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Journal of Chemistry and Chemical Sciences, Vol. 5(1), 5-17, January 2015 (An International Research Journal), www.chemistry-journal.org ISSN 2229-760X (Print) ISSN 2319-7625 (Online) Assessment of Heavy Metals Concentration Deposited in Roadside Tea Cultivated Soil in Dibrugarh District of Assam, India Nath T. N. Associate Professor, Department of Chemistry, Moran College, P.O. Moranhat, District Sivasagar, Assam, INDIA. (Received on: November 28, 2014) ABSTRACT Concentration of four typical heavy metals (Cd, Cr, Ni and Pb) in roadside tea cultivated soils close to national highway (NH 37) in the Dibrugarh district of Assam were investigated in this study. Soil samples were collected from both sides of the national high way at the distances of 100 m, 200 m and 300 m respectively and another is a nearby tea estate area which served as the reference site. A total of sixty samples from both sides of the road collected systematically. The heavy metal concentrations of Cd, Cr, Ni and Pb in the soil sample were analyzed using atomic absorption spectroscopy (AAS). The result of the analysis showed that as the roadside distance increases from the road edge the metal concentration decreases in a constant pattern. The concentration of Cd, Cr, Ni and Pb in soil varied within the range of 1.34 ±0.26 to 1.68 ± 0.38, 34.12 ± 8.54 to 40.18 ± 11.46, 24.48 ± 3.42 to 28.46 ± 5.12 and 27.78 ± 3.16 to 34.72 ± 4.14 mg/kg respectively from Moran to Dibrugarh. Result indicates that heavy metal concentration decreases in the order of Cr>Pb>Ni>Cd. Concentration of Cd, Cr , Ni and Pb of control site soil were found to be 1.06, 29.85, 20.56 and 24.02 mg/kg respectively. The concentrations of heavy metals in roadside tea cultivated soil were higher as compared to reference soil levels. This suggests that automobiles are major source of these metals in roadside soil. Keywords: Heavy metals, roadside soil, AAS, analyzed, automobile. INTRODUCTION Tea is a popular healthy and cheap drink. Tea is one of the commonly consumed beverages for its desirable aroma, taste and pulative positive physiological functions 1, 2 . January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org 6 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) After water, tea is the most widely consumed beverage in the world 3. It is used as folk medicine for headache, digestion, dieresis, immune defences, energizer and longevity of life is well known4.The growing interest in drinking tea for its polyphenol antioxidative activity and fighting the harmful influence of environmentally generated free radicals5. The chemical composition of tea leaves consist of tanning substances, flavonols, alkaloids, proteins and amino acids, enzymes, aroma-forming substances, vitamins minerals and trace elements6. The associated chemical components in tea received a notable concern as it is related to human health. Extensive study on potential health implication of heavy metals in tea has been carried out as tea bush is known to accumulate trace metal 4,7,8,9,10 . The main sources of heavy metals in plants are their growth media, nutrients, agro inputs and soil 11. Heavy metals are considered as soil contaminates due to their widespread occurrence, acute and chronic toxicity 12,13. The contamination of agricultural soils with heavy metals has always been considered a critical challenge in scientific community 13a. Due to their cumulative behaviour and toxicity, they have a potential hazardous effect not only on vegetation but also on human health and also trees in cities are more prone to heavy metal pollution due to pervasive pressure of auto vehicular emissions 13,14. Among heavy metals lead and cadmium toxicity has become important due to their constant increase in the environment 13a . Pollution of the natural environment by heavy metals is a universal problem because these metals are indestructible and most of them have toxic effects on living organisms, when permissible concentration levels are exceeded 15. The pollution of soils and vegetation by trace metals from automobile sources is a serious environmental issue 16. Heavy metal present in the roadside soils and grasses may be transported through the food chain to the human body and have a significant toxicity to people 17,18. With the rapid industrialisation and urbanization trend, the increment of traffic activities substantially contributes to the accumulations of micronutrients discharged by vehicles in roadside environment. High concentration of heavy metals may affect the ecosystem and human health 18. Heavy metal pollution in agricultural areas owing to traffic emissions may contaminate the crops growing near the roadways 19. Vehicle exhausts, as well as several industrial activities emit these heavy metals so that soils, plants and even residents along roads with heavy traffic loads are subjected to increasing levels of contamination with heavy metals 20. Roadside soils often show a high degree of contamination that can be attributed to motor vehicles 15. The source of heavy metal emissions from vehicles include fuel combustion, lubricating oil consumption, tire wear, brake wear, roar abrasion, etc 21,22,23,24,25. Cd and Pb are the major metal pollutants of the roadside environments and are released from burning of fuel, wearing out of tyres, leakage of oils, and corrosion of batteries and metallic parts such as radiators etc 16,24,26,27,28 . Various researchers have found that the concentration of the metals Pb, Cu, Zn, Cd and Ni decrease rapidly within 10 to 50 m from the roadsides 29,30. The pollution of roadside soils and plants by combustion of leaded petrol products is localized and usually limited to a belt of several metres wide on either side of the road, and that for similar topography and vegetation, the level of pollution decreases with the distance from the road 31 . Road traffic activities are the major source of heavy metals emission to roadside soils 32. January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) 7 In agricultural areas, uptake of heavy metals through the soil- crop system could play a predominant role in human exposure to heavy metals 33. Numerous previous studies have investigated the influencing mechanism of vehicle emissions on concentrations of micronutrients in roadside soils 34,34a. The concentration of heavy metal decreases with increasing roadside distance 35,36. Therefore, assessment of heavy metals in soil is essential for understanding their toxic importance. The present study assessed heavy metal concentration of Cd, Cr, Ni and Pb on roadside tea cultivated soil. MATERIALS AND METHODS Study Area This study was conducted in tea plantation areas inside the national highway. Tea estates are selected for study in the Dibrugarh district of Assam. Dibrugarh district is situated in the eastern part of Assam. The district extends from 27005.38/ N to 27042.30/ N Latitudes and 94033.46/ E to 95029.80/ E Longitudes. The geographical area covered by Dibrugarh district is 3381 sq km. The area of the Dibrugarh district 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 in this district is 276 cm with a total number of 193 rainy days. Physico-chemical properties of soil The soils of the area are basically the products of the fluvial processes of the Brahmaputra and its tributaries. The plains are composed of alluvium which may be classified as new and old. The new alluvium varies mostly from clayey to sandy loam in texture and is slightly acidic in reaction. In certain parts, both the old and new alluvium are so combined that it is difficult to distinguish them. The pH ranges between 4.2 and 5.5. The new alluvium is less acidic as compared to the old alluvium. Its pH value varies from 5.5 to 9.9. Tea is abundantly grown in the old alluvium as it has high percentage of acid. The tea estates are located over relatively high lands with discernible slopes containing both old and new alluvium. Soil sampling and Laboratory analyses A total of 60 topsoil samples were collected from the roadside tea cultivated soils of Dibrugarh district of Assam during the January 2014. For each sampling site (both sides of road, NH 37), three topsoil ( 0-20 cm) samples were collected according to 100 m, 200 m and 300 m roadside distances. Composite soil samples were taken and prepared for necessary analysis in the laboratory 37,38. Samples from the control sites were collected following the same procedure. 1.0 g air dried sieved soil sample was placed in 100 ml beaker with 15 ml of concentrated HCl, 5 ml concentrated HNO3 and 3 ml concentrated H2SO4 and heated at 95January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org 8 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) 1000 C on hot plate. After proper digestion, the digest was made up to 50 ml with deionised water. The extract was analysed using AAS (Varian Spectra AA 220). Same procedure was carried out on control soil sample. The locations of sampling stations were determined by using Global Positioning System (GARMIN e-Trex 30). RESULT AND DISCUSSION The results of analysis of tea cultivated soil samples are presented in tables 1, 2, 3 and 4.The results of analysis of control soil is presented in table 5. There was wide variation in the heavy metals concentration of tea cultivated roadside soils. The results indicated that the concentration of of Cd, Cr, Ni and Pb in soil were different for the different soil sampling locations. The concentration of Cd measured in left and right sides of the national highway were 1.42 ± 0.36 to 1.68 ± 0.38 and 1.34 ± 0.26 to 1.60 ± 0.42 mg/kg respectively. The concentrations of Cr were 36.14 ± 9.62 to 40.18 ± 11.46 and 34.12 ± 8.54 to 38.58 ± 10.36 mg/kg respectively. The concentrations of Ni were 24.72 ± 3.96 to 28.46 ± 5.12 and 24.42 ± 3.42 to 27.54 ± 4.98 mg/kg respectively. The concentrations of Pb were 28.04 ± 4.74 to 34.72 ± 4.14 and 27.78 ± 3.16 to 32.02 ± 5.64 mg/kg respectively. It was observed that chromium (Cr) has the highest concentration level in all the samples analysed followed by lead (Pb), then nickel (Ni) and cadmium (Cd). Therefore, the concentration of the heavy metals in decreasing order is given as Cr > Pb > Ni > Cd. These level agreement in the typical ranges of the average concentration in the Earth’s crust 39. These levels are not as high as the ranges reported in roadside soils of England (Pb 25.0- 1198.0 mg/kg and Cd 0.3-3.8 mg/kg). The concentration of Pb in tea cultivated soil was higher than the level in the reference soil. It was reported that soils within 40 m from the highway having at least 2 to 6 times higher concentration of Pb than the background level 40. It was reported that on the use of Pb as an antiknock agent in gasoline which result in its release during emissions from fossil combustion 16,40,41,42. Pb is reported as one of the heavy metals with highest affinities for soils moreover it becomes stabilized on the surface of soil through hydrolysis reaction 43. The presence of mobile forms of Pb indicate toxic risk both in the food chain and its migration downwards the soil profile44.The concentration of Pb in soil ranging from 25.0 to 1198.0 mg/kg have been reported on roadside soil in England, 0 to 50 mg/kg in India, 78.4 to 832 mg/kg in Tanzania. The concentration of Cd in tea cultivated soil was higher than the level in the reference soil but low in permissible limit. It was reported similar low level of Cd in soil samples in French major highway 29. Cd concentration was ranging from 0.3 to 3.8 in England 16 and other researchers reported levels lower than the general soil level of 0.1 gm/kg, 0.3 to 1.33 mg/kg in studies on heavy metal contamination of soil on major highway in Lagos, Nigeria 41,45 while it was found that Cd concentration levels which were higher than FAO/WHO recommended limits in Kaduna Metropolis, Nigeria 46. In the absence of any major industry in the sampling sites, the levels of Cd could be due to engine oil consumption and the wearing of tyres. Similar findings have been reported previously 42,45,47. It was mentioned that 0-1.0 mg/kg of Cd in soil indicates non contamination, 1-3 mg/kg January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org 9 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) indicates slight contamination of soil and 3-10 mg/kg indicates contaminated soil 48. Therefore, when the values obtained for Cd from this research are compared to these values, in can be stated that the tea cultivated soil is not contaminated with Cd and also did not exceed the tolerance or permissible level. The concentration of Cr in tea cultivated soil was higher than the level in the reference soil but low in permissible limit. It was reported that natural chromium concentration of surface soil is 60 mg/kg 49. When the Cr concentration of soil in this research are compared with stated above, it appears that the values are far less than the natural concentration of Cr in soil 49 . The concentration of Ni in tea cultivated soil was higher than the level in the reference soil but low in permissible limit. Ni is absorbed easily and rapidly by plant 50. It was reported that airborne particles emitted by brakes and wears from vehicles tyres can contain considerable amounts of nickel 41. All of the heavy metal concentrations show a declining trend with the increase of distance from the road (Fig. 1 to 8). The heavy metal concentration is higher near the roadside soil and gradually decreases as the distance increases. The possible accumulations of the roadside soil occur due to continual usage of the road by automobile. The heavy metals are emitted from various sources into the atmosphere. Most studies have used soil samples to monitor their metallic levels 44,51,52. The metallic levels of the studied soil were higher than the control sample. These observations indicate some level of contamination possibly from aerial deposition of metal particulates in roadside environment mainly automobiles. Tea cultivated soils have generally high concentration of heavy metal due to frequent application of fertilizers and pesticides to high yields of tea leaves. It was reported that trees growing linearly along the roadways can effectively reduce the heavy metal concentration in the roadside agricultural soil 47. The correlation analysis of heavy metals concentration in roadside soils indicates that the concentration of of Cd, Cr, Ni and Pb are significantly correlated with each other, as shown in Table 6. The similar conclusions were also obtained from many researchers studies 18,47 . There are no any industrial factories and farmlands in the study area, road traffic is the most probable source of these metals 18,33. The correlation analysis of heavy metals confirms the enhancement of heavy metal concentration of tea cultivated roadside soil. Table 1 . Concentrations of Cd and Cr in roadside tea cultivated soils in mg/kg (from Moran to Dibrugarh, NH 37 left side) Variable Level 100m Distance 200m 300m Range 1.68 ± 0.38 (1.30 – 2.06) 1.50 ± 0.34 (1.16 – 1.84) 1.42 ± 0.36 (1.06 – 1.78) Cd SD 3.46 2.96 3.05 Range 40.18 ± 11.46 (28.72 – 51.64) 38.92 ± 10.74 (28.18 – 49.66) 36.14 ± 9.62 (26.52 – 45.76 ) January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org Cr SD 5.48 4.78 5.22 10 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) Table 2 . Concentrations of Ni and Pb in roadside tea cultivated soils in mg/kg (from Moran to Dibrugarh, NH 37 left side) Variable Level 100m Distance Ni Pb Range SD Range SD 28.46 ± 5.12 5.25 34.72 ± 4.14 5.12 (23.34 – 33.58) 200m (30.58 – 38.86) 26.04 ± 4.68 5.42 (21.36 – 30.72) 300m 30.16 ± 3.84 4.94 (26.32 – 34.00) 24.72 ± 3.96 4.88 (20.76 – 28.68) 28.04 ± 4.74 5.34 (23.30 – 32.78) Table 3. Concentrations of Cd and Cr in roadside soils in mg/kg (from Moran to Dibrugarh, NH 37 right side) Variable Level 100m Distance Cd Cr Range SD Range SD 1.60 ± 0.42 2.96 38.58 ± 10.36 4.68 (1.18 – 2.02) 200m 1.40 ± 0.28) (28.22 – 48.94)) 2.36 37.56 ± 9.68 (1.12 – 1.68) 300m 1.34 ± 0.26 4.28 (27.88 – 47.24) 3.25 34.12 ± 8.54 (1.08 – 1.60) 4.92 (25.58 -42.66) Table 4. Concentrations of Ni and Pb in roadside soils in mg/kg (from Moran to Dibrugarh, NH 37, right side) Variable Level Ni Range 100m Distance 200m Range SD 4.32 27.54 ± 4.98 SD 32.02 ± 5.64 (22.56 – 32.52) 4.75 (26.38 –37.66) 25.62 ± 3.26 (22.36 – 28.88) 300m SD Pb 29.54 ± 4.32 4.42 24.48 ± 3.41 (21.07 – 27.89) (25.22–33.86) 27.78 ± 3.16 5.08 4.14 (24.62 -30.94) January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org 4.64 11 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) Table 5. Concentrations of Cd, Cr, Ni and Pb in control soil sample in mg/kg Sl. No Heavy metal Concentration 1 Cd 1.06 2 Cr 29.85 3 Ni 20.56 4 Pb 24.02 Table 6. Correlation between concentration of Cd, Cr, Ni and Pb Cd Cr Ni Pb Cd 1.00 0.82 0.90 0.92 Cr 0.82 1.00 0.86 0.83 Ni 0.90 0.86 1.00 0.89 Pb 0.92 0.83 0.89 1.00 Fig 1. Concentration of Cd in mg/kg on the roadside (left) tea cultivated soil Fig 2. Concentration of Cr in mg/kg on the roadside (left) tea cultivated soil January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org 12 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) Fig 3. Concentration of Ni in mg/kg on the roadside (left) tea cultivated soil Fig 4. Concentration of Pb in mg/kg on the roadside (left) tea cultivated soil Fig. 5. Concentration of Cd in mg/kg on the roadside (right) tea cultivated soil January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) Fig 6. Concentration of Cr in mg/kg on the roadside (right) tea cultivated soil Fig 7. Concentration of Ni in mg/kg on the roadside (right) tea cultivated soil Fig 8. Concentration of Pb in mg/kg on the roadside (right) tea cultivated soil January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org 13 14 Nath T. N., J. Chem. & Cheml. Sci. Vol.5 (1), 5-17 (2015) CONCLUSION The result of this work show that the concentration levels of heavy metals on the study area as a result of vehicular emissions has not rich to a dangerous level at the moment.The concentration of the heavy metals in the tea cultivated roadside soil is comparatively high but lower the permissible limits. The heavy metal concentration is higher near the roadside soil and gradually decreases as the distance increases. The correlation coefficients show positive correlations for most of the heavy metal pairs.The concentrations of the metals in the soils are in the order Cr>Pb>Ni>Cd. 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