COMPARATIVE STUDY OF PHYSICO-CHEMICAL PROPERTIES OF CONTAMINATED SITES OF RANIPET, TAMILNADU, INDIA

V.L.Nirmal Bhargavi*, Dr.P.N.Sudha *Global Institute of Engineering & Technology, Melvisharam, Vellore PG & Research Department of Chemistry, DKM College, Vellore Abstract A soil pollutant is any factor which deteriorates the quality, texture and mineral content of the soil or which disturbs the biological balance of the organisms in the soil. Pollution in soil has adverse effect on plant growth. Ranipet industrial area, Vellore District, Tamil Nadu, India is found to be worlds fifth largest polluted area and has vast agricultural lands, in the uncultivable condition due to heavy metal and other pollution. The study was performed at sites affected by the heavy metal pollution. The study was performed at sites affected by the heavy metal pollution due to the discharge of effluents from various industries in Ranipet Industrial Town. Hence the present investigation has been focused on the analysis of physico-chemical factors and heavy metals in the soil and water due to the pollution caused by the industries in Ranipet like Malladi drugs and pharmaceuticals, Thirumalai chemicals limited, a dyeing unit and also tanneries. The effluents from the industries have caused irreversible damage to the environment. Productive soils are necessary for agriculture to supply the world with sufficient food. Regular monitoring of the situation is highly necessary to stop the damage caused by the industries. Key words: heavy metal pollution, physico chemical parameters, heavy metal speciation. Introduction Soil pollution is the contamination of soil by human and natural activities, resulting in change of soil quality, which is likely to affect the normal use of the soil or endangering public health and the living environment. Soil physicochemical properties are adversely affected by high concentrations of heavy metals, rendering contaminated soils unsuitable for crop production. Soil is the thin layer of organic and inorganic materials that covers the Earth's rocky
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surface. The organic portion, which is derived from the decayed remains of plants and animals, is concentrated in the dark uppermost topsoil. The inorganic portion made up of rock fragments, was formed over thousands of years by physical and chemical weathering of bedrock. Thus soil consists of a mixture of weathered minerals and varying amounts of organic matter. Soils can be contaminated as a result of spills or direct contact with contaminated waste streams such as airborne emissions, process solid wastes, sludges, or leachate from waste materials. The solubility of metals in soil is influenced by the chemistry of the soil and groundwater (Sposito, 1989). The most common chemicals involved in causing soil pollution are Petroleum hydrocarbons, Heavy metals, Pesticides and solvents. This occurrence of this phenomenon is correlated with the degree of industrialization and intensities of chemical usage. If contaminated soil is used to grow food, the land will usually produce lower yields than it would if it were not contaminated. This, in turn, can cause even more harm because a lack of plants on the soil will cause more erosion, spreading the contaminants onto land that might not have been tainted before. In addition, the pollutants will change the makeup of the soil and the types of microorganisms that will live in it. If certain organisms die off in the area, the larger predator animals will also have to move away or die because they've lost their food supply. Thus it's possible for soil pollution to change whole ecosystems. The industries in Ranipet are Malladi drugs and Pharmaceuticals, manufacturing various drugs; Thirumalai Chemicals Limited (TCL) manufacturing organic compounds; Parry & Company (Ceramics); Ultramarine (Dyes); finished leather industries; Foundries; Dying units; about 140 tanneries are established under SIPCOT and TIDCO, the Government enterprises. Some of them are under private sectors too. Tanneries generate wastewater in the range of 30 35 L/kg skin / hide processed with variable pH and high concentrations of suspended solids, BOD, COD, tannins including chromium (Nandy et al. 1999). The smudges of The Tamil Nadu Chromate and Chemicals Limited (TCC) (which was temporarily closed in the year 1995 due to the heavy damages on aquatic and terrestrial environments manufactured sodium di chromate, the basic tanning powder) also contaminate the soil in Karai, a village in Ranipet. These industries are surrounded by number of villages and theirs agricultural fields, irrigation wells and irrigation reservoirs.
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MATERIALS AND METHODS Soil and Water samples were collected from lakes of the five areas of Ranipet namely (1) Karai (2) Pulianthangal (3) Bharathi nagar (4) Tandalam and (5) Maniyambat. The samples were brought to the laboratory and the following physico-chemical characteristics of the soil and water were analyzed. a) Physico-chemical characteristics and heavy metals of water samples such as pH, Electrical conductivity (EC), Dissolved Oxygen (DO), Biochemical Oxygen Demand (BOD), Chemical Oxygen Demand (COD), Total Dissolved Solids (TDS), Total Suspended Solids (TSS), Total Solids (TS), Alkalinity, Chloride, Hardness, Sodium and heavy metals such as cadmium, copper, cobalt, nickel, chromium lead and zinc were analyzed as per the methods of APHA (1998).The Extracts from five different fractions were analysed for heavy metals such as Cadmium, Chromium, Copper, Cobalt, Lead, Nickel and Zinc using Atomic Absorption Spectrophotometry. b) Physico-chemical factors of soil such as pH, Electrical conductivity (EC), moisture, porosity, specific gravity, calcium, nitrogen, phosphorous, potassium (NPK values) and heavy metals such as cadmium, copper, cobalt, nickel, chromium, zinc and lead were analyzed as per the standards of APHA (1990). The heavy metal concentration was estimated using Atomic Absorption Spectroscopy (Varian AAA 220 FS). RESULTS AND DISCUSSION Soil and water sample (1) collected from karai lake is polluted by the effluents of Thirumalai chemicals and leather factories, Phase I. Soil and water sample (2) collected from Pulianthangal is affected by leather factories, Phase II. Soil and water sample (3) is collected from Bharathi nagar which is contaminated by Malladi drugs. Soil and water sample (4) collected from Tandalam is polluted by Malladi drugs and Stahll India pvt ltd. Soil and water sample(5) is collected from Muniyambat contaminated by Leather industries, Phase II.

Table 1: Physico chemical parameters of water samples of the five areas: (1) Karai Parameters pH Electrical conductivity ( mhos/cm) Total Dissolved Solids mg/lit Turbidity mg/lit BOD mg/lit COD mg/lit Total alkalinity mg/lit Total Hardness mg/lit Ammonia mg/lit Nitrite mg/lit Nitrate mg/lit Potassium mg/lit Phosphorus mg/lit Calcium mg/lit Sodium mg/lit Chloride mg/lit Chromium mg/lit Cadmium mg/lit 7.8 915 (2) Pulianthangal 8.5 4160 (3) Bharathi nagar 7.65 7480 (4) Tandalam 6.70 3150 (5) Muniyambat 7.5 726

749 2 310 787 188 220 0 12 73 112 0.323 125 125 210 241 12

2212 2 755 1874 811 2400 27 613 118 543 0.04 1640 1822 1750 1247 79

5443 3 450 745 724 1110 0 63 23 184 0.04 475 989 1370 4594 78

3405 2 539 1290 936 920 24 250 436 112 0.05 912 1748 1540 2125 147

664 2 420 1326 268 300 11.5 4.7 115 117 0.60 336 158 270 168 39

Physico-chemical characteristics of water samples 4

Electrical conductivity was found to be high in the water samples collected from Pulianthangal, Bharathi nagar, and Tandalam. Total dissolved solids were found to be very high in Bharathi nagar sample. Tandalam and Pulianthangal samples also showed higher values of TDS. Total hardness was in the order II > III > IV > V> I. The highest value of total hardness in site II is attributed to the usage of calcium salts in dehairing the hides. COD values were found to be in the order II> V> IV >I >III. This may be because sites II and V are highly polluted by the effluents from tanneries. Table 2: Physico chemical parameters of soil samples of the five areas:

(1) Karai Parameters pH Electrical Conductivity ( mhos/cm2) Moisture % Porosity Alkalinity mg/Kg Salinity mg/Kg Organic matter % Nitrite mg/Kg Ammonia mg/Kg Nitrate mg/Kg Phosphorous mg/Kg Potassium mg/Kg Sodium mg/Kg Calcium mg/Kg Chromium mg/lit Cadmium mg/lit 8.1 315 31 3.15 382 54.2 4.0 91.3 92.4 945 123 91 442 1045 241 12

(2) Pulianthangal 7.4 3110 32 3.11 411 543.9 6.0 71.5 51.2 404 912 172 964 1031 1247 42

(3) Bharathi nagar 8.1 3450 26 3.4 403 252.4 2.5 142.2 17.32 1410 627 91 1758 1322 4594 35

(4) Tandalam (5) Muniyambat 7.7 3721 28 2.24 441 460.1 9.1 95 94.2 1013 396 301 1124 1010 2125 76 7.4 428 35 3.81 381 123.4 8.1 78.2 71.4 863 212 228 933 910 168 15

Physico-chemical characteristics and heavy metals of soil samples

The analysis of the results of physico-chemical properties and heavy metals in the soil samples collected from the sites showed significant increase in pH, Electrical conductivity, alkalinity etc. The pH shows alkalinity in the two sites Karai and Bharathi Nagar. Electrical conductivity values were found to be very high in all the samples except Karai. The samples showed very high sodium as sodium chloride is being used in the preservation of hides.
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High concentration of heavy metal chromium was recorded in the samples collected from Pulianthangal, Bharathi nagar and Tandalam since sodium dichromate is used as a basic tanning powder in the chrome tanning process. On comparison of all the samples, Tandalam soil showed high concentration of heavy metal cadmium. The discharge of wastewater into water bodies may cause a drop or increase their pH affecting size and activities of microbial populations therein. Alkaline tannery wastewater was reported by (Shukla and Shukla 1994, Kadam 1990, Sastry 1986, Sakthivel and Sampath 1990) and in the present study the soil and water samples are alkaline.

Increase in EC values indicates presence of higher concentrations of ions. The quantity of dissolved solids in parts per million (ppm) or mg/L by weight is directly proportional to conductivity in millimhos (mMhos) per unit volume. However the electrical conductivity (EC) varies not only to the concentration of salts present, but also to the chemical composition of the nutrient solution. In the present study, all the samples show higher values of electrical conductivity than the accepted limit of 75-200 mhos/cm. At present, the EC of water is one of the important parameters used to determine the suitability of water for irrigation. Water having EC more than 20 mhos/cm have not been found suitable for irrigation purpose. (Trivedi, R.K and P. K. Goel. 1986) Alkalinity in wastewater results from the presence of the hydroxides [OH- ], carbonates [CO32-], and bicarbonates [HCO3-]. Alkalinity is the capacity of wastewaters to neutralize acids, and is undesirable (Trivedy and Goel 1986). Pulianthangal lake water shows high BOD and COD values. The high BOD levels are indications of the pollution strength of the wastewaters. The determination BOD involves the measurement of the dissolved oxygen used by microorganisms in the biochemical oxidation of organic matter. The analysis of the results reveals that the BOD values of all the samples are very high. The COD test is used to measure the oxygen equivalent of the organic material in waste
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water that can be oxidized chemically using dichromate in an acid solution, when the organic nitrogen is in the reduced. High COD levels indicate toxic state of the wastewater along with presence of biologically resistant organic substances (Sawyer and McCarty 1978). Increase in COD indicates the levels of organic and inorganic pollutants in the effluents (Trivedy and Goel., 1986) Organic matter contributes to plant growth through its effect on the physical, chemical, and biological properties of the soil. Soil organic matter gives the ability withhold water and nutrients, therefore giving plants the capacity for growth. Another advantage of organic matter is that it helps the soil to stick together which allows nematodes, or microscopic bacteria, to easily decay the nutrients in the soil. The percentage of soil organic matter is found to be very low in all the samples in the present study. The total dissolved solids were found to be very high in Bharathi Nagar sample. This may increase salinity of the water and thus may render it unfit for irrigation and drinking purposes. Consumption of water with high concentrations of total dissolved solids has been reported to cause disorders of alimentary canal, respiratory system, nervous system, coronary systems, besides, causing miscarriage and cancer (Reddy and Subba Rao 2001). The chloride contents in tannery effluents were higher (1370-1750 mg/l) as also reported by other workers (Dikshit and Shukla 1989, Sakthivel and Sampath 1990). Chloride is used in its salt form to preserve the hides. According to Environment Protection Agency (2002) permissible limits of nitrate in wastewater for discharge on land should be less than 10 mg/l as high concentrations of nitrates can cause serious health problems, when used for various purposes such as irrigation or drinking purposes. Soil sample of Bharathi nagar (1410 ppm) and water sample of Tandalam (436 ppm) show very high concentrations of nitrate.

Cr (VI) is the more toxic form of chromium and is also more mobile. (Chrotowski et al., 1991).The results showed a wide variation in the concentration of heavy metals. Hellawell (1988) and Avila et al. (1999) reported that heavy metals toxicity is affected by temperature, DO concentrations and pH and an increase in pH generally decreases the solubility of many toxic heavy metals. In general, all the samples had higher concentration of cadmium and chromium.

CONCLUSION: The above research work forms an authentic scientific report on the various contaminated sites. Thus, from the above discussion, it was found that all the physico-chemical parameters of the effluents are very high than the permissible limits and thus it is inferred that the effluents from the above said industries are discharged without proper treatment. Since, Ranipet Industrial area is highly polluted by the effluents from various industries, which had caused irreversible damage to the agricultural lands, it becomes necessary to analyze the water resources and to monitor the physico-chemical factors and heavy metals in soils of this area.

REFERENCES: 1. Sposito, G. (1989), The Chemistry of Soils, Oxford University Press, New York, 277 p.
2. Nandy, T., S.N. Kaul, S. Shastry, W. Manivel and C.V. Deshpande. 1999. Waste-

water management in cluster of tanneries in Tamil nadu through implementation of common treatment plants. Journal of Scientific and Industrial Research 58: 475- 516. Wastewater. Washington, D.C 20th edition, New York.Tessier et al.,(1979).

3. APHA, AWWA and WPCF. 1998. Standard Methods for the Examination of Water and

4. Shukla, A. and N. P. Shukla. 1994. Tannery and electroplating effluent treatmentPrecipitation of Chromium and Nickel. Indian Journal of Environmental Protection 14 (6): 457-461.

5. Trivedi, R.K and P. K. Goel. 1986. Chemical and Biological methods for the water pollution studies. Environment Publication, Karad. 6. Hellawell MJ (1988). Biological Indicators of freshwater pollution andEnvironmental Manegement, Pollution Monitoring Series, 50: 61-85. 7. Avila-Perez P, Balcazar M, Zarazua-Ortega G, Barselo Quintal I, Diaz-Deldago C (1999). Heavy metal concentrations in water and bottom sediments of a Mexican reservoir. Sci. Total Environ. 234: 185-196. 8. Sawyer, C.C. and P.L. McCarty. 1978. Chemistry for Environmental Engineers. McGraw Hill, New York. pp 331-514. 9. Reddy, P.M. and N. Subba Rao. 2001. Effects of industrial effluents on the groundwater regime in Vishakapatnam. Pollution Research 20(3): 383 - 386. 10. Dikshit, V.P. and N. P Shukla. 1989. Waste recycling and pollution control in Indian tanneries. Indian Journal of Environmental Protection 9(3): 182-186.
11. Sakthivel, M. and K. Sampath. 1990. Respiration, blood cells and food conversion

efficiency in Cyprinus carpio exposed to sublethal concentrations of tannery effluents. In: P.B. Deshmukh, AT. Mathai, R.C. Dalela and K.S. Pillai (Eds.), Environment and Experimental toxicology, Jai Research Foundation, Valvada, pp. 139 I50. 12. Environmental Protection Act 2002. Standards for Effluent Discharge Regulations. General Notice No. 44. of 2003. 13. Chrotowski.P., Durda, J.L., and Edelman.K.G. (1991), The Use of Natural Processes for the Control of Chromium Migration, Remediation, 2, pp. 341-351

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