântânele Street, 400294, Cluj-Napoca, Romania
2National Environmental Protection Agency, 99-101 Dorobanţilor, Cluj-Napoca, Romania
3Babeş-Bolyai University, Botanical Garden, 42 Republicii, Cluj-Napoca, Romania
Abstract
With the aim of contribute to a bioremediation technology drafting, this paper presents a preliminary research on bioremediation
of wastewaters polluted with heavy metals and other toxic contaminants. Bioremediation tests were performed with aquatic species
Lemna minor, Vallisneria spiralis, Eichhornia crassipes, Hydrilla verticillata, Pistia stratiotes, Cladophora glomerata, on samples
of contaminated waters resulting from the toxic pond of waste landfill Şomârd-Mediaş, Sibiu County, Romania, during the 2012-
2013 period. The studies were conducted in microcontainers with contaminated water using constructed wetlands. In order to check
the phytoextraction and bioremediation potential of these species, a comparative analysis of water samples was performed, based
on the determination of heavy metals and different pollution parameters. The results on phytoextraction tests have shown that: L.
minor plants were able to extract Cu, Fe and Pb; V. spiralis plants were able to extract Cu, Fe, Zn and Ni; H. verticillata, E.
crassipes, P. stratiotes and green algae C. glomerata were able to extract Cu, Fe and Zn. This research has shown that the aquatic
plants grown for two weeks in the toxic pond water have important effects on wastewater bioremediation. All species have shown
a significant decrease of NH4+ concentration. L. minor, V. spiralis, H. verticillata, E. crassipes, P. stratiotes have determined the
increase of Eh and the decrease of CCO-Mn, TDS, EC. Stronger effects of bioremediation in the tests with ½ diluted water from
the toxic pond were recorded. The results prove the significance of the bioremediation of contaminated waters using aquatic species
for constructed wetlands in order to implement this biotechnology.
Key words: bioremediation, Eichhornia crassipes, Lemna minor, Pistia stratiotes, Vallisneria spiralis
Received: February, 2014; Revised final: September, 2014; Accepted: October, 2014; Published in final edited form: July 2018
∗
Author to whom all correspondence should be addressed: e-mail: danamalschi@yahoo.com, Phone: +40745 367373, Fax: +40264-30 70 30
Malschi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1753-1764
bioaccumulation, metals accumulation and Various toxic pollutants and heavy metals have
wastewater treatment (Dosnon-Olette et al., 2011; accumulated in this pond causing an important
Malschi et al., 2013; Rahmani and Sternberg, 1999; environmental problem, which has been intensely
Rahman et al., 2007; Willey, 2007). Bioremediation studied (Mihăiescu et al., 2010; Muntean, 2003; Oprea
research has revealed the effect of aquatic species such et al., 2010).
as eel grass Vallisneria spiralis L. (Hydrocharitaceae) Lemna minor, Vallisneria spiralis, Eichhornia
(McCutcheon and Schnoor, 2004; Masi et al., 2002; crassipes, Hydrilla verticillata, Pistia stratiotes and
Núñez et al., 2011; Sim et al., 2007 etc.) on metals Cladophora glomerata have been used to study the
hyperaccumulation (Malschi et al., 2013; Oprea et al., bioremediation and phytoextraction of water
2013); water hyacinth Eichhornia crassipes (Mart.) pollutants, in micro containers tests such as
Solms (Pontederiaceae) on biosorption and metals constructed wetlands. The biologic material of the
accumulation (Buta et al., 2011); waterthyme Hydrilla aquatic species has been grown under greenhouse
verticillata (L.f.) Royle (Hydrocharitaceae), water conditions at the Botanical Garden of the Babeş-
lettuce Pistia stratiotes L. (Araceae) (Stoica et al., Bolyai University, Cluj-Napoca. During the
2009) and green algae Cladophora glomerata (L.) experiment, the best conditions for plant growing in
Kütz. (Chlorophyta) (Yalçına et al., 2008) on metals laboratory were provided in transparent plastic pots
accumulation and wastewater treatment. adequate as volume for the waters as follows: 700 mL
Studies on biological pollution indicators in the for L. minor variants, 1 liter for P. stratiotes variants,
aquatic environment reveal an important interest due 2 liters for the variants of E. crassipes, V. spiralis, H.
to the significance of biomonitoring in pollution verticillata, 400 mL for C. glomerata variants. The
assessment, determination of ecotoxicity and experimentation time was of two weeks for each
development of bio- and eco-technologies (Glick and aquatic species (24.10.2012-07.11.2012) with
Stearns, 2011; Malschi, 2009; Oros, 2002, 2011; Oros additional light for 16 hours daily. Three types of
and Drăgici, 2002; Pavel et al., 2012). experimental waters for each species were placed in
Constructed wetlands are used for the micro containers: 1. drinking plain water as blank; 2.
decontamination of industrial wastewater and leachate water collected from the toxic pond of Şomârd waste
from wastes landfills (Jing et al., 2001; Kuschk et al., landfills; 3. water with the 1/2 dilution from the toxic
2005; Masi et al., 2002; Sim et al., 2007). The pond of Şomârd waste landfills. The development of
constructed wetlands provide the biological processes plants phytotoxic effects of water samples subjected to
determining biological degradation, transformation, testing and the phytoremediation effects were
biosorption and phytoextraction of pollutants by highlighted by photographing the visible differences
aquatic species (Dyck et al., 2009; Juang and Chen, between the samples compared to the situation in the
2007). The use of constructed wetlands (composed of unpolluted blank sample.
water plants, green algae, cyanobacteria and various Before and after phytoremediation and
species with high biological effect of pollutants phytoextraction tests, analysis of water quality
bioaccumulation) can remove various heavy metals parameters of the samples were conducted. A
and other pollutants (Jing et al., 2001; Kuschk et al., multiparameter type WTW Multi 350 was used for the
2005; Malschi, 2009; Malschi et al., 2013; Oprea et following parameters: the values of O2, Eh-redox
al., 2013; Xu et al., 2016). potential, CCO-Mn, EC-electrical conductivity, TDS-
This paper presents preliminary research to total dissolved solids, S–salinity.
prove the importance of the contaminated waters The concentrations of anions (F-, Cl-, NO2-,
bioremediation technology using aquatic species for NO3-, SO42-) and cations (Li+, Na+, K+, Mg2+, Ca2+,
constructed wetlands. The novelty of the paper NH4+) have been determined using ICS 1500 Dionex
consists in controlling the heavy metals Ion Chromatography (IC) analysis method. Water
phytoextraction potential of the tested species and samples were filtered with qualitative filter paper 125
measuring the bioremediation potential of waste mm and before analyzing were diluted to an electrical
waters quality parameters. In order to check the conductivity lower than 100 µS/cm. An analytical
phytoextraction and bioremediation potential of these column IonPac AS23 for ion exchange was used for
species, the experimental tests were performed with L. the separation of the major anions. The suppressor was
minor, V. spiralis, E. crassipes, H. verticillata, P. an ASRS 300 ULTRA II (4 mm) Anions Self
stratiotes, C. glomerata. Regenerating Suppressor. As anion mixture standard
Seven Anion Standard II (Dionex, USA) was used.
2. Material and methods The injection volume was 25 μL, and the flow rate 1.0
mL/min, the eluent was an aqueous solution consisting
During the 2012-2013 period, researches on of 4.5 mM Na2CO3 and 0.8 mM NaHCO3.
bioremediation of polluted waters were conducted in For the separation of the major cations, an
the Biotechnology Laboratory of the Faculty of Analytical column IonPac CS12A for ion exchange
Environmental Science and Engineering within the was used and a CSRS 300 ULTRA II (4 mm) Cations
Babeş-Bolyai University, Cluj-Napoca. The polluted Self Regenerating Suppressor. Six Cation II Standard
water samples were collected from the toxic pond of (Fluka, Germany) has been used as cation standard
municipal and industrial waste landfill Şomârd- mixture. The eluent was an aqueous solution
Mediaş, Sibiu County. consisting of 20 mM methanesulfonic acid.
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Research on wastewaters bioremediation with aquatic species for constructed wetlands
Heavy metal concentrations (Pb, Cu, Zn, Ni, county, during 2012-2013. In order to study the
Fe) have been determined with atomic absorption phytoextraction and bioremediation potential of
spectrometry (AAS) (ZEEnit 700 Analytik Jena) aquatic species, a comparative analysis was performed
method for determination of trace elements from between the samples of polluted water and control
solution (flame method, mg/L). Before analyzing, the unpolluted water, in terms of pollution parameters
water samples were acidified with HNO3 65% at a pH modifications depending on plants activity.
between 2 and 3 and filtered with qualitative filter The experimental data obtained indicate that
paper of 125 mm. significant effects on heavy metals phytoextraction
and biosorption were noticed in L. minor, V. spiralis,
3. Result and discussions E. crassipes, H. verticillata, P. stratiotes, C.
glomerata. Biotransformation of some toxic
Previous studies performed in 2009-2010 on contaminants and their removal from the water in a
the bioaccumulation potential of pollutants film of oil on the water surface has been shown for V.
recommend the cultivation of L. minor plants as a spiralis, H. verticilata, E. crassipes, C. glomerata
method of bioremediation. Bioaccumulation of heavy (Fig. 6B). Present experimental results have illustrated
metals and metalloids was studied on L. minor plants that L. minor, V. spiralis, E. crassipes, H. verticillata,
grown in polluted waters. L. minor was noticed to be P. stratiotes, C. glomerata have a very important role
a very good bioaccumulator for Cr, Mn, Zn, As, Ba in the bioremediation of wastewater pollution with
and a moderate bioaccumulator of Cu, Pb, V from the various toxic compounds and heavy metals, and are
polluted waters in the waste heaps and tailings dams recommended for use in micro ecosystems of
areas of mining operations, toxic ponds and waste constructed wetlands (Fig. 7).
platforms in the chemical industry (Malschi et al.,
2013). The study on the parameters of polluted water 3.1. Phytoextraction/biosorption of heavy metal with
revealed an extremely high level of heavy metals (Fe, aquatic species with plants and green algae
Cd, Zn) pollution in the water samples collected from
Şomârd-Mediaş municipal waste landfill, in Sibiu The concentrations of heavy metals in water
county, also mentioned in previous studies (Mihăiescu samples collected from the Şomârd/Mediaş landfill
et al., 2010; Muntean, 2003; Oprea et al., 2010). The toxic pond in 2012 exceeded the maximum permitted
results obtained after applying the Pb, Cd, Zn limits for surface waters (Ord. 161, 2006). Toxic pond
phytoextraction and bioremediation tests (Oprea et al., water has such concentrations of heavy metals that it
2013) proved the role of the wastewater fitted the 5th water quality class for Cu and Pb, the 3rd
bioremediation treatment using L. minor and V. water quality class for Ni and the 2nd water quality
spiralis as component of constructed wetlands in lab. class for Zn, Fe.
micro containers. After two weeks of bioremediation By biosorption and phytoextraction on the
with V. spiralis it was noticed that these plants have a experimental tests (during the 24.10.2012-07.11.2012
great capacity to biotransform the pollutants and to period), the plants of L. minor, V. spiralis, H.
make them form a viscous oil film on the water verticillata, E. crassipes, P. stratiotes and the green
surface. algae C. glomerata were able to extract copper. Only
The new tests of bioremediation and L. minor plants extracted lead and only V. spiralis
phytoextraction with L. minor (Fig.1), P. stratiotes plants extracted nickel. The plants of L. minor, V.
(Fig. 2), E. crassipes (Fig. 3), V. spiralis (Fig. 4), H. spiralis, H. verticillata, E. crassipes, P. stratiotes and
verticillata (Fig. 5), C. glomerata (Fig. 6A) were green algae C. glomerata were able to extract iron. V.
performed on waste water samples collected from spiralis, H. verticillata, E. crassipes, P. stratiotes
historically polluted sites, from the toxic pond of plants and C. glomerata were able to extract zinc (Fig.
municipal and industrial waste landfill Şomârd, Sibiu 8).
1 2 3 1 2 3
(a) (b)
1 2 3 1 2 3
(c) (d)
Fig. 1. Phytoextraction and biomonitoring with Lemna minor in water from Şomârd waste landfills: (a) Phytoextraction tests
during 23-29.10.2012; (b) Phytoextraction tests during 23.10-6.11.2012; (c) Biomonitoring tests/29.10.2012; (d) Biomonitoring
tests/6.11.2012. 1=Control, 2=water from toxic pond, 3=the 1/2 dilution of water from the toxic pond
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Malschi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1753-1764
1 2 3 1 2 3
(a) (b)
Fig. 2. Phytoextraction tests with Pistia stratiotes in water from Şomârd-Mediaş waste landfills: (a) Before
phytoextraction/23.10.2012; (b) After phytoextraction tests/6.11.2012. 1=Control, 2=water from the toxic pond, 3= the 1/2
dilution of water from the toxic pond
1 2 3
(a)
1 2 3 1 2 3
(b) (c)
Fig. 3. Phytoremediation tests with Echhornia crassipes in water from Şomârd-Mediaş waste landfills.
a) and b) Phytoextraction tests/29.10.2012; c) After phytoextraction/13.11.2012. 1=Control, 2=water from the toxic pond, 3= the
1/2 dilution of water from the toxic pond
1 2 3 1 2 3
(a) (b)
Fig. 4. Phytoremediation tests with Vallisneria spiralis in water from Şomârd-Mediaş waste landfills. a) Before
phytoextraction/24.10.2012; b) After phytoextraction/6.11.2012. 1=Control, 2=water from the toxic pond, 3=the 1/2 dilution of
water from the toxic pond
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Research on wastewaters bioremediation with aquatic species for constructed wetlands
1 2 3 1 2 3
(a) (b)
Fig. 5. Phytoremediation tests with Hydrilla verticillata in water from Şomârd-Mediaş waste landfills.
a) Phytoextraction/29.10.2012; b) After phytoextraction/6.11.2012. 1=Control, 2=water from the toxic pond, 3= the 1/2 dilution of
water from the toxic pond
1 2 3 1 2 3
(a) (b)
Fig. 6. Bioremediation with Cladophora glomerata in water from Şomârd waste landfills
a) Bioremediation tests with Cladophora glomerata, after phytoextraction/15.11.2012. 1- control, 2 - water from the toxic pond,
3 - the 1/2 dilution of water from the toxic pond, b) Biotransformation of pollutants from waste water after phytoremediation.
Isolation of pollutants oily film after the treatment with: 1=Cladophora glomerata, 2=Hydrilla verticillata; 3=Valisneria spiralis
Fig. 7. Bioremediation in laboratory micro-constructed wetlands consisting in aquatic species associations: Lemna minor,
Valisneria spiralis, Eichhornia crassipes, Hydrilla verticillata, Pistia stratiotes, Cladophora glomerata in toxic pond polluted
water from Şomârd-Mediaş waste landfills. 1- bioremediation tests /14-25.11.2012 / with species association in 1/2 dilution toxic
pond water. 2 - bioremediation tests /14-25.11.2012 / with species association in 1/4 dilution toxic pond water
Preliminary results on phytoextraction tests plants have extracted Cu, Zn, Fe, Ni, H. verticillata, E.
during 24/10/2012 - 07/11/2012 have shown that: L. crassipes, P. stratiotes and C. glomerata have
minor plants have extracted Cu, Fe and Pb, V. spiralis extracted Cu, Zn and Fe (Fig. 8, Table 1)
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Malschi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1753-1764
Fig. 8. Laboratory tests with Lemna minor, Vallisneria spiralis, Eichhornia crassipes, Hydrilla verticillata, Pistia stratiotes,
Cladophora glomerata used in heavy metal biosorption from the Şomârd landfill toxic pond water /24.10.2012-07.11.2012.
Heavy metal concentrations:
a) Before phytoextraction / 24.10.2012;
b) After phytoextraction with plants / 07.11.2012
Table 1. Chemical quality standards for some heavy metals increase of SO42-and decrease of Cl-, F-. V. spiralis
to set out the ecological status of surface waters / maximum plants in drinking water type determined the increase
limits / quality classes (Ord. 161, 2006) concentrations of F-, SO42-, decrease of Cl- and fixing
N to NO2- during testing. In the toxic pond water and
Quality
U/M Quality classes in 1/2 dilution toxic pond water, V. spiralis determined
indicator
Heavy
the increase of SO42- and decrease of Cl-, F-. H.
metals
1 2 3 4 5 verticillata determined the increase of Cl-, F-
> concentration, decrease of SO42-. H. verticillata
Cu µg/L 20 30 50 100 determined the increase of SO42- and decrease of Cl-,
100
> F- in the toxic pond water and the ½ dilution toxic pond
Zn µg/L 100 200 500 1000
1000 water. The E. crassipes plants determined the increase
Pb µg/L 5 10 25 50 > 50 of Cl-, F-, SO42- concentrations in drinking water,
Cd µg/L 0,5 1 2 5 >5 while E. crassipes plants determined the increase of
> SO42-, Cl- and a decrease of F- in the toxic pond water
Ni µg/L 10 25 50 100
100 and the 1/2 dilution toxic pond water.
Fe2+ + > The activity of P. stratiotes plants in drinking
µg/L 300 500 1000 2000
Fe3+ 2000
water determined the increase of Cl-, F-, SO42-
concentrations and fixing of N to NO2-. P. stratiotes
3.2. Bioremediation of wastewater from the toxic pond plants have determined the increase of SO42- and
of Şomârd/Mediaş landfills with aquatic species L. decrease of F-, Cl- in the toxic pond water, while in the
minor, V. spiralis, E. crassipes, H. verticillata, P. 1/2 dilution toxic pond water, the plants have
stratiotes, C. glomerata determined the increase of SO42-, Cl- and a decrease of
F-. C. glomerata produced the increasing of Cl-, F-,
In 2012, the water from Şomârd/Mediaş SO42- concentrations and fixing N to NO2-. C.
landfills toxic pond had very high concentrations of glomerata algae have determined the increase of Cl-,
anions Cl-, F-, SO42- fitting the 5th quality class (poor) SO42- and decrease of F- in toxic pond water and in ½
for surface waters (Ord. 161, 2006). After the dilution toxic pond water (Tables 2, 3).
phytoremediation experimental tests, in case of the Very high concentrations of SO42-, Cl- and F-
control samples with drinking water, the N-NO2- were in toxic pond waters before the experiment. After
appears in Lemna, Vallisneria, Pistia, Cladophora. phytoremediation experiments, the concentration of
The presence and activity of these species have led to SO42- increased. The concentration of Cl-, F- and salt
the accumulation of nitrogen in the form of NO2-, in were variable in different waters types of tests (Tables
unpolluted waters. The environmental effect of 2, 3). Preliminary research on phytoremediation of
nitrogen fixation does not occur in the toxic pond environmental status of waters have shown that: in the
waters (Tables 2, 3). The presence of L. minor plants toxic pond water and the 1/2 dilution toxic pond water,
in drinking water determined the increase of L. minor, V. spiralis and H. verticillata, plants have
concentrations of Cl-, F-, SO42- and fixing N to NO2-. determined the increase of SO42- and decrease of Cl-,
In the toxic pond water and in the ½ dilution toxic F- anions, while E.crassipes and C. glomerata have
pond water, L. minor plants have determined the determined the increase of Cl-, SO42- and the decrease
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Research on wastewaters bioremediation with aquatic species for constructed wetlands
of F-. P. stratiotes plantsproduced the increase of SO42- P. stratiotes has decreased the concentration of
and decrease of Cl-, F- anions in the toxic pond water. K+, Ca2+, Mg2+, Na+, Li+ and more pronounced Mg2+.
L. minor caused the decrease of Ca2+, Mg2+
3.3. Cations bioremediation with aquatic species concentration and the increase of K concentration; V.
+
Table 2. Laboratory tests for phytoremediation with aquatic species Lemna minor, Vallisneria spiralis, Eichhornia crassipes,
Hydrilla verticillata, Pistia stratiotes, Cladophora glomerata of the anions environmental status of water
from the Şomârd waste landfills toxic pond
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Malschi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1753-1764
Table 3. Chemical and physicochemical quality standards for some nutrients to set out the ecological status of surface
waters/maximum limits/quality classes (Ord. 161, 2006)
Table 4. Laboratory tests for phytoremediation with aquatic species Lemna minor, Vallisneria spiralis, Eichhornia crassipes,
Hydrilla verticillata, Pistia stratiotes, Cladophora glomerata of the cation environmental status of water from the Şomârd waste
landfills toxic pond
Table 5. Chemical and physicochemical quality standards for some cations to set out the ecological status of surface
waters/maximum limits/quality classes (Ord. 161, 2006)
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Research on wastewaters bioremediation with aquatic species for constructed wetlands
L. minor decreased amount of K+, Ca2+, Mg2+, and P. stratiotes caused the increase of K+. C.
Na+, Li+; V. spiralis and H. verticillata caused the glomerata caused the increase the concentration of K+,
decrease of Ca2+, Mg2+, Na+, Li+ and the increase of Ca2+, Mg2+, Na+, Li+.
K+; while E. crassipes decreased amount of Mg2+. P.
stratiotes increased the concentration of Mg2+, K+ and 3.4. Bioremediation of wastewater by means of
decreased Ca2+ (Tables 4, 5). Stronger effects of aquatic species: L. minor, V. spiralis, E. crassipes, H.
bioremediation in the tests with aquatic plants grown verticillata, P. stratiotes, C. glomerata
for two weeks in ½ dilution water from the toxic pond
as compared to the control samples were recorded. H. The toxic pond water from the Şomârd/Mediaş
verticillata, E. crassipes, P. stratiotes and C. waste landfills, as compared to the control unpolluted
glomerata have decreased to zero the amount of NH4+. water samples, shows lower values of O2 mg/L and of
L. minor and V. spiralis significantly decreased Eh - oxidation-reduction potential and higher values
amount of NH4+. L. minor decreased the amount of of CCO-Mn, of EC - electrical conductivity, of TDS -
Ca2+, Na+, K+; V. spiralis and H. verticillata caused the total dissolved solids and of S – salinity, in 2012 (Fig.
decrease of Ca2+ and Na+. V. spiralis, H. verticillata 9).
(a)
(b)
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Malschi et al./Environmental Engineering and Management Journal 17 (2018), 7, 1753-1764
284
A.1 C ontrol-Drinking water 338 568
B .1 L emna minor 299 675
B .1 Vallisneria spiralis 340 598 E C µS /cm
B .1 Hydrilla verticillata 316 680
B .1 E ichhornia crassipes 351 632 TDS mg /L
B .1 P istia stratiotes
B .1 C ladophora g lomerata 315 701
E xperim ental variants
630
6085 12170
A.2 Water from bund
B .2 L emna minor 5680 11360
B .2 Vallisneria spiralis 5950 11900
B .2 Hydrilla verticillata 5905 11810
B .2 E ichhornia crassipes 6645 13290
B .2 P istia stratiotes 6175 12350
B .2 C ladophora g lomerata 7360 14720
3615
A.3 Dilution 1/2 bund water 3140 7230
B .3 L emna minor 6280
B .3 Vallisneria spiralis 3315 6630
B .3 Hydrilla verticillata 3245 6490
B .3 E ichhornia crassipes 3385 67706770
B .3 P istia stratiotes 3385
B .3 C ladophora g lomerata 3340 6680
0 2000 4000 6000 8000 10000 12000 14000 16000
(c)
Fig. 9. Laboratory tests for phytoremediation of the environmental status of waters from the Şomârd Mediaş waste landfills toxic
pond, with aquatic species Lemna minor, Vallisneria spiralis, Eichhornia crassipes, Hydrilla verticillata, Pistia stratiotes,
Cladophora glomerata.
A. Before phytoremediation / 24.10.2012; B. After phytoremediation / 7.11.2012.
1. Control-Drinking water; 2.Water from the pond; 3. 1/2 dilution toxic pond water.
Quality parameters: 9 a - dissolved O2 mg/l; CCO-Mn; Eh–redox potential; 9 b - pH; S-salinity; 9 c - TDS-total dissolved solids;
EC-Electrical conductivity
Plants evolution in control samples with stratiotes, C. glomerata for use as constructed
unpolluted water shows that after phytoextraction, L. wetlands method (Fig. 9).
minor, V. spiralis, H. verticillata, E. crassipes, P.
stratiotes and C. glomerata have determined the 4. Conclusions
increase of the dissolved O2, CCO-Mn, EC and S and
the decrease of Eh - redox potential. H. verticillata, E. Research results proved the importance of the
crassipes, P. stratiotes and C. glomerata have also bioremediation applied for constructed wetlands
determined the increase of TDS. polluted with heavy metal ions, by using aquatic plants
Preliminary tests on bioremediation have Lemna minor, Vallisneria spiralis, Eichhornia
shown that in the samples with water from the toxic crassipes, Hydrilla verticillata, Pistia stratiotes and
pond and with ½ dilution water from the toxic pond: green algae Cladophora glomerata, producing the
L. minor plants, V. spiralis, H. verticillata, E. improvement of environmental status of wastewater.
crassipes, P. stratiotes have determined the increase Strong effects on heavy metals
of Eh, the decrease of CCO-Mn, TDS and EC. In the phytoextraction, the increase of Eh, the decrease of
samples with water from the toxic pond: P. stratiotes CCO-Mn, TDS, EC and significant decrease of NH4+
have determined the decrease of salinity, as well as a were recorded. These plants and algae can be used in
slight decrease of O2; E. crassipes and C. glomerata biotechnological systems of constructed wetlands for
have determined the increase of salinity and ecological restoration.
conductivity, as well as a slight decrease of TDS and
O2. References
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Jersey.
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Environmental Engineering and Management Journal July 2018, Vol.17, No. 7, 1765-1771
http://www.eemj.icpm.tuiasi.ro/; http://www.eemj.eu
“Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection,
Department of Natural and Synthetic Polymers, 73 Prof.dr.doc. Dimitrie Mangeron Street, 700050 Iasi, Romania
Abstract
One of the main causes of global climate change is deforestation. Wood is largely used in construction, furniture, and pulp and
paper industries, which consume hundred of millions of cubic meter of wood year by year. Forest surfaces decrease rapidly at
global level and this reality is of crucial importance for world global ecological footprint. Shortage of pulpwood for paper industry
became a great challenge and, for this reason, other raw materials must be taken into consideration. Recovered paper is the most
important raw material for paper industry, but low paper grades can be produced only. Collection rate of recovered paper is high
in most countries and there are no additional quantities to assure the large requirements of the paper industry. Today, nonwood
plants are considered more and more important raw material for this industry. Wheat and rice straws are used for decades to produce
chemical pulp in many Asian and European countries.
This paper investigates the possibility of replacing pulpwood with corn stalks as raw material in producing chemical pulp for paper.
Corn stalks are abundant agricultural waste in Romania, since more than 12 million tones of stalks were generated in 2017. It was
found that corn stalks contain less lignin than wood and can be delignified using less chemicals, at lower temperatures and in
shorter time. Moreover, corn stalks can be processed using ordinary reagents like sodium hydroxide, and pulps with different yields
and lignin content can result. Natron pulping of corn stalks offers pulps with reasonable strength properties which can replace wood
pulp in obtaining papers for corrugated board.
Received: December, 2017; Revised final: May, 2018; Accepted: June, 2018; Published in final edited form: July 2018
∗
Authors to whom all correspondence should be addressed: e-mail: gda@tuiasi.ro
Cheșcă et al./ Environmental Engineering and Management Journal 17 (2018), 7, 1765-1771
Fisher, 2012; Gimona et al., 2012). In the last decades, of paper manufacture is necessary (Gavrilescu et al.,
the woodland of EU countries has continually 2014).
decreased and now its surface represents no more than Virgin cellulosic fibres are produced from
34% from the EU countries surface. (FAO, 2014). pulpwood or nonwoods. Corn stalks are among the
Pulp and paper sector needs large volumes of nonwood waste with great potential to be used as
wood. To obtain a tone of pulp, 5-6 m3 of pulpwood resource for virgin fibers. Romania is an important
are necessary, so that a pulp mill consumes up to one producer of corn among EU countries, since more than
million cubic meters of timber per year (Gavrilescu 14 million tones were produced in 2017 (Eurostat,
and Craciun, 2012; Hetemaki et al., 2013). According 2018). The corn stalks yield was estimated at more
to Confederation of European Paper Industries than 12 million tones and represents a valuable
(CEPI), around 150 million m3 of softwood and agricultural waste. There are several traditional ways
hardwood were consumed in 2016 by the pulp and to use the corn stalks: to feed animals, for
paper sector of European Union countries (CEPI, incorporation into soil to regenerate soil humus, or for
2017). This high level of wood consumption can not household heating. A new direction refers to chemical
be overcame without serious environmental processing of stalks to obtain bio-based chemicals
consequences. Wood has become deficient and (Puitel et al., 2012).
expensive and, for this reason, paper producers have The goal of this paper is to investigate the
sought solutions to replace it. Recovered paper can posibility to replace wood with corn stalks as resource
replace wood pulp in production of many paper grades for fibrous materials required in the production of
and this raw material is largely used by paper paper used in corrugated board manufacturing.
manufacturers (Bajpai, 2015; Ghinea et al., 2014; Chemical composition of corn stalks collected from
Puitel et al., 2014; Scott, 2011). However, recovered Moldova region of Romania was determined. Natron
paper can be used in production of low quality paper pulping using sodium hydroxide was selected in order
grades and it is available in limited quantities. to estimate its delignification potential. A large range
Another solution involves the fabrication of of pulps in terms of yield and lignin content was
chemical pulp from nonwood raw materials (Kassim obtained. The strength properties of pulps were
et al., 2015; Leponiemi, 2008). Nonwood plants are of determined and the possibility for their use in
increasing interest as a potential cellulosic fiber obtaining papers for corrugated board is discussed.
resource and these include cereal straw (wheat and
rice), flax, cotton, corn stalks, rapeseed stalks, 2. Materials and methods
bagasse, reed etc. (Marin et al., 2017; Gavrilescu et al.,
2009). Stalks from current production of corn (Zea
Chemical pulp is largely obtained from wood mays L.) in Moldova region of Romania were
by means of suitable delignification processes naturally dried in laboratory and then chipped at 3-5
(Gavrilescu, 2013). Romania was a forest-rich cm length. The average moisture of stalks was 10%.
country, but the forests surface decreased from 40% in Chemical composition of stalks was determined,
1900 to 28% in 1948. According to Romsilva, the according to the standards listed in Table 1.
surface of Romanian forests accounted 25% in 2013 The corn stalks pulp was obtained using a 10L
(Romsilva, 2015). The main causes of deforestation in laboratory rotating digester with automatic control of
Romania in last decades were excessive logging and temperature (Puitel et al., 2015). An amount of 400 g
deficient reforestation. As a consequence, wood oven dried (o.d.) stalks was filled in the digester and
consumption in industry decreased year by year. Due 120-220 g o.d. pulp was obtained, depending on the
to the lack of wood and the continuously increasing of pulping conditions. Cooking liquor was prepared in
pulpwood price, Romanian pulp mills were gradually the laboratory by dissolving NaOH in tap water. The
closed, so that no pulp mill is working anymore today. following cooking conditions were used:
For this reason, Romanian paper mills were obliged to - heating time: 25-40 min., depending of cooking
replace the pulpwood with recovered paper as fibrous temperature;
source (Vlase et al., 2012). - sodium hydroxide addition: 12-16% on o.d. stalks;
Paper recycling is environmental friendly, but - cooking temperature: 120-160 oC;
involves large investment in new plants and - time at cooking temperature: 30-90 min.
implementation of appropriate technologies for paper
production. Compared to the chemical pulp, Table 1. Standards used for chemical composition
secondary fibres represent an inferior raw material and of corn stalks
only low-grades quality of paper can be produced.
Because recovered paper is used several times in Component, % Standard
producing paper, the cellulosic fibres gradually lost Cellulose TAPPI T 17 wd-70, 1970
their papermaking potential. Periodically, a certain Pentosans TAPPI T 223 cm-01, 2001
quantity of secondary fibres must be replaced with Lignin TAPPI T 222 om-02, 2002
virgin fibers (chemical pulp) in order to assure the Extractives TAPPI T 204 cm-07, 2007
required quality of fibrous raw materials. For this Ash TAPPI T 211 om-02, 2002
reason, addition of virgin fibers in the fibrous circuit
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Environmentally friendly cellulosic fibers from corn stalks
After digestion, the brown stock was defibered The lower content of cellulose, the high content
and washed with water until no color in the resulting of extractives and ash are the main drawbacks of corn
liquor was observed. Washed pulp was screened using stalks as a pulping raw material. Table 5 illustrates the
a vibratory screen with 0.25 mm slots. The screened pulping conditions and the main properties of natron
yield of pulps was gravimetrically determined and the pulp from corn stalks. As Table 5 shows, the yield and
screened pulps were analyzed for their lignin content lignin contents of pulps strongly depend on pulping
expressed as Kappa number (TAPPI T 236 om-06, parameters. The pulp yield ranges between 29.7-
2006). The pulps were refined in a Jokro mill and 55.1% and Kappa number between 21.4-64.4 units.
transformed in handsheets in accordance with the Pulp yield correlates with lignin content as Fig. 1
Rapid Köthen method (ISO 5269-3, 2008). The pulp shows. By using higher alkali addition (14-16%) and
handsheets were tested regarding their strength moderate temperatures (140-160oC), corn stalks can
properties according to the standards listed in Table 2. be delignified at low Kappa numbers (no more than 40
units), while the pulp yield ranges 30-40%. If the
Table 2. Strength properties testing of natron pulp cooking is performed at low alkali addition (12%
from corn stalks NaOH) and low temperature (120oC), pulps having
higher lignin content (Kappa number 40-65 units) and
Strength property Standard yields (40-55%) are obtained, depending on the
ISO 1924:3, cooking time. It is obvious that to obtain pulps having
Tensile strength better yields, low alkali addition and temperatures
2005
Bursting strength ISO 2758, 2014 must be used.
Corrugating Medium Test - CMT ISO 7263, 2011 It is known that lignin content is the one of
Short-span compression strength - SCT ISO 9895, 2008 main factor influencing pulp strength properties.
Figure 2 presents the influence of Kappa number on
3. Results and discussion tensile index of corn stalks pulp. It is evident that
lignin content has a great influence on pulp tensile
The corn at maturity is composed of root, index. As Fig. 2 shows, tensile index records the best
stalk, leaves, cobs and ear. After harvesting the cobs, values at pulp Kappa number of 35-45 units. A similar
the plant material taken from the field consists of behaviour was found regarding burst index of corn
stalks, leaves and ears, of which the stalks represent stalks pulps. As it is presented in Fig. 3, burst index
about 85% (by mass). Corn stalks contains pit, which values are the best at Kappa number of 30-45 units,
represents up to 90% of the stalk volume. Chemical and it is clear that tensile and burst indexes show the
composition of the constituent parts of corn stalks is same dependence on the pulp lignin content.
presented in Table 3. It is already known that both burst strength and
Corn stalks have a similar chemical composition short span compression strength are the most
related to other pulping raw materials. A comparison appreciated among strength properties of papers for
with Romanian pulpwood main species reveals that corrugated board (Campean et al., 2017; Gavrilescu
corn stalks have less cellulose, less lignin and higher and Toth, 2007). In addition, crushing resistance of the
content of pentosans and ash (Table 4). Comparative paper flutes is the key parameters of the corrugating
to wheat straw, corn stalks contain less cellulose, more medium (Gavrilescu, 2017). For these reasons, both
lignin and similar percentages of extractives and ash. short span compression strength (SCT) and crushing
The most important advantage of corn stalks is the resistance (Corrugating Medium Test – CMT) were
lower lignin content than that of wood. This means analyzed concerning their dependence on pulp lignin
that corn stalks can be delignified using less content. Fig. 4 shows the influence of lignin content
chemicals, lower temperatures and shorter time, on SCT index of pulp.
compared with wood delignification.
Chemical composition, %
Component Cellulose Lignin Pentosans Ash
(SiO2)
Stalks 39.4 20.1 25.2 0.81
Pit 31.6 17.0 27.3 0.79
Leaves 31.3 17.4 21.2 7.0
Table 4. Comparison between chemical composition of corn stalk and other raw materials for pulping
Chemical composition, %
Raw material
Cellulose Lignin Pentosans Extractives Ash
Corn stalk 38.0 18.5 26.0 6.0 5.1
Wheat straw* 43.1 17.5 27.7 5.5 5.3
Softwood** 48-53 27-33 7-11 0.5-1.6 0.1-0.4
Hardwood** 44-50 18-25 11-20 0.1-0.6 0.2-0.6
* Data according to Puitel et al. (2012); ** Data according to Petrovici and Popa (1997)
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Cheșcă et al./ Environmental Engineering and Management Journal 17 (2018), 7, 1765-1771
60
55
50
45
Pulp yield, %
40
35
30
25
20
15 25 35 45 55 65 75
Pulp Kappa number
70
Tensile index of pulp, N.m/g
65
60
55
50
45
40
15 25 35 45 55 65 75
Kappa number of pulp
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Environmentally friendly cellulosic fibers from corn stalks
Fig. 4 reveals that, by increasing pulp lignin This fact is of particular importance for the paper used
content, SCT index of the pulp handsheets increases, in corrugated board manufacture. It is obviuos that
but no maximum values is recorded. The same handsheets having higher SCT and CMT indexes are
evolution undergoes the dependence of CMT index on obtained from lignin-rich pulps, as resulted from Figs.
pulp lignin content (Fig. 5). CMT index of pulp 4 and 5.
continuously increases as the lignin content of pulp The strength properties of corn pulp presented
increases too. Comparing Figs. 4 and 5 it is in Figs. 3 and 4, comparative with the recommended
unequivocal that SCT and CMT indexes of pulp values of burst and SCT indexes listed in Table 5
depend in a similar manner on lignin content. The prove that corn straws pulp can be a valuable fibrous
explanation of this behavior is that the rigidity of source in producing of papers for corrugated board. In
cellulosic fibres boosts as lignin content increases, and this respect, corn pulp can be an attractive solution for
this determines the enhancing of handsheets rigidity. Romanian paper sector.
3.5
3
Burst index kPa.m2/g
2.5
1.5
1
15 25 35 45 55 65 75
Kappa number of pulp
40
37.5
35
SCT index, N.m/g
32.5
30
27.5
25
22.5
20
17.5
15
15 25 35 45 55 65 75
Kappa number of pulp
2.7
2.4
CMT index, N.m2/g
2.1
1.8
1.5
15 25 35 45 55 65 75
Kappa number of pulp
1769
Cheșcă et al./ Environmental Engineering and Management Journal 17 (2018), 7, 1765-1771
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