Investigation of effect of electrochemical process on detergent removal from synthetic wastewater by bioassay test

Abstract

LAS is an anionic surfactant which is widely used in household and industrial detergents usage and after use it usually finds a
way to the waste water treatment systems. Conventional treatment due to the long residence time and enlarged cost are not
recognized efficiently. So advanced oxidation processes including electrochemical techniques are important. In this paper,
electrochemical degradation of a synthetic solution of LAS with initial concentration 200 ppm has been investigated .The
experiment using eight stainless steel electrodes as the cathode and the anode and with the mono-polar arrangement was
performed. The effects of current density and current intensity as operational parameters on detergent removal efficiency were
studied. The results showed that at each current intensity, by reducing the current density, removal efficiency increases. So that
maximum removal efficiency 94 % was achieved at current intensity equal to 300 mA and current density equal to 6 mA/cm2.

1. Introduction

Municipal wastewater is one of the important pollution sources affecting the water quality adversely in many countries.
Especially wastewaters containing detergents are among the basic constituents of organic pollution and they cause great
environmental damage by entering the soil, sea, lakes and rivers (1). Surfactants are the active cleaning ingredients in synthetic
detergents used for all kinds of washing. Surfactants are amphiphilic substances of synthetic or natural origin, able to adsorb at
interfaces, thus reducing the surface or interfacial tension (2). They consist of a water-soluble (hydrophilic) and a water-
insoluble (hydrophobic) component.(3) . depending on the nature of the hydrophilic group, surfactants are classifed as
Anionic,Cationic,Nonionic and Zwitterionic (4) .

Anionic surfactants are the major class of surfactants used in detergent formulations(5) . LAS is the largest group of anionic
surfactants (6) . Over 40 years, LAS has been widely used in household cleaning detergents, personal care products and
industries such as textiles, paints, polymers, pesticide formulations, pharmaceuticals, mining, oil recovery and pulp and paper
(7). Surfactants find application in almost every chemical industry, including detergents, paints, dyestuffs, cosmetics,
pharmaceuticals, agrochemicals, fibres, plastics .(8) The annual European consumption of surfactants in 2011 was 2.95 Mt, of
which 1.40 Mt was non-ionic and 1.22 Mt was anionic according to the data reported by the European Committee of Organic
Surfactants and their Intermediates (9) Increased use of surfactants in various applications and the per capita increase in
consumption have increased the percentage of these compounds in sewage.(10)

After application LAS usually is discharged to the sewer system and appears in municipal wastewater treatment plants (11).
As common constituents in municipal effluents , concentrations of surfactants in municipal and industrial wastewaters,
especially those from laundries, appear to be very high. Concentrations of linear alkylbenzene sulfonates (LAS), a major
contributing anionic surfactant in laundry wastewater, can be as high as 116-454 mg/L . It is thus of significance and
indispensable to find effective ways to remove surfactants once released to water. (12) To minimize environmental problems,
this molecule has been the subject of a series of studies regarding its chemical, physical and biological removal. (13) So far,
various approaches such as ultrafiltration and ion-exchange (14) adsorption (15.) and etc. have been studied to remove
detergents from wastewaters .

In the past years, conventional biological and physical treatment methods (adsorption, ultrafiltration, coagulation, etc.) have
been used to remove the organic pollutants. These methods are not efficient and cost effective for wastewaters containing high
concentration of more toxic pollutants. This requires some novel techniques to transfer the highly toxic pollutants chemically
into benign species. (16 ) For this reason, many investigations are exploring the advanced oxidation processes for
degradation of surfactants. (17).

Advanced Oxidation Processes (AOPs) are considered to be the most promising alternative due to their high efficiency and
versatility . The AOP are based on the generation of hydroxyl radicals (HO ),which have a very high oxidation potential (E =
+2.80 V vs. SHE) and are capable of initiating a cascade of reactions that often results in the total degradation or
mineralization of the organic substance . (18) Advanced oxidation processes (AOPs) were first proposed in the 1980s for
potable water treatment . Later, AOPs were broadly applied for treatment of different types of wastewaters because the strong
oxidants can readily degrade recalcitrant organic pollutants and remove certain inorganic pollutants in wastewater. (19)

Electrochemical techniques have an important role among the advanced treatment technologies and offer a good opportunity to
prevent and remedy pollution problems . (20) The main advantage of this technology is that no chemicals are used. In fact,
only electrical energy is consumed for the mineralisation of organic pollutants . (21) Electrochemical technologies, such as
electro-oxidation (EO), electrochemical coagulation (EC) and electrochemical flotation (EF) have also received major attention
in recent years . Electrochemical techniques have been applied extensively to treat various wastewaters, disinfect drinking
water or enhance the remediation of polluted soils . (22)

Excessive use of any type of surfactants and their disposal in the environment, especially in aquatic bodies, could seriously
affect the ecosystem .(23) Suafactants can also affect living organisms and abiotic parts of the environment. They can be toxic
for different types of organisms (24) . Toxicity tests are desirable in water quality evaluations because chemical and physical
tests alone are not sufficient to assess potential effects on aquatic biota.(25)

Aquatic toxicity is usually measured on fish, daphnia and algae. The toxicity index is expressed as LC50 (for fish) or EC50 (for
daphnia and algea), where LC and EC stand for lethal and effective concentration, respectively. Values below 1 mg/L after 96
h testing on fish and algae and 48 h on daphnia are considered toxic.(8)

The aim of this work was to study the electrochemical degradation of a synthetic solution containing LAS . The influence of
operating parameters such as current density and current intensity were studied , in order to find the optimal conditions for
electrolysis. To assess toxicity of remaining solution after electrolysis , biological test were performed on samples . As a result
of the studies , the removal of surfactant of 200 mg/L was achieved with an efficiency of 94 % and energy consumption of 2.7
W.hr/gr .

2. Materials and methods

2.1 Reagents

Sodium dodecylbenzenesulfonate as a representative of LAS used in the present study was commercially obtained from
Sigma-Aldrich Co. and used without further purification. Methylene Blue reagent was commercially obtained from CARLO
ERBA. Other chemicals such as H2SO4, Phenolphthalein, CHCl3, NaOH and NaH2PO4.H2O were supplied by Merck Co.

2.2 Apparatus

The absorbance of solutions was measured by a spectrophotometer (DR/2010; HACH Co.)

Eight stainless steel electrodes were used as both the anode and the cathode. The experiments were conducted in ambient
conditions.

Fig. 1- Schematic of experimental set up

2.3 Experimental procedure

Step a. At first 2 liters tap water was taken from urban network and with the addition of the LAS synthetic wastewater with
certain concentration (200 mg/L) was prepared. The polluted water was poured in an electrolytic cell (a 2 liter beaker) and
using stainless steel electrodes (15 cm length, 3 cm width and 1 mm thickness) electrochemical process was applied on it. In
this run, 3 cm height of electrodes was submerged in the solution. The electrochemical process was done without, any changes
in pH (about 7-8), temperature (about 20 C) and electro conductivity (4400 scm-1), it was done by the aforementioned
electrodes at the current intensity of 200 mA for one hour. Then a sample was taken to determine the concentration of LAS
residue. The LAS residue was measured using Methylene Blue Active Substance (MBAS) on the basis of the 5540 C method
in the 22nd edition of Standard Methods for The Examination of Water and Wastewater book. Finally transferring the rest of
cell content to another vessel, a total of 10 fish was leaved in it. The experiments were repeated three times for good accuracy.

Step b. Such as step a. but with current intensity of 300,400,500,600,700,800 and 900 mA the experiments were done.

Step c. At this stage the submerged height of electrodes was increased to 6 cm and the steps a. and b. were repeated.
Step d. this stage is similar to the step c with the exception of 9 cm submerged electrodes height.

The energy consumption was calculated by following formula for each run.

U.I.t
Required energy = (C
0 C).V

Which, U is voltage, I is current intensity, t is period of process time, V is volume of sample , C0 is initial concentration of
LAS and C is final concentration of LAS .

Black molly fish (poecilia sphenops ) was applied to the bioassay test on treated and untreated synthetic wastewater samples.
Ten fish 51 cm length , 21 gr weight was leaved in each of them. The fish survival status was monitored up to 96 hours.
The number of dead and live fish at the end of each 24 hours was recorded.

3. Results and discussion

In this study the effect of electrochemical process to remove LAS from synthetic wastewater was investigated and bioassay test
was used for its detoxification confirmation.

Table 1 shows the remained LAS concentrations besides, energy consumptions according to electrical current intensity and
electrode immersion heights. It is noticeable that the initial concentration in all runs was 200 mgrL -1. It can be concluded that
tbe optimum electrical current and electrod height are 300 mAmp. and 9 cm respectively. In this condition the energy
consumption was calculated 2.7 Wh/gr per removed LAS.

Table 1- remained LAS and energy consumption in different

electrical current inensities and electrode immersion heights.
Current (mA) 200 300 400 500 600 700 800 900
Electrode
height (cm) N=4 N=4 N=4 N=4 N=4 N=4 N=4 N=4
remained
871 676 702 751 802 834 822 696
LAS (mgL-1)
3 energy
3.50.3 5.20.4 7.70.4 12.50.5 17.81 22.31.1 28.11 30.51.2
consumption
remained
843 364 473 662 713 793 684 544
LAS (mgL-1)
6 energy
2.90.2 3.80.2 6.00.4 8.80.7 10.90.8 15.40.8 16.40.9 18.20.9
consumption
remained
854 125 362 431 567 723 593 333
LAS (mgL-1)
9 energy
consumption
2.90.2 2.70.1 4.40.3 5.90.4 8.30.5 12.60.8 13.40.8 13.30.8

In Figure 2, the LAS removal efficiency in terms of current intensity for different electrode submersion heights has been
shown. As can be seen with increasing height of electrode immersion LAS removal efficiency was increased. Obviously the
optimum current intensity and electrode height was 300 mA and 9 cm respectively. In this condition, the maximum removal
efficiency of LAS was 94% which, the LAS concentration was reduced from 200 to 12 mgL-1.

100
3 cm electrode immersion height
6 cm electrode immersion height
90 9 cm electrode immersion height
LAS removal eff. %

80

70

60

50
100 200 300 400 500 600 700 800 900 1000
current intensity ( mA )

Figure 2, the LAS removal efficiency in terms of current intensity for

different electrode submersion heights
Fig. 3 shows the LAS removal efficiency vs current density, it can be concluded that the best efficiency is obtainable in
6mAcm-2.

100
95 3 cm electrode immersion height
90 6 cm electrode immersion height

LAS removal eff. %

85 9 cm electrode immersion height
80
75
70
65
60
55
50
0 5 10 15 20 25 30 35 40 45 50 55

current density ( mA/cm2 )

Fig. 3 - The LAS removal efficiency vs current density

To assess the electrolysis detoxification of LAS biological test carried out on samples using Molly fish ( poecilia sphenops ).
Ten fish were leaved in each 2 liter beaker containing the treated solution then the fish vital status after 24, 48, 72 and 96 hours
was evaluated. In parallel, this test was done on contaminated water without electrochemical process and raw water as control
groups. All fish leaved in uncontaminated water survived for 4 days while all in untreated contaminated samples died in early
minutes. Only under the optimum electrochemical process condition eight fish was survived until 4 days since the end of the
process and the statistical analysis showed a meaningful difference between optimum condition and the others for fish survival
(PV<0.05) .

10 3 cm electrode immersion height

6 cm electrode immersion height
N0. of live fishes

8
9 cm electrode immersion height
6
4
2
0
200 300 400 500 600 700 800 900
current intensity (mA)

4. Conclusion

The aim of this article was Investigation of effect of electrochemical process on LAS removal from synthetic wastewater by
bioassay test. In the first step determination of the optimal current intensity and current density stainless steel electrodes were
aimed. it can be concluded that LAS can be effectively removed from water by electrochemical process. In 300 mA electrical
current and 6mAcm-2 electrical current density the maximum efficiency ((94%) was obtained and the LAS concentration was
decreased from 200 to 12 mgL-1. This efficiency is compatible to what stated by Koparal et al (1) which could achieve a
similar efficiency (94%). The energy consumption in our research was calculated 2.70.1 Whr/gr it is much less than what
declared by Koparal et al(11.3 KWhr/gr). It is maybe because of different process condition, different electrods also, the initial
LAS concentration. It is noticeable that their experiments were done on 50 mgL-1 LAS. Onder et al (20) study which
conducted on removal of 10 mg/L LAS led to 100% removal efficiency after a period of one hour. The energy consumption of
about 6 KWhr/gr has been state by them.
We applied bioassay test for assessment of the effectiveness of electrochemical process on LAS detoxification. Results showed
that only under above mentioned optimum conditions eighty percent of fish was survived until 4 days since the end of the
process. From the stand point of bioassay test the difference between optimum and the other conditions was significant so it
can be concluded that the electrochemical process has a good capability to reduce the LAS toxicity as well as its concentration.
More research was not access able in international network system.
Acknowledgements

This paper is extracted from the results of research project No. 9522, which was conducted at Kashan University of Medical
Sciences . The authors are grateful to the deputy of research of Kashan University of Medical Sciences for fnancial support .

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Fig. 4 shows the LAS removal efficiency vs energy consumption

100
3 cm electrode immersion height
95
6 cm electrode immersion height
90 9 cm electrode immersion height
LAS removal eff. %

85
80
75
70
65
60
55
50
0 5 10 15 20 25 30 35

energy consumption ( W.hr/gr )

Fig. 4 the LAS removal efficiency vs energy

Because the voltage and current density are the main parameters for the computation of energy requirements in the figure 4, the
voltages vs current density for three submerged electrode heights has been compared.

10 3 cm electrode immersion height y = 0.0072x + 2.4833

6 cm eelctrode immersion height R = 0.987
potential different ( volt )

9 cm electrode immersion height

8
y = 0.0031x + 3.0536
R = 0.9389
6

4 y = 0.0025x + 2.65
R = 0.9528

2
100 200 300 400 500 600 700 800 900 1000
current intensity ( mA )

Fig. 4 comparison of needed voltages in term of current intensity

for different submerged electrodes height
the contaminated water samples that the electrochemical process applied to them , showed a good alignment between chemical
test results the and bioassay results . These findings suggest that detoxification of LAS has happened to the fish in optimum
conditions and only 80 percent of the fishes survive in these conditions . Fisher's test results showed significant differences in
optimal conditions and other process conditions ( PV < 0.05 ) .

In the below figure , the number of live fishes in terms of current intensity and and different electrode immersion heights has
been showed .