International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 215 HEAVY METALS CONTAMINATION OF TEA ESTATES SOIL IN SIVASAGAR AND DIBRUGARH DISTRICTS OF ASSAM, INDIA T.N. Nath Associate Professor , Department of Chemistry, Moran College, Sivasagar, Assam, India. taranathnath@yahoo.co.in K.G.Bhattachayya Professor, Department in Chemistry, Gauhati University, Guwahati, Assam, India. Abstract: The aim was to determine the concentration of heavy metals in tea estates soil in the Dibrugarh and Sivasagar districts of Assam, India. Soil samples from twenty tea estates and a control site were analysed for selected heavy metals namely: Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn. Soil samples were obtained triplicates and at depths of 0 to 15(surface), 15 to 30(subsurface I) and 30 to 60(subsurface II) cm respectively in the month of December every year from 2007 to 2009. According to the results, Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn contents of soils ranged from 1.52 to 2.83, 1.28 to 2.80 and 1.19 to 2.69 mg/kg; 68.73 to 102.02, 56.0 to 94.07 and 46.58 to 88.93 mg/kg; 16.73 to 36.33, 15.35 to 31.73 and 13.17 to 29.13 mg/kg; 4.933 to 10.766, 4.405 to 9.962 and 3.206 to 8.531 mg/g; 25.17 to 52.88, 20.17 to 41.67 and 16.97 to 33.70 mg/kg; 118.53 to 420.53, 103.73 to 390.33 and 92.07 to 377.50 mg/kg; 34.40 to 65.37, 30.67 to 60.00 and 19.13 to 46.27 mg/kg and 21.43 to 65.20, 21.07 to 56.47 and 17.70 to 48.87 mg/kg for the surface, subsurface (I) and subsurface (II) soil respectively. Evidence of contamination of these soils was obvious when these values were compared to the control soil. The results revealed that the concentration of the heavy metals were below the typical agricultural soil critical level but higher the soil control. Among these Cu, Fe, Mn and Zn are micronutrients and Cd, Cr, Ni and Pb are soil pollutants. Heavy metals can create some harmful effects on the eco- system and cause the environmental pollution due to their toxic impacts on plants, animals and human beings. Keywords: Heavy metal, micronutrients, soil pollutants, eco-system, environmental pollution and toxic impacts. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 216 Introduction: Soil testing is a key weapon in assessing the fertility of soil [40]. Soil testing results can be effectively used for assessing plant nutrient requirement [53]. To increase the tea production, a huge amount of fertilizers are applied in the tea estates soil. Fertilizers can enhance the soil fertility and also yield the productivity of tea. But fertiligers itself contain sufficient amount of heavy metals. Therefore, the heavy metal concentrations in soils gradually increased. Soil is a medium of acting as a sink for natural and anthropogenic pollutants [18]. Humans are introducing heavy metals into the environment. Heavy metals were no longer restricted to local area but were distributed over a wide area by means of air, water and soil. When the heavy metals are carried into the soil, they will accumulate there with time and enter into the ecosystem or the food chain causing harm to human health [27], [82]. Soil heavy metal contamination has occurred since prehistoric times, but the extent of contamination has increased by the geogenic, rate of urbanization and several anthropogenic activities. The anthropogenic activities such as mining and smelting operation, application of sewage sludge, inorganic fertilizers animal wastes and pesticides [4], [55] ,[38], [54]. Anthropogenic contamination with heavy metals is a worldwide problem that causes massive water and soil pollution [16], [66]. Heavy metals that have contaminated industrialized areas, roadside soils, riverbanks, and urban areas are among the most serious environmental hazards [45]. The management of metal-polluted soils is now of major concern for most industrialized countries because of the ubiquity of the metals, their environmental persistence and their hazardous effects for the environment and human health [28], [20], [64], [23]. Various remediation methods, such as soil excavation and land filling, may be very helpful to contribute to restore metal-polluted soils [52]. These methods are usually expensive and some of them have unfortunately induced adverse effects on the biological activity, the structure and the fertility of soils. An alternative stagedy is the use of plant species to stabilize or remove pollutants from soils, defined as phytoremediation [69]. Phytoextraction technology is defined as the use of plants to remove metals from soils into the harvestable part of their biomass [21]. Heavy metal uptake and accumulation by plants depends on metal speciation, mixed contamination, soil factors (pH and CEC) and plant characteristics (root depth, species, age etc.) [9], [15]. One of the key steps in phytoextraction remains the selection of plant species [52] Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 217 Unlike other heavy metals such as Cu, Zn, Mn and Fe that are essential to living cells at low concentrations, Pb does not have any known biological role [67]. While the introduction of unleaded gasoline has contributed to the decrease of lead emissions into the environment, lead pollution is still significant due to historical loads as well as to the continuing deposition from other sources including, mining, smelters, and batteries disposal [1]. A debate exists among researchers whether absorbed metals are bioavailability, while some claim that only soluble metals are available [1], [33], [65]. Others demonstrated that some metals e.g. Cd and Pb are bioavailable even when absorbed to particulate matter [34], [13]. Such discrepancies on the need, scale, costs, and clean up goals of contaminated soils [12]. Numerous studies on contaminated soil suggest that physiochemical soil properties such as pH and clay and organic matter content are the major factors controlling heavy metal toxicity and bioavailability [36], [61], [60]. It was demonstrated that only desorbed Pb is bioavailable, while bound Pb is not [45]. Because of their enormous adsorption capacity, organic matter and Fe-oxide are capable of taking up very large amounts of Pb and do not release any detectable Pb to solution, diminishing the bioavailability of Pb [25], [71], [31]. The bioavailability of Pb depends on the type of the soil and the components it contain. Arid and semiarid soils which contain large amount of carbonates and have little organic matter will effect differently the solubility of Pb and hence its bioavailability compared with temperate soils which usually lack pedogenic carbonate but have large amount of organic matter [45]. Sewage sludge, an envitable by product of waste-water treatment, contains high proportions of organic matter and plant nutrients [79] [49], [70]. The use of it improve the physical and chemical properties of soil is recommended [46], [74]. It contains contaminants, and excessive salts, which much also be considered in its agricultural use [58]. Heavy metals in sewage sludge may enter the food chain through crops and affect human health [75]. The physicochemical effects of the long-term use of sewage sludge in the amendment of topical soils are still uncertain [48], [56],[77]. The accumulation of heavy metals in plants has been a serious environmental concern because their uptake by plants from contaminated soils is the principal processes by which heavy metals enter the food chain and then to men and animals and are relatively toxic at levels slightly above than those required for maintaining normal Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 218 metabolic activities of body [32], [62], [24], [18], [36]. The uptake of heavy metals by plants from soil depends on their concentration in soil, organic matter, soil, clay content and on their specific geochemical properties [8]. Plants species differ not only in heavy metals’ uptake but also with respect to the translocation of metals to various plant organs [42] which influence heavy metal concentration in food chain and food stuffs [43]. The degree of toxicity depends upon the form in which they are present. Thus, organo-lead is much more poisonous than the inorganic form. The oxidation state of metals also plays an important role in this regard. So, the hexavalent chromium is more toxic than its trivalent forms [6]. The present work is an attempt to study the census of heavy metal concentration of tea estates soils in Dibrugarh and Sivasagar district. Materials and Methods: The studies were conducted in twenty tea estates soil which covers approx 7000 hectares of land in Dibrugarh and Sivasagar districts. Sivasagar district is one of the most important historic and industrial City of Assam. The Sivasagar district is located from 25 045 / to 27 015 / N latitude and 94025/ to 95 025 / E longitude. It has elevation of 86.6 Mts. above the sea level. It is surrounded by Lakhimpur district and Dibrugarh district in the north, Arunachal Pradesh and Dibrugerh district in the east, Arunachal Pradesh and Nagaland in the south and Jorhat in the west. The geographical area covered by sivasagar district is 2668 sq km. The physiography of Sivasagar district is mainly valley. The tributaries of Brahmaputra River like dimow, Darika, Disang, Dikhow etc. flows through this district. Sivasagar district carries a pleasant weather throughout the year. The temperature ranges from 80C to 180C in winter and 150C to 35 0C during summer. The district is characterized by highly humid atmosphere and abounded rains. The average rainfall is about 230 cm. The regular rains of the summer generally prevent the prevalence of the hot weather. There are 119 tea estates in Sivasagar district which covered the area of 88008 Hectares land. Besides these tea estates, 80 registered small tea growers and 4004 small tea growers, this covers the 5356 Hectares of land in this district. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 Fig.1 Location of study area and soil sampling stations. Copyright © 2013 SciResPub. 219 International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 220 Dibrugarh, the head quarter of Dibrugarh district is famous as the “Tea City of India”. Dibrugarh district is situated in the eastern part of Assam. The Dibrugarh district extends from 27 005.38/ N to 27 042.30 / N Latitude and 94 033.46/ E to 95029.80/ E Longitude. It is surrounded by Dhemaji district and a part of Lakhimpur district in the North, Tirap district of Arunachal Pradesh and a part of Sivasagar district in the South, Tinsukia district in the East, and Sivasagar district in the West. The geographical area covered by Dibrugarh district is 3381 sq km. The physiography of Dibrugarh district is mainly valley. The Dibrugarh district is located in the north eastern corner of the Upper Brahmaputra valley south with an altitude ranging between 99 and 474 meters. A major part of it is and extensive plain formed by the Brahmaputra and its major south bank tributary –the Buri-Dihing. Being located on the north of the 270N latitude and with its unique physiographic elements, the area experiences subtropical monsoon climate with mild winter, warm and humid summer. Rainfall decreases from south to north and east to west in the area. The average annual rainfall of the Dibrugarh city in the north is 276 cm with a total number of 193 rainy days, while at Naharkatia in the south; it is 163 cm with 147 rainy days. The temperature generally decreases from south to north. The average annual temperature in Dibrugarh and Naharkatia is 23.9 0C and 24.30C respectively. There are 139 tea estates in Dibrugarh district which covered the area of 120489 Hectares land. Besides these tea estates, there are 104 registered small tea growers and 6530 small tea growers, which covering the 11798 Hectares land. In the plains of Dibrugarh and Sivasagar districts, the soil is Alluvial. The soil in adjacent to the river banks is sandy and away from the bank is muddy. The main crops grown in this district are tea and rice. Tea is the most important cultivation in this area. The districts are the largest producer of tea in Assam (about 70% of the total production). The productivity of tea is about 1850 kg per hectare. The tea estates which are selected for studies (Figure 1) are (1)Sepon tea estate: 27007.105 / N and 0940 50.466/ E (2) Moran tea estate: 27007.391/ N and 094052.943/E (3) Doomar Dullung tea estate: 27007.609 /N and 094 052.903 / E (4) Hingrijan tea estate: 27008.618 / N and 094056.628 / E (5) Khumtai tea estate: 27009.548 / N and 094056.236 / E Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 221 (6) Teloijan tea estate: 27013.596/ N and 094057.759/ E (7) Thowra tea estate: 27007.222/ N and 094049.922 / E (8) Mahkhooti tea estate: 27006.498/ N and 094048.459/ E (9) Maskara tea estate: 270 07.298/ N and 094043.647 / E (10) Rajmai tea estate: 27005.975 / N and 094042.789 / E (11)Amarawati tea estate: 27016.276/ N and 094055.761/E (12)Borboruah tea estate: 27024.554 /N and 094 053.237/E (13)Bamunbari tea estate: 27014.415/ N and 094059.018/ E (14)Khowang tea estate: 27014.936 /N and 094053.311 /E (15)Duliabam tea estate: 27016.364 /N and 094055.277/E (16) Diksam tea estate: 27012.710/N and 095001.684/E (17)Ghoorania tea estate: 27021.378 /N and 094 052.188 /E (18)Durgapur tea estate: 27023.506/N and 094052.443 /E (19) Dirai tea estate: 27 012.070 / N and 095 002.030 / E (20)Lepetkata tea estate: 27022.649 /N and 094 052.139/E A total of 60 surface soil samples (0-15) cm, corresponding 60 subsurface (I) soil samples (15-30) cm and 60 subsurface (II) soil samples (30-60) cm were collected from the different area of the twenty tea estates. Soil samples were collected every year at the same time, in the months of January and February, because no fertilization or compost was applied during these months in the tea estates. Soil control sample was equally collected from the nearby the tea estate area with no fertilization. The collection of soil samples is done by using a soil auger. Several samples are collected from a single station from three grids (7×10 m) within each field and these are then mixed together to obtain a composite representative samples. The effective size reduction was done by coning and quartering method. Preliminary treatment of the soil samples after collection, preservation and analysis are carried out by following standard procedures [35], [10], [30]. The total organic matter was estimated by Walkley-Black method [78]. For heavy metals, about 1g of the sieved air dried soil samples were transferred to 100 ml beaker. A triacid mixture [63] about 25-30 ml consisting of Conc.H2SO4, Conc. HCl and Conc. HNO3 in the ratio of 4:2:1 was added to each beaker.The mixture was heated on a hot plate gently at first and then more strongly until white fumes were no longer Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 222 evolved. The digested soil was treated with hot dilute HCl (1:1) and kept overnight and filtered through a Whatman No 42 filter paper and washed several times with distilled water.The filtrates were diluted so as to get an adequate volume of solution for analysis. The dilution factor was noted. The digested extracts were then analyzed for the concentration of heavy metals (Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn) by atomic absorption spectrophotometer (Varian Spectra 220). Result and Discussion:The experimental results of the analysis at three depths (0-15) cm, 15-30) cm and (30-60) cm are presented in table 1 to 11 for the tea estate soils. Table 1. Total organic carbon content (%) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 2.3 1.52 1.2 2 2.81 1.53 1.48 3 2.8 1.98 1.65 4 2.72 1.9 1.61 5 2.22 1.49 1.12 6 2.07 1.31 0.97 7 3.05 2.27 1.92 8 3.23 2.41 2.11 9 2.02 1.28 0.96 10 2.97 2.14 1.81 11 2.16 1.47 1.09 12 3.6 2.81 2.46 13 1.91 1.27 0.9 14 3.21 2.4 2.08 15 2.96 2.14 1.71 16 1.87 1.19 0.88 17 2.64 1.85 1.54 18 2.12 1.4 1 19 2.15 1.44 1.02 20 2.76 1.96 1.63 Control 1.34 1.2 0.8 Values are means of three measurements. Table 2. Cadmium content (mg/kg) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 2.19 1.9 1.83 2 2.48 2.3 2.29 3 2.4 2.25 2.14 4 2.31 2.11 1.97 5 2.11 1.86 1.71 6 1.78 1.57 1.44 7 2.73 2.51 2.47 8 2.82 2.69 2.61 9 1.65 1.51 1.4 10 2.67 2.45 2.4 11 2.06 1.79 1.62 12 2.83 2.8 2.69 13 1.61 1.43 1.26 14 2.8 2.59 2.54 15 2.57 2.38 2.33 16 1.52 1.28 1.19 17 2.27 2.06 1.87 18 1.86 1.66 1.5 19 1.98 1.76 1.56 20 2.35 2.16 2.06 Control 1.42 1.06 0.96 Values are means of three measurements. The percentage of total organic matter ranged from 1.87 to 3.60%, 1.19 to 2.81% and 0.88 to 2.46% for the surface, subsurface (I) and subsurface (II) soil respectively. The organic carbon of the soil samples were higher in tea estate soil, this may be due to Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 223 addition of fertilizers, animal wastes, tea leaves and branches into the soil. The percentage of organic carbon decreased as soil depth increased. Similar evidences have been reported by many researchers [8] that organic carbon was more in the top soils and decreased as depth increased. It was found that the percentage of total organic matter of the tea estate soil increases during the study period from 2007 to 2009. Table3. Chromium content (mg/kg) of soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 82.42 72.92 63.7 2 91.9 82.43 74.07 3 90.53 80.53 72.5 4 86.38 76.33 68.17 5 80.92 70.83 61.57 6 74.58 63.97 54 7 96.93 89.13 82.4 8 99.8 92.67 87.77 9 72.18 60.38 50.38 10 95.28 87.9 80.53 11 79.83 68.5 59.03 12 102.02 94.07 88.93 13 70.97 58.3 48.83 14 98.3 91.1 84.87 15 93.6 85.83 78.13 16 68.73 56 46.58 17 84.5 75.03 66.13 18 76.23 64 55.5 19 78.1 66.47 56.72 20 88.37 78.37 71.07 Control 42.2 34.6 28.4 Values are means of three measurements. Table4. Total copper content of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 24.12 20.6 17.2 2 27.89 23.83 21.23 3 27.4 23.17 20.03 4 25.97 22.23 18.88 5 23.93 20.37 16.93 6 21.5 17.33 14.53 7 30.77 27.53 24.6 8 34.52 29.9 26.83 9 19.93 16.4 13.9 10 30.03 26.73 23 11 23.5 19.87 16.27 12 36.33 31.73 29.13 13 18.67 15.77 13.43 14 31.9 28.07 25.33 15 28.85 25.23 22.07 16 16.73 15.35 13.17 17 25.03 21.83 17.9 18 22.57 19.13 15.27 19 23.2 19.77 15.87 20 26.75 22.93 19.33 Control 12.8 10.5 8.4 Values are means of three measurements. The concentration of Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn were varied from 1.52 to 2.83, 1.28 to 2.80 and 1.19 to 2.69 mg/kg; 68.73 to 102.02, 56.0 to 94.07 and 46.58 to 88.93 mg/kg; 16.73 to 36.33, 15.35 to 31.73 and 13.17 to 29.13 mg/kg; 4.933 to 10.766, 4.405 to 9.962 and 3.206 to 8.531 mg/g; 25.17 to 52.88, 20.17 to 41.67 and 16.97 to 33.70 mg/kg; 118.53 to 420.53, 103.73 to 390.33 and 92.07 to 377.50 mg/kg; 34.40 to 65.37, 30.67 to 60.00 and 19.13 to 46.27 mg/kg and 21.43 to 65.20, 21.07 to 56.47 and 17.70 to 48.87 mg/kg for the surface, subsurface (I) and subsurface (II) soil respectively. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 224 The heavy metals fraction of the soil showed largest variation from metal to metal and tea estate to tea estate. The heavy metals can enter the soil by a number of pathways and their behaviors and fate in soils differ according to their sources and species. Once heavy metals are introduced into the soil they accumulate in the soil system. Table 5. Iron content (mg/g) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 7.475 6.6 5.115 2 9.366 8.436 6.964 3 8.952 8.069 6.625 4 8.108 7.194 5.705 5 7.194 6.352 4.897 6 6.051 5.182 3.687 7 10.232 9.281 7.808 8 10.632 9.775 8.358 9 5.582 4.623 3.533 10 9.975 9.122 7.636 11 6.808 5.963 4.521 12 10.766 9.962 8.531 13 5.197 4.415 3.287 14 10.485 9.592 8.138 15 9.755 8.86 7.407 16 4.933 4.405 3.206 17 7.809 6.945 5.404 18 6.437 5.579 4.116 19 6.56 5.605 4.156 20 8.615 7.715 6.275 Control 4.052 3.68 3.022 Values are means of three measurements. Table 6. Manganese content(mg/kg) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 260.33 238.63 210.13 2 333.2 307.93 277.73 3 318.5 288.63 267.93 4 288.73 260.27 235.4 5 245.93 223.53 197.8 6 174 157 144.2 7 373.7 357.4 328.73 8 404.6 383.6 356.8 9 153.4 144.8 123.3 10 360 349.53 310.87 11 230.67 207.3 185.6 12 420.53 390.33 377.5 13 138.07 120.3 101.8 14 390.13 373.13 343.07 15 347.33 322.8 290.47 16 118.53 103.73 92.07 17 274.07 248.3 225.3 18 196.1 183 158.8 19 215.23 191.57 171.53 20 302.47 276.27 247.07 Control 98.04 86.28 78.8 Values are means of three measurements. The content of solid-phase humic substances is greatly affecting the adsorption capacity for heavy metals by cation exchange and formation of chelate complexes. Carboxy groups play a predominant role in metal binding in both humic and fulvic acid [3]. Presence of dissolved organic matter, may, on the contrary, also decrease heavy metal adsorption, as found for copper by some workers [51]. It was investigated that the sorption of heavy metals (including Cu, Cr, Pb and Zn) to humic acid at different pH values and found that Pb was adsorbed to the highest extent in the pH range 2.4 to 5.8 and Zn to the least extent [72]. The influence from organic matter on the overall adsorption is dependent on the actual heavy metal [57]. Different mechanisms are Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 225 responsible for the adsorption and retention of heavy metals in polluted soils such as specific adsorption, cation exchange capacity, organic complexation and coprecipitation [2], [3]. The affinity of different heavy metals for adsorption to different soil particles is a highly complex Table 7. Nickel content(mg/kg) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 49.63 44.43 33 2 57.9 45.13 38.3 3 56.6 48.07 37.2 4 52.8 46 35.43 5 48.7 43.27 31.8 6 43.1 37.07 27.4 7 61.1 51.83 41.63 8 63.67 55.27 44.47 9 40.43 36.13 25.33 10 60.07 50.77 40.53 11 46.93 41.93 31 12 65.37 60 46.27 13 36.9 33 22.5 14 62.5 53.07 43.03 15 59.13 49.73 39.3 16 34.4 30.67 19.13 17 51.33 45.33 34.6 18 44.9 39.67 28.93 19 45.87 41 30.27 20 55.1 46.97 36.5 Control 26.54 24.2 23.8 Values are means of three measurements. Table 8. Lead content (mg/kg) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 36.77 29.4 24.83 2 44.08 30.07 28.7 3 42.17 33.78 28.2 4 39.77 31.77 26.82 5 35.98 28.05 23.97 6 30.58 24 20.23 7 47.85 37.8 30.93 8 50.9 40.55 32.97 9 28.4 22.73 19.23 10 46.73 36.87 30.33 11 34.97 27.03 23.13 12 52.88 41.67 33.7 13 26.67 20.95 17.83 14 49.22 38.5 31.97 15 45.4 36 29.6 16 25.17 20.17 16.97 17 38.53 30.52 25.83 18 32.22 25.03 21.13 19 34.02 25.95 22.6 20 41.28 32.53 27.53 Control 20.34 18.8 17.12 Values are means of three measurements. matter [57]. Lead adsorbed to a high extent as the only heavy metal to iron oxides, whereas, e.g., Cd, Cr, Cu, Ni, Pb and Zn all adsorbed to vermiculite in a study of different heavy metals to individual soil components [19]. Uptake of Cadmium depends upon the content of Zinc in the soil, and plants generally take up more Cadmium if Zinc content is low [41]. The retention of heavy metals in a specific soil depends on the soil composition as well as on the actual heavy metal [57]. It was also investigated the relation between pH and Zn solubility in spiked acid and calcareous soils [68]. Zinc was solubilised at a slightly higher pH in the calcareous soils than in the acid soils [47]. Lead and nickel occur at the highest concentrations, usually near the roadsides, Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 226 associated with Zinc and Cadmium [14], their amounts decrease with increasing distances from the road and with increasing depth in soil [59], [76]. Table 9. Zinc content (mg/kg) of the soil samples at three depths. Sample Surface Subsurface I Subsurface II 1 41.97 39.53 29.83 2 51 49.27 37.93 3 47.8 46.27 36.3 4 45.53 43.53 33.3 5 40.57 37.83 27.73 6 33.03 30.07 22.93 7 58.27 52.13 41.73 8 62.8 55.07 46.4 9 30.9 27.17 20.8 10 55.77 50.73 40.27 11 38.4 36.37 26.6 12 65.2 56.47 48.87 13 25.57 22.67 19.47 14 60.43 53.5 44.2 15 52.87 50.1 39 16 21.43 21.07 17.7 17 44.23 41.57 31.77 18 34.97 31.47 23.9 19 37.1 34.33 25.47 20 46.6 44.6 34.8 Control 20.82 18.68 16.9 Values are means of three measurements. Table 10. Probable background levels and typical concentration of some heavy metals in soils Heavy metal Cd Cr Cu Ni Pb Zn Background concentration(mg/kg) 0.1 to 40 80 to 200 6 to 60 1 to 100 12 to 20 17 to 125 Source: [14],[6], [33] [2],[47] Copyright © 2013 SciResPub. Typical concentration (mg/kg) 0.1 to 50 5 to 1500 2 to 250 2 to 1000 2 to 300 10 to 300 International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 Table 11. Maximum and minimum measured values of heavy metals contents(mg/kg) of soils Sample Measured limits 1 Max. Min. 2 Max. Min. 3 Max. Min. 4 Max. Min. 5 Max. Min. 6 Max. Min. 7 Max. Min. 8 Max. Min. 9 Max. Min. 10 Max. Min. 11 Max. Min. 12 Max. Min. 13 Max. Min. 14 Max. Min. 15 Max. Min. 16 Max. Min. 17 Max. Min. 18 Max. Min. 19 Max. Min. 20 Max. Min. Control Max. Min. Cd Cr Cu Fe(mg/g) Mn 227 Ni Pb Zn 2.19 82.42 24.12 7.475 260.33 49.63 36.77 41.97 1.83 2.48 2.29 2.4 63.7 91.9 74.07 90.53 17.2 27.89 21.23 27.4 5.115 9.366 6.964 8.952 210.13 333.2 277.73 318.5 33 57.9 38.3 56.6 24.83 44.08 28.7 42.17 29.83 51 37.93 47.8 2.14 2.31 1.97 2.11 72.5 86.38 68.17 80.92 20.03 25.97 18.88 23.93 6.625 8.108 5.705 7.194 267.93 288.73 235.4 245.93 37.2 52.8 35.43 48.7 28.2 39.77 26.82 35.98 36.3 45.53 33.3 40.57 1.71 1.78 1.44 2.73 61.57 74.58 54 96.93 16.93 21.5 14.53 30.77 4.897 6.051 3.687 10.232 197.8 174 144.2 373.7 31.8 43.1 27.4 61.1 23.97 30.58 20.23 47.85 27.73 33.03 22.93 58.27 2.47 2.82 2.61 1.65 82.4 99.8 87.77 72.18 24.6 34.52 26.83 19.93 7.808 10.632 8.358 5.582 328.73 404.6 356.8 153.4 41.63 63.67 44.47 40.43 30.93 50.9 32.97 28.4 41.73 62.8 46.4 30.9 1.4 2.67 2.4 2.06 50.38 95.28 80.53 79.83 13.9 30.03 23 23.5 3.533 9.975 7.636 6.808 123.3 360 310.87 230.67 25.33 60.07 40.53 46.93 19.23 46.73 30.33 34.97 20.8 55.77 40.27 38.4 1.62 2.83 2.69 1.61 59.03 102 88.93 70.97 16.27 36.33 29.13 18.67 4.521 10.766 8.531 5.197 185.6 420.53 377.5 138.07 31 65.37 46.27 36.9 23.13 52.88 33.7 26.67 26.6 65.2 48.87 25.57 1.26 2.8 2.54 2.57 48.83 98.3 84.87 93.6 13.43 31.9 25.33 28.85 3.287 10.485 8.138 9.755 101.8 390.13 343.07 347.33 22.5 62.5 43.03 59.13 17.83 49.22 31.97 45.4 19.47 60.43 44.2 52.87 2.33 1.52 1.19 2.27 78.13 68.73 46.58 84.5 22.07 16.73 13.17 25.03 7.407 4.933 3.206 7.809 290.47 118.53 92.07 274.07 39.3 34.4 19.13 51.33 29.6 25.17 16.97 38.53 39 21.43 17.7 44.23 1.87 1.86 1.5 1.98 66.13 76.23 55.5 78.1 17.9 22.57 15.27 23.2 5.404 6.437 4.116 6.56 225.3 196.1 158.8 215.23 34.6 44.9 28.93 45.87 25.83 32.22 21.13 34.02 31.77 34.97 23.9 37.1 1.56 2.35 2.06 56.72 88.37 71.07 42-2 15.87 26.75 19.33 12.8 4.156 8.615 6.275 4.052 171.53 302.47 247.07 98.04 30.27 55.1 36.5 26.54 22.6 41.28 27.53 20.34 25.47 46.6 34.8 20.82 28.4 8.4 3.022 78.8 23.8 17.12 16.9 1.42 0.96 Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 228 Table12 Range of concentration of heavy metals in some fertilizers and lime materials in mg/kg. Elements Cd Cr Cu Ni Pb Zn Na .05—8.5 0.3—2.9 1--15 7--34 2--27 1--42 Pb 0.1--170 66--245 1--300 7--38 7--225 50--1450 NPK b 1--10 20--72 4--38 9--20 10--130 22--350 Lime a 0.1—24 10—15 2—125 10—20 20—250 10--450 a= [39] b=[29] If the contaminats are bound strongly to the soil and their desorption does not occur, ground water pollution may not be a problem. On the other hand, if desorption takes place easily, the contaminants could become mobile and contaminate water supplies. The concentration of heavy metals Cd, Cr, Cu, Fe, Pb, Mn, Ni and Zn increases with increase in organic matter content in the soil [80] The soil samples showing high levels of heavy metal concentration had high organic matter content. A complexation reaction occurs between heavy metals and organic matter content and results in the retention of heavy metal in the soil [50], [44]. Increase in pH in the soil results in increase heavy metal concentration in the soil. Even though the higher pH favors the heavy metal retention in soil, it limits the heavy metal uptake by plants. The heavy metal uptake by plants decreases as the pH value increases. The acidic pH favors the uptake and causes harmful effect to the living beings through the food chain. The pH value of the tea estate soil was found to be acidic. This indicates that the uptake by plants was high and the biological system was contaminated by the heavy metals. Soil pH and high total organic matter content have a higher retention capacity of heavy metal in soil. The present studies agree with the findings of workers [81], [8] ,[80]. All the heavy metals decreased in concentration as soil depth increased. It was found that the concentration of heavy metals of the tea estate soil increases during the study period. According to the following workers [73], [22] a good correlation is predicted if the linear regression co-efficient “r” is ≥ .7. A positive and significant correlation between total organic matter and available heavy metals Cd to Zn are 0.95, 0.96, 0.96, 0.96, 0.97, 0.96, 0.96 and 0.96 respectively. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 229 The movement of heavy metals within a region is influenced by wind, water and gravity. The movement of heavy metals within the soil mass will be principally in the solution phase [17]. The movement of heavy metal or potentially toxic element in the soil is of concern due to potential impact on the environment through contamination of ground water by leaching. The degree of soil pollution by heavy metals from various anthropogenic activities, such as application of inorganic fertilizers, animal wastes and pesticides [38], [54]. A large amount of heavy metals enrich in the tea estates soil by fertilizers. The range of concentration of heavy metals in some fertilizers and lime material in mg/kg is given in the table 12 [29], [47]. Conclusion The results indicate that the soil had slightly increasing trends of heavy metal concentration but still within tolerable levels. However, the obtained mean values of heavy metals in the study sites are higher that found in the control site.Among these heavy metals Ni, Cr, Pb and Cd are soil pollutants and Cu, Zn, Mn and Fe, and are known as micronutrients or trace elements as these are required in small quantities. The micronutrient elements in minute quantities produce optimum effects. On the other hand, even a slight deficiency or excess is harmful to the plants. By the application of fertilizers, animal wastes and fungicides into the soil not only supply the essential nutrients but also enrich the soil with the heavy metals. These are capable of interfering with biological activities, persistent toxicants within ecosystems and create acute health hazards for humans, animals and plant kingdoms. Therefore, there is a need for optimization of fertilizers, animal wastes and fungicides for improvement of the soil productivity without creating environmental problems. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 230 References : [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] Adriano , D.C. (2001). Trace elements in the terrestrial environment: biogeochemistry, bioavailability and risk of metals, 2nd edn. New York: Springer. Alloway, B.J. (1990). Heavy Metals in soils. Blackie, London. Alloway, B.J. (1995). Soil processes and the behaviour of heavy metals. In B.J.Alloway (Ed.), Heavy metals in soils. London: Blackie Academic and Professional. Arendit, F., Hinsenveld, M and Van Brink, (1990). In: Contaminated Soil, Kluwer Academiv, Dordrecth. The Netherlands. Balsberg-Pahlsson, A.M., Lithner, G and Tyler, G.(1982). Krom i iljon,Statens Naturvardsverk Rapport SNV pm 1570, Solna, Sweden ( in Swedish) Benerji,S.K.( 2007). Environmental Chemistry, second edition, Prentice-Hall of India Private Limited, New Delhi. Bansal, R.L., Nayar, V.K and Takkar, P.N. 1992). Accumulation and bioactivity of Zn, Cu, Mn and Fe in soil polluted with industrial waste water, Journal of the Indian Society of soil Science, 40 (4): 796-799. Bansal, O.P. (2004). Uptake of heavy metals by crops plants, Poll Res. 23 (3): 501-506. Bargagli, R.( 1998). Trace elements in terrestrial plants. An ecophysiological approach to biomonitoring and biorecovery, pp 324. Berlin, Springo. Baruah, T.C. and Borthakur, H.P.(1997) In: A textbook of soil chemical analysis, Vikash Publishing, New Delhi. Bowen,H.J.M.(1979). Environmental chemistry of the Elements. Academic Press,Troy, MO. Bradham, K.D., Daylon, E.A., Basta, N.T., Schroder, J., Payton, M. and Lanno,R.P. (2006). Effect of soil properties on lead bioavailability and toxicity to earth-worms. Environmental Toxicology and Chemistry, 25, 769-775. Brandt, K.K., Holm, P.E. and Nybroe, O. (2006). Bioavalability and toxicity of soil particle-associated copper as determined by two bioluminescent. Pseudomonas fluorescence biosensors strain, Environmental Toxicology and Chemistry, 25, 1738-1741. Bretzel, F. and Calderisi, M. ( 2006).Metal contamination in urban soils of coastal Tuscahy (Italy). Environmental Monitoring and Assessment, 118, 319335. Brooks, R.R.( 1998). Plants that hyperaccumulate heavy metals, pp 289-312. Wallingford: CAB International. Caussy, D. , Gochfeld, M. , Gurzau, E. , Neagu,C. and Ruedel, H. ( 2003). Lessons for case studies of metals: investigating exposure,bioavailability and risk.Ecotoxicology and Environmental Safety, 56, 45-51. Chitdeswari ,T and Jegadeswari, D. (2007), Hazardous Issues of Heavy metals to Ecosystem and Humah Health. Pollution Management. Pointer Publishers, Jaipur (Raj) India, pp 77-8 6 Chakraborty, Rahul., Dey, Sudip., Dkhar, S., P,Tibah., R.C, Myrboh.,B, Ghosh., and Sharma,D.K.(2004).Determination of few heavy metals in some vegetables fromNorth Eastern Region of India in relation to Human Health. Poll.Res. 23(3):537-547). Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] 231 Covelo, E.F., Vega, F.A and Andrade,M.L. ( 2007). Competitive sorption and desorption of heavy metals by individual soil components. Journal of Hazardous Materials, 140, 308-315. Cui, Y. , Zhu, Y.G. , Zhai, R. , Huang, Y. , Qiu, Y. and Liang, J. ( 2005). Exposure to metal mixture s and humans health impacts in a contaminated area in Nanning, China.Environment International, 31, 784-790. Cunningham, S.D. , Berti, W.R. and Huang, J.W. (1995). Phytoremediation of contaminated soils. Trends in Biotechnology, 13, 393-397. Das Gupta, Adak. M. and Purohit, K.M. ( 2000). Correlationcoefficients of some physicochemical characteristics of surface and ground water on Rajgangpur. Part-1,Indian,J.Environ. Protec. 20 (9) : 681-687. Douay, F. , Roussel, H. , Pruvot, C. , Loriette, A. and Fourrier, H. (2008).Assesment of a remediation technique using the replacement of contaminated soil in kitchen gardens nearby a former lead smelter in Northern France. The Science of the Total Environment, 401, 29-38. Dudka .S., Piotrowska .M and Terelak ,H (1996). Transfer of cadmium,lead and zinc from industrially contaminated soil to crop plants-A field study.Env. Poll, 94(2):181- 188. Erel, Y. and Morgan, J.J. (1992). The relationships between rock-derived lead and iron in natural fresh water symtems. eochemical et Cosmochimica Acta, 56,4157-4167. Fergusson, J.E. ( 1990). In: The heavy elements, chemistry, Environmental impact and health effects. Pregamon Press. Oxford. Galvex, F. ( 1998). ‘Rev. of Introduction to Metal Pollution by Kruus et al., 1991’ . Metal Pollution. Yhode Bookstocks Qh 545, pp 105-128. Granero, S. and Domingo, J.L. (2002).Levels of metals in soils of Aleada de Henares, Spain: Human health risks. Environment International, 28, 159-164. Gunnarsson, O.(1983). Heavy metals in fertilizers: Do they cause environmental and health problems. Fertlizers and Agriculturae 85: 27-42. Gupta.P.K. (2007). Method in Environmental analysis water,soil and air, Secod Edition, Agrobios(India) Halim, C.E., Scott,J.A., Amal, R., Short, S.A., Beydoum, D., Low, G. (2005). Evaluating the applicability of regulatory leaching tests for assessing the hazards of Pb- contaminated soils. Journal of Hazardous Materials, 120, 101-111. Hapke, H.J. (1991). Metal accumulation in the food chain and load of feed and food. In Meals and their compounds in the environment. E.Merian. VCH. NY. Pp 469-489. Hund-Rinke, K. and Kordel, W. (2003). Underlying issues in bio-accessibility and bioavailability, Ecotoxicology and Environmental Safety, 56,52-62. Ivask, A., Francois, M., Kahru, A., Dubourguir, H.C., Virta, M. and Douay, F.( 2004).Recombinant luminescent bacterial sensors for the measurement of bioavailability of cadmium and lead in soils polluted by metal smelters. Chemosphere, 55, 147-156. Jackson,M.L. (1973). Soil chemical analysis. Prentice Hall of India Private Ltd, New Delhi Jacob.C and Joseph,P.V,2008, Study of heavy meyal levels in the soils of Pala Municipality, Kerala. Poll.RES. 27(2) :279-283. Jacob, C. and Joseph, P.V. (1994). Study of heavy metal levels in the soils of Pala Municipality, Kerala. Poll. Res. 27 (2): 279-283. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 [37] [38] [39] [40] [41] [42] [43] [44] [45] [46] [47] [48] [49] [50] [51] [52] [53] [54] 232 Janssen, R.P.T., Posthuma, L.,Baerselman, R. and Den Hollander, H.A.( 1997). Equilibrium partitioning to heavy metals in Dutch field soils.II. Prediction of metal accumulation in earth-worms.Environmental Toxicology and Chemistry, 16, 2479-2488. Jeevan Rao. (1998). Heavy metal inputs to soil by agricultural activities. Env. Geochemistry.1:15-18. Kabata-Pendias, A and Pendias, A. 1984).Trace Elements in soils and plants. CRC Press,Boca Raton, Fla. Kanwar, J.S. ( 1977). Int. Sym. Soil fert. Evaluation. Proceedings, Vol. 1, pp 1103-1113. Kirkham, M.B. (2006). Cadmium in plants on polluted soils: Effects of soil actors,hyperaccumulation, and amendments, Geoderma, 137, 19-32. Klein, H., Priebe, A. and Jaeger, H.J. (1981). Greuzen der Beastbarkeit von Kulturpflanzen mit dem Schwermetall Cadmium, Angewandle Botanik 55, 295-308. Li, Z. and Shuman, L.M. (1996). Heavy metal movement in metal contaminated soil profiles. Soil Sci. 161, 656-666. Kumari T.K, Rao, B.M and Ranganavakulu,N. (2001).Characterzation and Distribution of cationic micronutrients in typical soil profile of Tirumala Hills. IJEP 21(9) pp 847-849. Magrisso, S., Belkin, S., Erel, Y. (2009). Lead Bioavailability in Soil and Soil Components, Water Air Soil Pollution, 202: 315-323. Mantovi, P. , Baldoni, G. and Toderi, G. (2005). Reuse of liquid, dewatered, and composted sewage sludge on agricultural land: effects of long-term application on soil and crop. Water Research, 39, 289-296. Martinez, C.E. and Motto, H.L. (2000).Solubility of lead , zinc and copper added to mineral soils. Environmental Pollution, 107, 153-158. Mbila, M.O. , Thompson, M.L. , Mbagwu, J.S.C. and Laird, D.A. (2001). Distribution and movement of sludge derived trace metal in selected Nigerian Soils. Journal of Environmental Quality, 30,1667-1674). McBride, M.B. (2003). Toxic metals in sewage sludge- amended soils: has promotion of beneficial use discounted the risk. Advances in Environmental Research, 8, 5-19. McLaren, R.G. and Crawford, D.V. (1973) Studies on soil copper. The fractionation of copper in soils. J. Soil. Sci. 24, 172-181. Mesquita,M.E. and Carranca, C. (2005). Effects of dissolved organic matter on copper zinc competitive adsorption by a sandy soil at different pH values. Environmental Technology, 26(9), 1065-1072. Migeon, A. , Guinet, F. , Chalol, M. and Blaudez, D. ( 2009). Metal Accumulation by woody species on contaminated sites in the North of France. Water Air Soil Pollution, 204, 89-101. Motsana, M.R. and Joginder Singh. (1981) Indian Fmg., 31: 3-12. Mulligan, C.N. ,Young, R.N. and Gibbs, B.F. (2001). Remediation Technologies for metalcontaminated soils and groundwater. An evaluation, Engineering Geology. 60, 193-207. Narasimbha Rao,S.L and Sharma, D.R.R.(1998). Trace metalsin soil near an industrial belt in Visakhapatram, Poll. Res. 7(4):377-380. Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 [55] [56] [57] [58] [59] [60] [61] [62] [63] [64] [75] [66] [67] [68] [69] [70] [71] [72] 233 Nriagu,J.O. (1991). Human influence on the global cycling of trace metals.In heavy metals in the environment (vol 1), Ed J.G.Farmer. CEP consultants Ltd, Edinburgh, U.K. pp 1-5. Oliveria, F.C. , Mattiazzo, M.E. ,Marciano, C.R. and Abreu Junior, C.H. (2002). Movement of heavy metals in an Oxisol fertilized with municipal solid waste compost. Pesquisa, Agropequria Bersileira, 37 (12),1787-1793). Ottosen,L.M., Hasnsen, H.K. and Jensen, P.E. ( 2009). Relation between pH and Desorption of Cu, Cr, Zn and Pb from Industrially Polluted Soils. Water, Air Soil Pollution, 201: 295- 304. Paramasivam, S. , Sajwan, K.S. and Alva, A.K. (2006). Incinerated sewage sludge products as amendments for agricultural soil: leaching and plant uptake of trace elements. Water, Air and Soil Pollution, 171 (1-4), 273- 290. Paterson, E., Sanka, M. and Clark, L. (1996). Urban soils as pollutant sink- a case study from Aberdeen, Scotland. Applied Geochemistry, II, 129-131. Peijnenburg, W.J.G.M. ( 2002).Bioavailability of metal to soil in verbrates. In H.E. Allen (Ed.), bioavailability of metals in terrestrial ecosystems: importance of artitioning for bioavailability to inverbrates, microbes, and plants. Pp 89-112. Pensacola: SETAC. Peijnenburg, W.J.G.M., Baerselmen, R.,de Groot, A.C., Jager, T., Posthuma, L. and Van Veen,R.P.M. ( 1999). Relating environmental availability to bioavailability: Soil-type dependent metal accumulation in the Oligochaete Eiseniandei, Ecotoxicology and Environmental Safety, 44, 294-310. Piotrowska, M. and Dudka, S .(1994). Estimation of maximum ermissible levels of cadmium in a light soil by using cereal plants. Water, Air and Soil Poll., 73 (1-4) : 179-188. Pinta, M. ( 1975). Detection and determination of trace elements, ANA, Arbor Science Publication INC. Pruvot, C. ,Douay, F. , Herve, F. , and Waterlot, C. (2006). Heavy metals in soil, crops and grass as a source of human exposure in the former mining area. Journal of Soils and Sediments, 6, 215-220. Rensing, C. and Maiver, R.M. (2003). Issues underlying use of biosensors to measure metal bioavailability. Ecotoxicology and Environmental Safety, 56, 140-147. Robson, M. (2003). Methodologies for assessing exposure to metals: human host factor. Ecotoxicology and Environmental Safety, 56, 104-109. Rodney, R., Piepenbrink, D.S. and Piepenbrink, M.S.(2006). Lead and immune function. Critical Reviews in Toxicology, 36, 359-385. Saeed,M. and Fox, R.L. (1977). Relation between suspension pH and Zn solubility in acid and calcareous soils. Soil Science, 124, 199-204. Salt, D.E. , Smith, R.D. and Raskin, I.(1998). Phytoremediation. Annual Review of Plant Physiology and Plant Molecular Biology, 49, 643-668. Sanchez-Monedero, M.A. , Mondini, C.de Nobile, M. , Reita, L. and Roig, A. (2004). Land application of biosolids. Soil response to different stabilization degree of the treated organic matter, Waste Management, 244, 325-332. Sauve, S. (2002). Speciation of metals in soils. In H.A.Alle (Ed.), bioavailability of metal in terrestrial ecosystem: importance of partitioning for bioavailability to invertebrates, microbes, and plants, pp 7-37, Pesacola: SETAC. Schnitzer, M. and Kerndorff, H. (1980). Effects of pollution on humic Copyright © 2013 SciResPub. International Journal of Advancements in Research & Technology, Volume 2, Issue4, April-2013 ISSN 2278-7763 [73] [74] [75] [76] [77] [78] [79] [80] [81] [82] 234 substances. Environ Sci Health B,15(4), 431-456. Singanan, M.K., Somasekhara and Rambabu.(1995). A correlation study on physicochemical characteristics of ground water in Rameswaram Island. Indian J. Environ. Protec. 15 (3) : 213-217. Stabnikova, O. , Goh, W.K. , Ding, H.B. , Tay, J.H. and Wang, J.Y. ( 2005). The use of sewage sludge and horticultural waste to develop artificial soil for plant cultivation in Singapore. Bioresearch Technology, 96(9); 1073-1080). Su, D.C. and Wong, J.W.C.( 2003).Chemical speciation and phytoavailability of Zn, Cu, Ni and Cd in soil amended with fly ash- stabilized sewage sludge. Environment International, 29, 895-900. Sutherland, R.A. and Tolosa, C.A. (2001). Variation in total and extractable elements with distance from roads in an urban watershed, Honolulu, Hawaii. Water, Air and Soil Pollution, 127, 315-338. Udom, B.E. , Mbagwu, J.S. ,Andesodun, J.K. and Agbim, N.N. (2004).Distribution of Zn,Cu, Pb and Cd in a topical ultisol after long-term disposal of sewage sludge.Environment International, 30 (4), 467-470. Walkey, A. and Black, C.A. (1974). Critical examination of rapid method of determining organic carbon in soil. Soil Sc. 63: 251-164. Wang, M.J. ( 1997). Land application of sewage sludge in China. Science of the Total Environment, 197, 149-160. Wesley, S.G. ( 2004). Bioaccumulation of Heavy metals by the intertidal Molluscs of Konyakumari waters, Indian Pollution Research, 23(1): 37-40. William, C.H. and David. D.( 1976). Study on accumulation in soil of Cd residues from phosphate fertilizers and their effect on Cadmium content of plants. Soil Sci., 121: 86-93. Xing,G.X and Chen, H.M.(2004). Environmental impacts of metal and other inorganic on soil and ground water in China. Lewis publishers, Boca Raton, London, 167-200. Copyright © 2013 SciResPub.