Progress of Cryogenics and Isotopes Separation Volume 15, issue 1/2012

THE HAZARDOUS S UBS TANCE ENVIRONMENTAL IMPACT IN THE

INDUS TRIAL AREA OF RM. VALC EA

Mihaela Iordache 1,2, Ioan Viorel Branzoi 2, Ioan Iordache 3*, Nicoleta Georgeta
Dobre 2, Georgeta Totea2
1
National Research and Development Institute for Industrial Ecology Ramnicu Valcea
Subsidiary, 1 Uzinei Rm Valcea,240050

ABSTRACT

This study aims to establish the environmental impact on the degree of accumulation of
priority hazardous substances soil, water and sediment in the industrial platform Ramnicu Valcea.
Water and sediment sampl es were collected in two campaigns, in May and August 2011, and soil
samples was collected in May and October 2011. Nickel, copper, cadmium, 1,2 dichloroethane,
trichlorethylene, 1,2,4 trichlorobenzene and perchlorethylene were analyzed from water, soil and
sediment.
Concentrations of priority hazardous substances in water, upstream and downstream of the
industrial area showed lower limits than those indicated in the National Legislation. The results
show that heavy metals in sediments collected from the Olt River, (Priza Olt and Cremenari),
generally fall within the limits imposed in National Legislation. It also observed that in all three
points, 1,2 dichloroethane, 1,1,2 trichlorethylene, perchlorethyl ene, 1,2,4 trichlorobenzene taking
values below the detection method. From soil samples analyzed is found insignificant soil pollution
with heavy metals (nickel, copper, cadmium) and the organochlorine substances (1,2
dichloroethane, 1,1,2 trichlorethylene, perchlorethylene, 1, 2,4 trichlorobenzene).

Keywords: organochlorine substances, heavy metals, surface water, sediments, Olt River

1. INTRODUCTION

Freshwater scarcity is among the greatest environmental problems currently

faced by mankind, and several factors (e.g., population growth, surface-water and
groundwater pollution, and climate change) are expected to increase water stress in
many regions of the world in the coming decades [M unoz, 2006; Gasperi, 2008].
Chemical pollution of surface waters presents a threat to the aquatic
environment with effects such as acute and chronic toxicity to aquatic organisms,
accumulation in the ecosystem and losses of habitats and biodiversity, as well as a
threat to human health [Tueros, 2009; Facchinelli, 2001].

*
Corresponding author: Ioan Iordache, phone: 0040 250 732 744, fax: 0040 250 732 746 E-
mail: iordache.ioan@icsi.ro
2
Polytehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7,
Polizu Street, Sector1, Bucharest, 011061, Romania
3
National Institute for Research and Development for Cryogenics and Isotopic Technologies - ICIT
Rm. Valcea, Uzinei Street no. 4, P.O. Box Raureni 7, 240050, Ramnicu Valcea, Romania
79
 THE HAZARDOUS SUBSTANCE ENVIRONMENTAL IMPACT IN THE
INDUSTRIAL AREA OF RM. VALCEA

The Water Framework Directive 2000/60/EC is probably the most

significant European legislation introduced in the field of water in many years. This
policy requires further specific measures for pollution control and sets
environmental quality standards for 33 priority substances and certain other priority
pollutants, which are established in the more recent Directive 2008/105/EC. These
priority pollutants are characterized by high toxicity, high environmental
persistence or/and high hydrophobicity [Crini, 2005; Fu and Wang, 2011].
Water pollution due to toxic metals and organic compounds remains a
serious environmental and public problem. M oreover, faced with more and more
stringent regulations, water pollution has also become a major source of concern
and a priority for most industrial sectors. Heavy metal ions, aromatic compounds
(including phenolic derivatives, and polycyclic aromatic compounds) and dyes are
often found in the environment as a result of their wide industrial uses. They are
common contaminants in wastewater and many of them are known to be toxic or
carcinogenic. For example, chromium (VI) is found to be toxic to bacteria, plants,
animals and people. M ercury and cadmium are known as two of the most toxic
metals that are very damaging to the environment. In addition, heavy metals are not
biodegradable and tend to accumulate in living organisms, causing various diseases
and disorders. Therefore, their presence in the environment, in particular in water,
should be controlled [Acosta, 2010; Bonanno and Giudice, 2010; Chen, 2007;
Christophoridis, 2009].

2. MATERIALS AND METHODS

2.1. S tudy area

The studied area was a portion of 20 km long in the lower basin of Olt
River. This area is located at south at 12 km of the city of Ramnicu Valcea and in a
closer vicinity of a industrial platform. Olt River is one of the most important rivers
in Romania and is the largest and the longest Romanian tributary of the Danube
River. It flows through the counties of Harghita, Covasna, Brasov, Sibiu, Ramnicu
Valcea, Olt and Teleorman. Olt River flows into the Danube near Turnu M agurele,
Islaz. It has a length of 615 km.
The purpose of the present study was to evaluate the status of priority
pollutants contamination in soil, water, sediments. The sampling points were
selected for this study because it is situated near the industrial area.
The local economy is mainly influenced by the great undertakings of the
chemical industry, which makes 46.49% of the county's industrial production. The
wastewater effluents of the industrial (chemical) platform are discharged into the
Olt River. The lower course of Olt River includes 15 lakes in order to produce
electricity and for irrigation water. The average flow of Olt River is 140 m3/s, with
variations from month to month, 25-300 m3/s.
The largest amount of the annual volume of the Olt River flow it is in the
M ay - about 15% - when the melting snows in the mountains, adds abundant spring
rains, when it can exceed several times the average annual flow. M aximum
recorded at Ramnicu Valcea reached 2580 m/s. The lowest flows are registered in
80
 Iordache Mihaela , Branzoi Ioan Viorel, Iordache Ioan,
Dobre Nicoleta Georgeta, Totea Georgeta
September-October after the period of minimum precipitation and evaporation in
August and September and strong before winter maximum rainfall event. The
thermal regime of the rivers freeze and the county Valcea is closely related to air
temperature, altitude, topography, slope longitudinal profile, flow and water flow
rate. Average temperatures of Olt River are rising from January to July to August
(from 0.7C to 19.1C) with a faster growth between M arch and April (3.7C -
8.8C) and a decrease more pronounced from August to December (19.1C -
1.6C).

2.2. S amples collection and preparation

Water and sediment samples were collected in two campaigns, in M ay and

August 2011, and soil samples was collected in M ay and October 2011. Nickel,
copper, cadmium, 1,2 dichloroethane, trichlorethylene, 1,2,4 trichlorobenzene and
perchlorethylene were analyzed from water, soil and sediment. The surface water
samples and sediments samples were collected in 3 sections, distributed upstream
and downstream of chemical industrial area. This points was: Priza Olt (PO), 45
2'20"N, 2418'41"E; Cremenari (C), 4458'50"N, 2416'56"E; and Babeni-M arcea
(M ), 4455'3"N, 2414'52"E.
The soil samples were collected in eight sites, on two levels deep, level I
(10 cm) and level II (30 cm) respectively, from the industrial area (platform) of
Ramnicu Valcea, 45 2'22"N, 2415'0"E. The soil samples were collected into
polyethylene plastic bags, and taken to the laboratory.
The concentrations of Cu, Ni and Cd were determined with atomic
absorption spectrometer (ATI UNICAM 929 SOLAAR), equipped with an air-
acetylene flame. Organic compounds were determined by gas chromatography
flame method (GC-FID) and electron capture (GC-ECD). Concentrations of heavy
metals and organic compounds in the water, sediment and soil were assessed
according to the standards by the environmental legislation, respectively.

3. RES ULTS AND DISCUSS ION

3.1. The content of priority hazardous substances in surface water

They water samples was collected from the River Olt, one point upstream
and two points downstream of the industrial area (platform). The distribution of
those points was conditioned by hydro-geographical characteristic of Olt River
basin in above mentioned area: flow, effluents, dams, etc.
Concentrations of priority hazardous substances in effluents from chemical
platform are presented in Table 1. The concentration of nickel was lower than 0.28
mg/l, the concentration of copper lower than 0.06 mg/l, and cadmium concentration
was lower than 0.11 mg/l, respectively. Concentrations of priority hazardous
substances in industrial effluents, indicated in the table were close to or lower than
standard values (range).
Table No. 2 shows the concentrations of priority hazardous substances in
the three collecting point named: Priza Olt (PO), Cremenari (C), Babeni- M arcea
81
 THE HAZARDOUS SUBSTANCE ENVIRONMENTAL IMPACT IN THE
INDUSTRIAL AREA OF RM. VALCEA

(M ). Concentrations of priority hazardous substances in water, upstream and

downstream of the industrial area showed lower limits than those indicated in the
Romanian environmental surface waters, values that are similar to European
legislation (Order No. 161-2006).

3.2. The content of priority hazardous substances in sediments

To assess the degree of contamination of sediments in the studied area were

sampled from the upper layer of sediment. Table No. 3 shows the concentrations of
priority hazardous substances in sediment of Olt River. Nickel concentration was
between 11.8 and 40.211 mg/kg D.W. compared to the standard value (35 mg/kg
D.W.), copper concentration was between 8.93 and 79.5 mg/kg D.W. compare to
the standard value (40.0 mg/kg D.W.), cadmium concentration was lower method
detection limit compare to the standard value (0.8 mg/kg D.W).
The results show that heavy metals in sediments collected from the Olt
River, (Priza Olt and Cremenari), generally fall within the limits imposed in
National Legislation. It also observed that in all three points, 1,2 dichloroethane,
1,1,2 trichlorethylene, perchlorethylene, 1,2,4 trichlorobenzene taking values below
the detection method.

Table no. 1. Concentrations of priority hazardous substances in

effluents of industrial area
Effluent 1 Effluent 2 Limits
Nr. Indicators (mixing cha mber) (Biological T. Plant) outlet
UM Method of analy sis
crt. analy zed
03.05 09.08. 03.05 09.08. mg/l
1 Nickel mg/l <0.01* 0,1 0.28 0.28 0.5
SR ISO
2 Copper mg/l <0.01* <0,01* 0.061 0.06 0.2
8288:2001
3 Cadmium mg/l <0.005* 0.027 0.063 0.11 0.1
SR ISO
4 pH U.pH 9.5 10.1 11.0 11.5 6.5 8.5 10523:1997
5 1,2 Dichloroethane mg/l 0.006 0.00116 0.00006 0.00012 2,0
SR EN ISO
6 1,1,2 Trichlorethy lene mg/l 0.0006 <0.00005* 0,008 <0,00005* 0,5 10301:2003
7 Perchlorethy lene mg/l 0.03 <0.00005* 0,03 <0,00005* 0,5
SR EN ISO
8 1,2,4 Trichlorobenzene mg/l <0.000005* <0.000005* <0,000005* <0,000005* 0,05 6468:2000
*method detection limit

Table no.2. Concentrations of priority hazardous substances in water (Olt River)

PO C M
No. Indicators
UM Class Class Class Class Method of
crt. analy zed PO/I PO/II C/I C/II M/I M/II Class I
II III IV V analy sis
SRISO
1 pH U.pH 7.47 7.41 7.26 7.33 7.41 7.33 6.5 8.5
10523:1997
2 Nickel mg/l <0.01* <0.01* <0.01* <0.01* <0.01* <0.01* 0.01 0.025 0.05 0.1 >0.1
SRISO
3 Copper mg/l <0.01* <0.01* <0.01* <0.01* <0.01* <0.01* 0.02 0.03 0.05 0.1 >0.1
8288:2001
4 Cadmium mg/l <0.005* <0.005* <0.005* <0.005* <0.005* <0.005* 0.0005 0.001 0.002 0.005 >0.005
5 1,2 Dichoro- mg/l 0.4 0.35 0.5 0.52 0.2 0.24 10
ethane
1,1,2 Trichlor- SR EN ISO
6 mg/l <0.05 <0.05 <0.05*
* *
<0.05 *
<0.05 *
<0.05 *
10
ethy lene 10301:2003
7 Perchlor- mg/l <0.05* <0.05* <0.05* <0.05* <0.05* <0.05* 10
ethy lene
1,2,4 SR EN ISO
8 Trichloro- mg/l <0.002* <0.002* <0.002* <0.002* <0.002* <0.002* -
6468:2000
benzene
*method detection limit
82
 Iordache Mihaela , Branzoi Ioan Viorel, Iordache Ioan,
Dobre Nicoleta Georgeta, Totea Georgeta
Table no. 3. Concentrations of priority hazardous substances in sediment
determined in sections of Olt River
Sample name
Nr.
Indicators analyzed S-PO S-C S-M Standard limit value Method of
crt.
S-PO/I S-PO/II S-C/I S-C/II S-M/I S-M/II analysis
SR ISO
1 pH 8.73 7.47 8.17 7.58 8.05 7.36 -
10390:1999
2 Nickel
21.6 27.58 13.36 40.2 11.8 <1.0* 35.0
mg / kg D.W. SR ISO
3 Copper 11466:1999
79,5 8,93 30,9 25,7 26,8 <1.0* 40.0 SR ISO
mg / kg D.W.
4 Cadmium 11047:1999
<1,0* <1,0* <1,0* <1,0* <1,0* <1.0* 0.8
mg / kg D.W.
1,2 Dichloroethane
5 <0.02* <0.02* <0.02* <0.02* <0.02* <0.02* -
mg / kg D.W.
1.1.2 Trichlorethylene SR EN ISO
6 <0.02* <0.02* <0.02* <0.02* <0.02* <0.02* -
mg / kg D.W. 10301:2003
Perchlorethylene
7 <0.02* <0.02* <0.02* <0.02* <0.02* <0.02* -
mg / kg D.W.
1,2,4 Trichlorobenzene SR EN ISO
8 <0.01* <0.01* <0.01* <0.01* <0.01* <0.01* -
mg / kg D.W. 6468:2000
* method detection limit

3.3. The content of priority hazardous substances in soils

In order to investigate soil pollution with priority hazardous substances

there was collected samples from industrial area of Ramnicu Valcea. The soil
samples was collected from eight sites on two levels deep, level I (10 cm) and level
II (30 cm), between M ay and October 2011. The analysis on two level is
conditioned by environmental normative and is realized in order to verify the
circulation of hazardous pollutants in soil caused by precipitations and migration of
the soil microorganisms. The distribution of points was realized in order to cover
into a uniform manner all industrial area.
From the information presented is observed that the pollution with heavy
metals in both levels (I and II) dont respect a rule form point of view of
quantitative concentration, there are points where level I have higher concentration
than level II, but also the opposite is true. The same cannot be say about qualitative
concentrations, for all situations was observed that if one metal have a higher
concentration at one level in comparison with the opposite level, all heavy metal
pollutants will respect the same trend. This thing shows that heavy metals have the
same manner to migrate in soils.
In order to have good elements of comparison, the authors present in Table
7 reference values imposed by environment legislation. Table No.6 presents
concentrations of priority hazardous substances in soil collected from the studied
area. The analyses were performed compared with the environmental legislation
(Order No. 756-1997). Nickel concentration was between 12.84 and 68.15 mg/kg
D.W., cadmium concentration was lower method detection limit, copper
concentration was between 16.72 to 307.4 mg/kg D.W. It also observed that in all
three points, 1,2 dichloroethane, 1,1,2 trichlorethylene, perchlorethylene, 1,2,4
trichlorobenzene taking values below the detection method.
From soil samples analyzed is found insignificant soil pollution with heavy
metals (nickel, copper, cadmium) and the organochlorine substances (1,2
dichloroethane, 1,1,2 trichlorethylene, perchlorethylene, 1,2,4 trichlorobenzene).
83
 THE HAZARDOUS SUBSTANCE ENVIRONMENTAL IMPACT IN THE
INDUSTRIAL AREA OF RM. VALCEA

Table no.4. Concentrations of priority hazardous substances in soils

collected from the area studied
Nr. S1 S2 S3 S4 S5 S6 S7 S8 Method of
Contaminated
crt. I II I II I II I II I II I II I II I II analysis

pH SR ISO
1 7.04 7.61 7.10 7.65 6.91 7.40 7.19 7.67 7.76 7.86 7.65 4.57 8.42 7.26 7.48 7.37
Unit. pH 10390:1999

Nickel
2 26.3 36.72 13.68 27.27 17.7 56.65 54.3 68.15 21.6 21.0 44.5 12.84 29.25 38.6 22.16 19.0
mg/kg D.W.

SR ISO
Cadmium
3 <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* 2.07 <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* 11466:1999
mg/kg D.W.
SR ISO
11047:1999
Copper
4 29.45 102.5 16.72 16.72 21.1 71.7 23.4 35.4 31.8 307.4 38.43 78.4 89.9 201.3 38.6 88.65
mg/kg D.W.

1,2 Dichor-
5 ethane <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0*
mg/kg D.W.
1,1,2 Trichlor-
6 ethylene <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0*
mg/kg D.W.
SR ISO
Perchlor- 14507:2000
7 ethylene <1,0* 1,67 <1,0* <1,0* <1,0* 28,6 <1,0* <1.0* <1,0* <1.0* <1,0* <1,0* <1,0* <1.0* <1,0* <1.0* SR ISO
mg/kg D.W. 11423-2:2000
1,2,4
Trichloro-
8 <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0* <1.0*
benzene
mg/kg D.W.
*method detection limit

Table no. 5. Reference values imposed by the Order no. 756/1997

Thresholds for
Spoiler alert (P/A) intervention (P/I)
Types of uses
Nr. Limits Types of uses
Contaminated UM (mg/kg D.W.)
crt. outlet (mg/kg D.W.)
Less Less
Sensitive Sensitive
sensitive sensitive

1 pH Unit. pH - - - - -
mg/kg
2 Nickel 20.0 75.0 200.0 150.0 500.0
D.W.
mg/kg
3 Cadmium 1.0 3.0 5.0 5.0 10.0
D.W.
mg/kg
4 Copper 20.0 100.0 250.0 200.0 500.0
D.W.
1,2 Dichloroethane mg/kg
5 - - - - -
mg / kg D.W. D.W.
1,1,2 Trichlorethy lene mg/kg
6 - - - - -
mg / kg D.W. D.W.
Perchlorethy lene mg/kg
7 - - - - -
mg / kg D.W. D.W.
Trichlorobenzene mg/kg
8 <0.1 5.0 10.0 10.0 30.0
mg / kg D.W. D.W.

CONCLUS IONS

This study was realized in order to determine the degree of priority

hazardous substances pollution in the closer vicinity of the Ramnicu Valcea
industrial area (platform). Water and sediment samples was collected in two
campaigns, in M ay and August 2011, and soil samples was collected in M ay and
84
 Iordache Mihaela , Branzoi Ioan Viorel, Iordache Ioan,
Dobre Nicoleta Georgeta, Totea Georgeta
October Nickel, copper, cadmium, 1,2 dichloroethane, 1,1,2 trichlorethylene, 1,2,4
trichlorobenzene and perchlorethylene from surface water, soil and sediments were
analyzed. The results show that heavy metals in sediments collected from the Olt
River, have different concentration depending by the position from industrial area,
in ones point there are higher concentrations than in national legislation.
Concentrations of priority hazardous substances in water, also, have variations, but
were lower than the limits imposed by national legislation. In the points from
immediately vicinity of industrial area (PO, C) were found a degree of
accumulation of heavy metals higher in comparison with farthermost point (M ),
located in downstream of wastewater discharges of chemical platform.
From soil samples analyzed is found insignificant soil pollution with heavy
metals (nickel, copper, cadmium) and the organochlorine substances (1,2
dichloroethane, 1,1,2 trichlorethylene, perchlorethylene, 1,2,4 trichlorobenzene).

Acknowledgments

The authors acknowledge the support provided by Project: Doctoral

Scholarships: Investment in research and innovation and development for the future
(DocInvest), Project co-financed by European Social Fund Operational Programme
Human Resources Development 2007-2013, ID 76813.

REFERENCES

Acosta J. A., Faz A. and M artinez-M artinez S., 2010, Identification of heavy
metal sources by multivariable analysis in a typical M editerranean
city (SE Spain), Environ. Monit. Assess., 169 (1-4), 519-30.
Bonanno G. and Lo Giudice R., 2010, Heavy metal bioaccumulation by the organs
of Phragmites australis (common reed) and their potential use as
contamination indicators, Ecological Indicators, 10, 639-645.
Chen T. C. W, 2007, Distribution and accumulation of heavy metals in the
sediments of Kaohsiung Harbor, Chemosphere, 66, 1431-1440.
Christophoridis C., Dedepsidis D. and Fytianos K., 2009, Occurrence and
distribution of selected heavy metals in the surface sediments of
Thermaikos Gulf, N. Greece. Assessment using pollution
indicators, J. Haz. Mat., 168, 1082-1091.
Crini Gregorio, 2005, Recent developments in polysaccharide-based materials
used as adsorbents in wastewater treatment, Prog. Polym. Sci. 30,
38-70.
Facchinelli A., Sacchi E. and M allen L., 2001, Multivariate statistical and GIS-
based approach to identify heavy metal sources in soils,
Environmental Pollution, 114, 313-324.

85
 THE HAZARDOUS SUBSTANCE ENVIRONMENTAL IMPACT IN THE
INDUSTRIAL AREA OF RM. VALCEA

Fu F. and Wang Q., 2011, Removal of heavy metal ions from wastewaters: A
review, Journal of Environmental Management, 92, 407-418.
Gasperi J., Garnaud S., Rocher V. and M oilleron R., 2008, Priority pollutants in
wastewater and combined sewer overflow, Science of the total
environment, 407, 263-272.
M unoz I., Gomez-Ramos M . J., Aguera A., Garcia-Reyes J. F., M olina-Diaz A. and
Fernandez-Alba A. R., 2009, Chemical evaluation of contaminants
in wastewater effluents and the environmental risk of reusing
effluents in agriculture, Trends in Analytical Chemistry, 28, 6, 53-
64.
Tueros I., Borja A.l, Larreta J., Rodriguez J. G., Valencia V. and M illan E., 2009,
Integrating long-term water and sediment pollution data, in
assessing chemical status within the European Water Framework
Directive, Marine Pollution Bulletin 58, 1389-1400.

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