International Journal of Agricultural Science and Research (IJASR) ISSN 2250-0057 Vol.

2 Issue 4 Dec 2012 121-134 TJPRC Pvt. Ltd.,

UPTAKE OF METALS BY FOUR COMMONLY AVAILABLE PLANT SPECIES COLLECTED FROM CRUDE OIL CONTAMINATED SITES OF LAKOWA OIL FIELD (ASSAM)
1 1 2

MUKUT KALITA & 2ARUNDHUTI DEVI

RM&E Division, Institute of Advanced Study in S & T, Guwahati, India

RM&E Division, Institute of Advanced Study in Science and Technology, (An Autonomous Institute Under DST, Govt. of India) Paschim Boragaon, Guwahati-781035, Assam, India

ABSTRACT
Metals and other contaminants are released by oil field operations carried out at Group Gathering Stations (GGSs). Present study investigates the uptake of seven metals (Cd, Cu, Fe, Mn, Ni, V, and Zn) by plants grown in crude oil contaminated sites of Lakowa Oil Field (Assam). Plant samples of commonly available fruits and vegetables (Musa paradisiaca, Ziziphus jujuba Lamk, Solanum melongena Linn, Brassica juncea Hk F&Th) were collected from petroleum contaminated sites near the two Group Gathering Stations namely Lakowa GGS3 and Lakowa GGS9 of ONGCL at Lakowa Oil Field (Assam). Along with the plant samples, soil samples were also collected (at 0-45cm depth) from the corresponding growth sites for the measurement of soil metal contents. Accumulation of Cd in Brassica juncea, Hk. F. & Th. leaves is less though Cd is considered to be absorbed effectively by leaf system. In general, Cd is the least abundant element for all the plant samples. Brassica juncea, Hk. F. & Th. contains Zn in high abundance. Mn and Fe were present in all the plant samples in very high amount. Amongst them Brassica juncea, Hk. F. & Th. contains much more Mn and Fe than the other plant samples. From the present study it can be highlighted that plants grown in crude oil contaminated soils contain much higher concentration of Ni and V than those grown in uncontaminated soil. The uptake of metals by plants was found to be affected by the type of the plant species as well as metal species involved.

KEYWORDS: Oil Field, Pollution, Crude Oil, Soil Characteristics, Plants, Metal Uptake INTRODUCTION
Plants are dependent on a favorable combination of some six environmental factors: viz., light, mechanical support, heat, air, water and nutrients. With the exception of light, soils can supply each of these factors. The concentrations of plant nutrients in soil and the conditions, making them available to plants are of fundamental importance to plant growth (Epstein 1972). Sixteen chemical elements are known to be essential for the growth of plants. These plant nutrients are hydrogen, carbon, oxygen, phosphorous, potassium, calcium, magnesium, sulphur, iron, manganese, boron, molybdenum, copper, zinc, chlorine and nitrogen (Russell 1973). Out of the sixteen essential elements soil is the source of thirteen essential nutrients, viz., nitrogen, phosphorous, potassium, calcium, magnesium, sulphur, iron, manganese, boron, molybdenum, copper, zinc and chlorine. Six elements viz., nitrogen, phosphorous, potassium, calcium, magnesium and sulphur are used in relatively large amounts and are called macronutrients, while the other seven elements viz., iron, manganese, boron, molybdenum, copper, zinc and chlorine are needed only in small amounts and are called micronutrients. Cobalt is also often considered as a micronutrient. If the concentration of a given element in the plant root zone is too low or too high, the plant growth is restricted due to the deficiency or toxicity of that element.

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Crude oil contains a number of metals such as nickel, vanadium, zinc, lead, and copper. Metals can enter into the nearby areas of an oil collecting station through spills, leaks as well as through emissions from gas flaring and from effluents which are likely to pollute the environment. In general, due to crude oil spillage, inorganic ion concentrations of polluted soils and streams varied significantly from those of unpolluted soils and streams (Onyeike et al. 2002). In the oil polluted sites on the coast of Galicia (northwestern Spain) Andrade et al. (2004) found that oil pollution altered both chemical and physical properties of soil. The chromium, nickel, copper, iron, lead, and vanadium contents of polluted soils were between 2 and 2500 times higher than those of their unpolluted counterparts. Metals are primarily taken up by plants through roots. However, foliar absorption and stem uptake also represent potential mode of entry (Greger et al. 1993). Plants grown in metal-enriched substrates take up metal ions to varying degrees. This uptake is largely influenced by the bioavailability of the metals which is, in turn controlled by both external (soil-associated) and internal (plant-associated) factors (Saxena et al. 1999). The uptake of metals by plants is affected by various factors such as type of the plant species, the metal species involved, metal concentration in the medium, presence of other cations and anions in the medium, pH of the medium, light, temperature, relative humidity etc. In addition to uptake, there is also a release of metals back into the water and soil or to the air. These cause a net accumulation of the metal in the plant (Greger 1999). Whether essential or non-essential, metals in excess concentrations are toxic to both plants and animals. Metals can bind to functionally important domains of biomolecules and inactivate them. The result is, for instance, the inhibition of enzymatic action and a disturbance of metabolism (Van Assche and Clijsters 1986). Any change in the composition of membranes under metal stress would certainly have an influence on the membrane structure and function (Cooke and Burden 1990). Maintenance of membrane integrity under metal stress is the crucial factor in determining the tolerance of plants to metals (Demidchik et al. 1997). Most of the metals are required in trace levels for biochemical functions of living cells. Dar Hasan (1995) has demonstrated that metals added together are more toxic to soil ecosystems than the additive toxicity of individual metals. Metal intake by human via consumption of fruits and vegetables grown on contaminated land is a matter of great concern.

THE STUDY AREA AND EXPERIMENTAL METHODOLOGY

Site Selection In this investigation, Lakowa oil field (operated by the Oil and Natural Gas Corporation Limited) has been selected for carrying out the work. This field is located in the Sibsagar district, Assam. Field survey along with the collection of fruits and vegetables were carried out during the month of Nov, 2005. Two GGSs (Group Gathering Stationswhere the oil is stored and pump to the different laboratories), i.e., Lakowa GGS3 and Lakowa GGS9 were chosen for the collection of fruits and vegetables. The work started with a thorough survey of the study area based on visit to the selected GGSs. Leakage of crude oil is seen in different locations near the GGSs. The people living in the residential area near the GGSs complain that during high flood, oily water spread into the whole area. Different types of plants have been seen in these areas but the growth appears to be hampered. Vegetables and higher plants growing in the area are seen to have been seriously affected even at considerable distances. The plant leaves appear to have oil stains on them and people report that the leaves dry up very quickly. Local people reported deaths of animals from various diseases. Sampling Procedure Selection of a plant species in a particular contaminated site was based on its occurrence in the respective contaminated site. Plant samples of commonly available plant species Musa paradisiaca (Banana), Ziziphus jujuba Lamk

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(Assamese: Baguri), Solanam melongena Linn (Brinjal) and Brassica juncea Hk F&Th (Assamese: Laisak) were collected from the contaminated sites of Lakowa GGS3 and Lakowa GGS9. In a contaminated site near a GGS, the sub-samples of a plant species were collected from an area between 0-200 m distances from the GGS. The ages of the plant species and plant parts were not taken into account during the sample collection. Equal amounts of the sub-samples were mixed to obtain a composite sample of the plant species. In the surrounding area of a GGS different plant species grew in different positions. The contamination of soil may not be homogeneous throughout the area. So, extent of contamination for a composite sample of a plant species may be different from that of another plant species within the same but large area. For example, the samples of both Musa paradisiaca and Ziziphus jujuba Lamk were collected from the area between 0-200 m distances from the Lakowa GGS3. But they were collected from different positions within the same area. So, the composite sample of Musa paradisiaca may differ from the composite sample of Ziziphus jujuba Lamk with respect to extent of contamination. For the contaminated sites, therefore, the plant growth sites were designated by the names of the respective GGSs as well as the names of the plant species. Composite samples were also collected from the private gardens or agricultural fields situated at uncontaminated areas and they were considered as reference samples. For the uncontaminated sites, the plant growth sites were designated by the names of the respective oil fields as well as the names of the plant species. The designations of all the plant growth sites are shown below. Designation of the Plant Growth Sites at the Contaminated/Uncontaminated Sites of Lakowa Oil Field Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Sampling Station LGGS3 LGGS9 Lakowa * LGGS3 LGGS9 Lakowa* LGGS3 LGGS9 Lakowa* LGGS3 LGGS9 Lakowa* Collected Plant (part) Musa paradisiaca (Fruit) Musa paradisiaca ( Fruit) Musa paradisiaca (Fruit) Ziziphus jujuba Lamk (Fruit) Ziziphus jujuba Lamk (Fruit) Ziziphus jujuba Lamk (Fruit) Solanam melongena Linn (Fruit) Solanam melongena Linn (Fruit) Solanam melongena Linn (Fruit) Brassica juncea Hk F&Th (Leaves) Brassica juncea Hk F&Th (Leaves) Brassica juncea Hk F&Th (Leaves) Designation of Plant Growth Site LGGS3(Mus.p) LGGS9(Mus.p) L(Mus.p) LGGS3(Ziz.j) LGGS9(Ziz.j) L(Ziz.j) LGGS3(Sol.m) LGGS9(Sol.m) L(Sol.m) LGGS3(Bras.j) LGGS9(Bras.j) L(Bras.j) Plant Sample Number A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 Soil Sample Number B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12

*Uncontaminated site, LGGSLakowa GGS, Mus.p Musa paradisiaca, Ziz.j Ziziphus jujuba Lamk, Sol.m Solanam melongena Linn, Bras.j Brassica juncea Hk F&Th.

All plant samples were collected in clean paper bags and were carried to the laboratory. Along with the collection of plant samples, soil samples were also collected from the corresponding growth sites at a depth of 0-45 cm. Soil samples corresponding to a plant species from a particular area were mixed to obtain a composite sample. The soil samples were collected in clean polythene bags. Two samples of crude oil were also collected from the two selected group gathering stations under Lakowa oil field. Pretreatment, Drying and Homogenization of the Samples The plant samples were thoroughly washed to remove any substance on the surface of the specimen. The main edible parts of Musa paradisiaca (excluding skin part) and Ziziphus jujuba Lamk (excluding seed part) were separated out and taken into consideration for the metal estimation. Whole parts of the leaves of Brassica juncea Hk F&Th and fruits of

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Solanum melongena Linn were considered for the metal estimation. After pretreatment, the samples were air dried in sunlight. The samples were then dried in an oven at 450 C. The dried samples were ground finely in a mortar to obtain homogenized samples. A portion each of the soil samples collected was spread out thinly on a piece of stout paper and allowed to dry in air in a shade free from dust. During the process of drying, the lumps of soil samples were broken and then screened through a 2.0 mm sieve and plant roots, pebbles and other unwanted materials were discarded. The samples were then kept in clean polythene bags for metal analysis. Analysis of the Plant Samples Ashing and dissolution process for the estimation of the seven metals (Cd, Cu, Zn, Fe, Mn, Ni and V) present in the plant samples was carried out according to Jackson (1967). 1g (dry weight) finely ground sample was kept in a crucible and places into a muffle furnace at a temperature of 450-500 0C for a period of 4 hours. Thereafter the crucible was cooled and the residue was treated with an excess of 1 N HNO3, evaporated to dryness on a hot plate. The crucible was again placed in the muffle furnace at 400100C for about 10 minutes. The perfectly clean white ash was then cooled. The ash was further treated with about 5 ml of 1NHNO3 and swirled to dissolve the residue with addition of 5 ml of deionised water. The mixture was filtered a number of times by washing the residue with small amounts of deionised water. It is collected in a volumetric flask and was made up to the volume by adding deionised water. The metals were determined with AAS using the following formula (I): RxVxD Metal (mg/kg dry weight) = W Where R=AAS reading (mg/L), V=Fill up volume in sample dissolution (ml), D=Further dilution ratio and W=Weight of the sample (g).

In the present study, the concentrations of seven metals in plants are all dry-weight based and hence expressed in terms of mg/kg dry weight or mg/kgDW, where DW stands for dry weight. Analysis of the Soil Samples Air-dried soil samples were digested with a mixture of three acids, HCl, HNO3, and H2SO4. The advantages of the dissolution of metals in soil using concentrated inorganic acids are low cost and low salt matrix in the final solution for the determination of total heavy metal content. The method used for the extraction of metals [Cd, Cu, Fe, Mn, Ni, V, and Zn] from the soil samples and estimation of the metals is described below. 1g of the sample was digested with 30mL of the acid mixture [4 parts of H2SO4 (Sp. gravity = 1.84), 2 parts of HCl (Sp. Gravity = 1.19), and 1 part of HNO3 (Sp. Gravity = 1.40)]; the mixture was heated gently at first, and then more strongly until white fumes no longer evolved. The digested soil was taken up with hot dilute HCl (1:1) and filtered through a filter paper (Whatman No. 42) with several washings by distilled water. The volume of the filtrate was made up to 50-ml.

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The filtrate was then used for estimation of the metal by Atomic Absorption Spectrophotometer (VARIAN SpectrAA 220), using the above formula (I). Analysis of the Crude Oil Samples For the extraction of metals from the crude oil samples and estimation of the metals following method was applied. In order to extract metals, crude oil is decomposed by dry ashing. In this process 1g of crude oil was taken in a crucible and then the crucible was placed in a muffle furnace. The sample of crude oil was heated at 450-500C for about a period of four hours. After the completion of the ashing process, the crucible was allowed to cool and the ashes were dissolved in 10mL of 0.1N HCl and swirled to dissolve the residue. Then 5mL of deionised water was added and the solution was filtered a number of times by washing with small amount of water. The filtrate was collected in a 50mL volumetric flask and the volume was made up to the mark by adding deionised water. The filtrate was then used for estimation of the metal by Atomic Absorption Spectrophotometer (VARIAN SpectrAA 220), using the above formula (I). The crude oil samples collected from the two GGSs have been found to be identical with reference to the metals determined in this work. Average concentration value of a metal was calculated from the results obtained for the two crude oil samples.

RESULTS AND DISCUSSIONS

The analysis of the crude oil sample shows that crude oil contains substantial amounts of all the seven metals [Cd(6.49), Cu(122.88), Zn(276.75), Fe(3192), Mn(242.58), Ni(192.80) and V(1427), all values in mg/kg] and therefore, leakage and spills from the GGSs are quite likely to bring in large input of these metals into the nearby soil. The results obtained from the analysis of the soil samples (Table1-Table4) have clearly indicated that the metals (Cd, Cu, Zn, Fe, Mn, Ni and V) released by the oil field operations have spread into agricultural fields affecting the soil quality. Plants can take up metals from the growth soils. In a study of the pollution of soil and agricultural plants in the areas of petrochemical and oil-processing enterprises, Suleimanov et al. (1996) observed massive soil pollution in the adjacent 1-3km areas. They found that hydrocarbons and metals from wastes accumulate in onions, radish, potatoes, and apples. Poor growth and reduction in yield of vegetables due to heavy metal accumulation in plants have been reported by Benson and Ebong (2005). Osuji and Onojake (2004) determined the trace heavy metals like Ni, V, Cu, and Cd, which are normal constituents of crude oil, in the soils of oil-polluted sites in Niger Delta and found that Ni varied from 0.53 to 18.00 mg/kg, and Cu from 0.15 to 0.30 mg/kg in surface (0-15 cm) and subsurface (15-30 cm) soils, respectively; Cd and V were less than 0.20 mg/kg in all sampled plots. Street et al. (2008) studied the unsafe consequences of the South African practice of collecting medicinal plants from undisclosed locations and making these readily available to the public. Khan et al. (2008) also reported that accumulation of heavy metals in contaminated soils may pose health risks. The present study mainly describes the importance of accumulation of seven metals, namely Cd, Cu, Zn, Fe, Mn, Ni and V in plants grown on contaminated soils. Concentrations of seven metals (Cd, Cu, Zn, Fe, Mn, Ni and V) in Musa paradisiaca, Ziziphus jujuba Lamk, Solanum melongena Linn, and Brassica juncea, Hk F&Th are listed in the Table1Table4. Metal contents of the corresponding growth soils were also included in the tables. Cadmium According to Schachtschabel et al.(1984) Cd concentration of uncontaminated soils are usually below 0.5ppm but can be nearly up to 3ppm depending on geological background. Our results also reveal the similar type of concentrations. It

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is found contaminated soils as well as uncontaminated control soils contain appreciable amounts of cadmium. The results obtained from crude oil analysis reveal that crude oil contains appreciable amount of cadmium (Cd=6.49 mg/kg of crude oil). During the oil field operations the crude oil may accidentally enter the soils of the agricultural field near the GGS. Thus the soils of the agricultural field near the GGS may contain appreciable amounts of cadmium. In the present study cadmium contents (in mg/kg) of the contaminated soils are found in the ranges of 2.90-5.00. The Cd concentrations (in mg/kg) of the uncontaminated samples are found to be nearly same with an average value of 0.66 mg/kg. Cadmium is considered to be non-essential element for metabolic processes. It is the most ecotoxic metal that exhibit highly adverse effects on soil biological activity, plant metabolism, and the health of humans and the animal kingdom (Stoeppler 1991). Cd content in plants is of great concern as the pathway of Cd to man and animal. Plants are able to take up Cd from both air and soil by the roots and the leaves respectively. Leafy vegetables such as spinach and lettuce and root vegetables such as turnips, carrots and potatoes should be considered to be the main roots of Cd supply to man (Kabata-Pendias and Pendias 2001). The Cd concentrations (in mg/kg dry weight) in the uncontaminated samples of Mus.p, Ziz.j and Sol.m were found to be as follows: 1.19 (for Mus.p), 0.78 (for Ziz.j) and 1.40(for Sol.m). The cadmium contents (mg/kg dry weight) of the plant samples collected from the contaminated sites are found in the ranges of: 1.271.35(for Mus.p), 0.87-0.90(for Ziz.j), and 1.48-1.50(for Sol.m). Maximum cadmium content was recorded for Solanum melongena Linn (1.50 mg/kgDW) collected from contaminated sites. In the present study, accumulation of Cd in Brassica juncea Hk F&Th leaves was not detectable (below detection limit, <0.02 mg/L) though leaves are thought to be main routes of Cd supply to man. In general, Cd is the least abundant element in all the plant samples. The results indicate that the consumption of edible plant parts collected from contaminated area may pose a serious risk to human health. Copper According to Mortvedt et al. (1972) Concentration of Cu in normal soils ranges between 10-80ppm. Our results also reveal the similar type of concentrations. From the results obtained from crude oil analysis it was found that crude oil is a rich source of copper (Cu=122.88mg/kg of crude oil). Thus the oil contaminated soils of the agricultural field near the GGSs contain appreciable amount of copper. The copper contents (mg/kg) of the contaminated soils are found in the ranges of 17.60-22.05. From the tables it is seen that the uncontaminated soils recorded the minimum copper content (with an average value: 7.26 mg/kg). Copper is an essential element both for man and plants. According to available data about 30% of daily copper intake by adults in Europe is from cereals and potatoes (Kabata-Pendias and Pendias 2001). Uptake of Cu in plants is usually low. Excess Cu in soil is of special concern. Presence of large amount of Cu is harmful to organisms (Tiller and Merry 1981, Dixit and Witcomb 1983). Cu concentrations in the uncontaminated plant samples were: Mus.p: 1.65 mg/kg, Ziz.j: 4.50 mg/kg, Sol.m: 11.65 mg/kg, and Bras.j: BDL. The ranges of Cu concentrations in the contaminated samples were: Mus.p: 1.80-1.95 mg/kg, Ziz.j: 4.62-4.78mg/kg, Sol.m: 12.87-13.10 mg/kg, and Bras.j: BDL-BDL. Maximum concentration of Cu (13.10 mg/kg) was observed for Solanum melongena Linn. The concentration values of Cu in all the samples of Brassica juncea Hk F&Th leaves were found to be below detection limit. Zinc According to Mortvedt et al. (1972) Zn concentrations in most soils are between 10-300ppm. Present study reveals that uncontaminated as well as contaminated soils contain appreciable amount of zinc. Oil-polluted soils of the agricultural field near the GGS, in general, contain higher amounts of zinc than the uncontaminated soils. Presence of an appreciable amount of zinc in crude oil (Zn=276.75mg/kg of crude oil) was also observed during the analysis of crude oil.

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The contamination of soils by crude oil results in the increase of zinc content of soils. The zinc contents (in mg/kg) of the contaminated soils are found in the ranges of 38.9-94.35 whereas the uncontaminated soils have an average zinc concentration: 12.85mg/kg. Zinc is an essential element for both the plants and the animals. Most plant species and genotypes have great tolerance to excessive amount of Zn. Zn is not considered to be highly phytotoxic and zinc phytotoxicity is reported relatively often, especially for acid and heavily sludged soils (Kabata-Pendias and Pendias 1992). Environmental Zn pollution greatly influences the concentrations of this metal in plants. In the present study it was found that Zn is in appreciable amount in all the plant samples. Zn concentrations in the uncontaminated samples were: Mus.p: 5.70mg/kg, Ziz.j: 18.00mg/kg, Sol.m: 4.10mg/kg, and Bras.j: 13.21mg/kg. The ranges of Zn concentrations in the contaminated samples were: Mus.p: 5.93-6.00 mg/kg, Ziz.j: 18.20-18.25 mg/kg, Sol.m: 4.58-4.90 mg/kg, and Bras.j: 13.30-13.40 mg/kg. Ziziphus jujuba Lamk was recorded to contain maximum Zn content (18.25 mg/kg) while Solanum melongena Linn was recorded to contain minimum Zn content (4.10mg/kg). Iron Iron is a very abundant element of earths crust. The oil field contains large amounts of iron. This is due to the fact that crude oil is a rich source of iron content (Fe=3192mg/kg of crude oil). The soils of the agricultural field near the GGS have tendency to contain high iron content due to the spillage of crude oil during the oil field operations. The iron contents (mg/kg) are found in the ranges of 30045-60785 for the contaminated soils. The iron contents of uncontaminated soils are also high (Average: 15540mg/kg) but it is seen that the uncontaminated soils recorded the minimum iron content indicating the least effect of iron-rich crude oil at uncontaminated sites. Iron is essential for both the plants and the animals. However, excess of iron in plants can lead to browning of the leaves, known as bronzing (Mengel and Kirkby 1987). Iron is the most abundant metallic element in the human body. But, chronic excessive intake of iron may lead to hemosioderosis or hemochromatosis. Fe is present in all the plant samples in very high amount. In the present study it is found that the Fe concentrations in the uncontaminated plant samples were: Mus.p: 74mg/kg, Ziz.j: 119mg/kg, Sol.m: 112mg/kg, and Bras.j: 2510mg/kg. The ranges of Fe concentrations in the contaminated samples were: Mus.p: 112-114mg/kg, Ziz.j: 120-122 mg/kg, Sol.m: 129-135 mg/kg, and Bras.j: 2693-2762 mg/kg. Maximum iron content was recorded for Brassica juncea Hk F&Th leaves (2762mg/kg) and minimum for Musa paradisiaca (74mg/kg). Manganese From the results obtained from crude oil analysis it is found that crude oil contains a high amount of manganese (Mn=242.58mg/kg of crude oil). Thus the contamination of soils by crude oil will give elevated amount of manganese in the contaminated soils. According to Mortvedt et al.(1972) total manganese concentration in soils varies between 203000ppm. The soils of the agricultural field near the GGS have tendency to contain high manganese content due to the spillage of manganese-containing crude oil. The manganese contents (mg/kg) of the contaminated soils are found in the ranges of 151.2-223.1. It is seen that the soils of the unpolluted sites generally recorded the less manganese content (Average: 55.3mg/kg). Manganese is an essential element for both plants and animals. The high content of Mn in the plant tissues may result in Mn toxicity (Cobb et al. 2000) with time. In the present study, Mn contents in all the plant samples are found to be in appreciable amount. In the study it is found that the Mn concentrations in the uncontaminated samples were: Mus.p: 92mg/kg, Ziz.j: 20mg/kg, Sol.m: 19.1mg/kg, and Bras.j: 1065mg/kg. The ranges of Mn concentrations in the contaminated

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samples were: Mus.p: 168-171 mg/kg, Ziz.j: 21.3-22.0 mg/kg, Sol.m: 24-26 mg/kg, and Bras.j: 1185-1190 mg/kg. Among all the species studied maximum content of Mn (1190mg/kg) was obtained for Brassica juncea Hk F&Th leaves. Lowest value of Mn was observed for Solanum melongena Linn (19.1mg/kg). Nickel According to Schachtschabel et al.(1984) Ni concentrations in uncontaminated soils are generally between 550ppm. From the present study the nickel contents of uncontaminated soils are found to be below the detection limit. But it is found that contaminated soils contain appreciable amount of nickel. This indicates considerable input of nickel from the waste materials generated during the oil field activities. Presence of a high amount of nickel (Ni=192.80mg/kg of crude oil) in crude oil is also observed. Thus the oil-polluted soils of the agricultural field near the GGSs contain appreciable amounts of nickel. The nickel contents (mg/kg) of the contaminated soils are found in the ranges of 39.3-171.9. Nickel is an essential mineral trace nutrient found at low concentrations in most natural soils. However, it may reach toxic levels in certain areas and affect a number of biochemical and physiological processes in plants. Wilting and leaf necrosis have been described as typical visible symptoms of Ni2+ toxicity (Llamas et al. 2008). The Ni concentrations in the uncontaminated samples were: Mus.p: 5.15mg/kg, Ziz.j: 6.25mg/kg, Sol.m: 6.50 mg/kg, and Bras.j: BDL. The ranges of Ni concentrations in the contaminated samples were: Mus.p: 6.10-6.40 mg/kg, Ziz.j: 6.26-6.27 mg/kg, Sol.m: 6.77-7.12 mg/kg, and Bras.j: BDL-BDL. Maximum Ni content was recorded for Solanum melongena Linn (7.12mg/kg). Except Brassica juncea Hk F&Th leaves, other plant samples are important sources of nickel. Ni contents in all the samples of Brassica juncea Hk F&Th leaves were found to be below detection limit. Vanadium An especially great range of vanadium in some coals and crude oil has been reported. Increased V content of soil up to 110 ppm in the vicinity of a crude oil refinery was observed by Pawlak (1980). A high degree of association of V with Mn, and with the K content of soil has been reported by Norish (1975). In the present study vanadium contents of the uncontaminated soils are found to be below the detection limit. But it is found that contaminated soils contain appreciable amount of nickel. Presence of high amount of vanadium in contaminated soils indicates considerable input of this metal from oil field activities. Presence of a high amount of vanadium (V=1427mg/kg of crude oil) in crude oil was also determined. The vanadium contents (mg/kg) of the contaminated soils are found in the ranges of 240.5-352.0. Vanadium is an essential element for both the plants and animals. It is interesting to note that though the V concentrations in uncontaminated soils are found to be below detection limit but the element is found to be present in appreciable amount in the uncontaminated plant samples except Solanum melongena and Ziziphus jujuba Lamk This implies an appreciable uptake of V by plants from soils having less available V. The V concentrations in the uncontaminated plant samples were: Mus.p: 1.25mg/kg, Ziz.j: 0.20mg/kg, Sol.m: BDL, and Bras.j: 7.19mg/kg. The ranges of V concentrations in the contaminated plant samples were: Mus.p: 1.40-1.60 mg/kg, Ziz.j: 0.25-1.0 mg/kg, Sol.m: 0.100.20mg/kg, and Bras.j: 7.20-7.39mg/kg. Maximum amount of V was observed for Brassica juncea Hk F&Th (7.39mg/kg) and lowest for Solanum melongena Linn (BDL). Variations of Metal Contents in Soils and Plants Soil metal content is the measure of extent of pollution due to crude oil contamination. It was already mentioned that crude oil contains appreciable amount of all the metals under investigation and therefore it is observed that in all the cases contaminated soil samples contain more metals than the uncontaminated samples. Metal contents in the contaminated

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soils depend upon the extent of contamination of soil by crude oil. Concentrations of a metal in different contaminated soils (growth soil) vary as in the following order irrespective of the plant species: B3< B7< B1< B10< B5< B8< B2< B11. But the concentrations of a typical metal in plant samples of different plant species do not follow the above order of variation (i.e., do not follow the order A3< A7< A1< A10< A5< A8< A2< A11) due to the difference in ability of metal uptake by different plant species. This means that accumulation of a metal in a plant species is affected by the type of the plant species. But, the concentrations of a metal in a typical plant part collected from different growth sites vary in a common order as that of another metal [discussed in the next section]. Also, due to the absence of crude oil in the uncontaminated soils, negligible variations in metal concentrations in these soils (collected from different growth sites, i.e., 4 No. of composite samples: B3, B6, B9 and B12) are observed. Negligible variations in metal concentrations may be due to the differences in some other soil properties. In case of uncontaminated soils, therefore, the results have been discussed in terms of average value of the soil metal contents irrespective of growth sites. For example, the zinc contents (in mg/kg) of the uncontaminated soils have an average zinc concentration of 12.85mg/kg (B3:12.95, B6:12.86, B9:12.81, B12:12.79). Similarly, other uncontaminated soil metal contents (in mg/kg, average) are: Cd: 0.66, Cu: 7.26, Fe: 15540, Mn: 55.3, Ni & V: BDL. Comparison of the Metal Concentrations in Plants to the Metal Concentrations in Corresponding Growth Sites Depending upon the growth soils, a metal can accumulate in a plant part in different concentrations. it was found that in the uncontaminated area the variation in concentrations of a typical metal in a particular plant species with respect to different locations (sampling stations) was not very large and hence mean of the metal concentration values of the plant samples (of a particular plant species) collected from different locations within the same uncontaminated area (of Lakowa) were calculated as the reference value. Metal contents in the contaminated plants depend upon the extent of contamination of soil by crude oil. In a glasshouse study Gaw et al.(2008) found that concentrations of Cd and Cu in lettuce increased with increasing soil concentrations. In the present study it was observed that a plant tissue in contaminated sites contains more metal than in the uncontaminated sites. Also, in the different contaminated sites the variations in concentrations for metals are found to be significant. In general it was observed that with the increase in metal content of different contaminated growth sites, metal concentrations in plant parts were also found to be increased. For example, increasing orders of the concentrations of a typical metal in soil with respect to a plant species are as follows: (1). For the growth soils of Musa paradisiaca: B3<B1 <B2 (2). For the growth soils of Ziziphus jujuba Lamk: B6<B4<B9 (3). For the growth soils of Solanam melongena Linn: B9<B7<B8 (4). For the growth soils of Brassica juncea Hk F&Th: B12<B10<B11. Similarly, the concentration of the typical metal in a plant part increases in the same order, i.e., (1). For the plant samples of Musa paradisiaca: A3< A1< A2 (2). For the plant samples of Ziziphus jujuba Lamk: A6<A4< A5 (3). For the plant samples of Solanam melongena Linn: A9< A7< A9 (4). For the plant samples of Brassica juncea Hk F&Th: A12< A10< A11.

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Comparative Study of the different Metals within a Same Plant Species and Variation in Accumulation of a Metal in Different Plant Species The concentrations (all dry-weight based, i.e., DW) of seven heavy metals (Cd, Cu, Zn, Fe, Mn, Ni and V) in Musa paradisiaca for different locations are listed in the Table1. The element wise variations of metal concentrations in Musa paradisiaca samples are: (1). Mn >Fe > Ni >Zn > Cu >V > Cd (for A1 and A2) and (2). Mn >Fe >Zn > Ni > Cu >V > Cd (for A3). In this case, it was observed that in the uncontaminated (for A3) sample Ni content is lower than Zn content but in contaminated samples (for A1 and A2) Ni content is greater than Zn content. Thus, in these cases, with increase in contamination, Ni content in Musa paradisiaca is so highly increased that this reverses the usual trend of Zn to Ni concentration in uncontaminated samples. The concentrations (all dry-weight based, i.e., DW) of seven heavy metals (Cd, Cu, Zn, Fe, Mn, Ni and V) in Ziziphus jujuba Lamk for different locations are listed in the Table2. For all the plant samples of Ziziphus jujuba Lamk (Assamese: Baguri) fruit, the element wise variation of metal concentrations are found to be as follows: Fe > Mn> Zn > Ni > Cu > Cd > V (for A4, A5 and A6). It is important to note that vanadium in Ziziphus jujuba Lamk is found in very poor amount. The concentrations (all dry-weight based, i.e., DW) of seven heavy metals (Cd, Cu, Zn, Fe, Mn, Ni and V) in Solanum melongena Linn for different locations are listed in the Table3. In case of Solanum melongena Linn, the element wise variation of metal concentrations in plant samples collected from different locations are found to be same as follows: Fe > Mn> Cu > Ni > Zn > Cd > V (for A7, A8 and A9). Similar to Ziziphus jujuba Lamk, Solanum melongena Linn also contains vanadium in very poor amount. The concentrations (all dry-weight based, i.e., DW) of seven heavy metals (Cd, Cu, Zn, Fe, Mn, Ni and V) in Brassica juncea Hk F&Th (Assamese: Laisak) for different locations are listed in the Table4. The element wise variation of metal contents in Brassica juncea Hk F&Th, leaves for different locations are same and can be given as follows: Fe > Mn > Zn > V > Cu, Cd, Ni (for A10, A11 and A12). Two important findings are obtained from this observation. Firstly, in Brassica juncea, Hk F&Th leaves; copper, cadmium and nickel concentrations are below detection limit. Secondly, Brassica juncea Hk F&Th leaves are very rich source of iron and manganese. From the above findings it is seen that element wise variations in metal concentration is very complicated and different trends are observed among different plants and different growth sites.

CONCLUSIONS
Assam crude oil contains substantial amounts of all the seven metals (Cd, Cu, Zn, Fe, Mn, Ni and V) investigated in the present study. Therefore, oil-polluted soils of the agricultural field near the GGSs, in general, contain higher amounts of metals than the uncontaminated soils. From the present study the nickel & vanadium contents of uncontaminated soils are found to be below the detection limit. But they are present in appreciable amount in the contaminated soils. Presence of a high amount of vanadium and nickel in crude oil was also determined. Accumulation of metals in plants varies depending on the growth site. The results clearly revealed that with the increase in metal content of different contaminated growth sites, metal concentrations in plant parts were also found to be increased. Also, due to the absence of crude oil (containing metals) in the uncontaminated soils, negligible variation in

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metal concentrations was observed in these soils. Similarly, it was found that in the uncontaminated area the variation in concentrations of a metal in a particular plant species with respect to different locations was not very large. The present study indicates the presence of seven metals (Cd, Cu, Zn, Fe, Mn, Ni and V) in Musa paradisiaca, Ziziphus jujuba Lamk, Brassica juncea Hk F&Th, and Solanum melongena Linn in varying amount. Results revealed that in most of the cases Fe, Mn and V content are in appreciable amount. Fe is present in all the plant samples in very high amount. In general, Cd is the least abundant element in most of the plant samples. In Brassica juncea Hk F&Th leaves, copper, cadmium and nickel concentrations are below detection limit. But these leaves are very rich source of iron and manganese. Accumulation of Cd in Brassica juncea Hk F & Th leaves is less though Cd is considered to be absorbed effectively by leaf system. Uptake of nickel by Musa paradisiaca in the contaminated soils is of special interest as this reverses the usual trend of Zn to Ni concentration in uncontaminated samples. It is important to note that vanadium is found in very poor amount in Ziziphus jujuba Lamk and Solanum melongena Linn. It is important observe that plant uptake of a metal not only depends on the soil metal content but it also depends on the type of the plant species. The results also indicate that the extent of accumulation of a metal in different plant species varied depending on the type of the metal. It is seen that element wise variations in metal concentration is very complicated and different trends are observed among different plants and different growth sites. The results obtained from the present study indicate that the consumption of edible plant parts collected from contaminated area may pose a serious risk to human health due to toxic concentration of metals. Interesting results we have found that in the control samples concentration of cadmium in Musa paradisiaca (fruit part), Ziziphus jujuba Lamk (fruit part), Solanum melongena Linn (fruit part) was less than the concentration of the corresponding soil samples.But in case of Brassica juncea Hk F&Th (leaf part) the concentration of Cd was nil. This variation may perhaps be due to the accumulation capacity of fruit and leaf part of the different types of plants. It has been observed that the picture for concentration of the metal Ni in Musa paradisiaca (fruit part), Ziziphus jujuba Lamk (fruit part), and Solanum melongena Linn (fruit part) is the same as in V in Musa paradisiaca (fruit part), Ziziphus jujuba Lamk (fruit part), Brassica juncea Hk F&Th (leaf part).It is revealed from the result that Organic matter strongly bind heavy metals such as Cd, Ni, and V. Similar results have been observed in other studies (Temminghoff et.al 1997, Sauveet.al 1997, Christensen and Christensen 1999, Weng et.al 2002).

REFERENCES
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10. Gaw, S. K., Kim, N. D., Northcott, G. L., Wilkins, A. L. & Robinson G. (2008). Uptake of SigmaDDT, arsenic, copper, and lead by lettuce and reddish grown in contaminated horticultural soils. Agric. Food Chem. 56(15), 6584-93. 11. Greger, M., Johansson, M., Stih, A.,& Hamza, K. (1993). Foliar uptake of Cd by pea (Pisum sativum) and sugar beet (Beta vulgaris). Physiol. Plant. 88, 563-570. 12. Greger, M. (1999). Metal Availability and Bioconcentration in Plants. In Heavy Metal Stress in Plants From Molecules to Ecosystems, ed. M. N. V. Prasad and J. Hagemeyer, 1-27. Berlin Heidelberg New York: Springer Verlag. 13. Jackson, M. L. (1967). Soil Chemical Analysis. New Delhi: Prentice Hall of India Pvt. Ltd. 14. Janiyani, K. L., Wate, S. R., Muthal, P. L. & Joshi, S. R. (1992). Hydrocarbons in oil and oil sludge from refinery. Indian J. Environ. Hlth. 34, 169-179. 15. Kabata-Pendias, A. & Pendias, H. (2001). Trace elements in soils and plants (3rd edn). Boca Raton-London-New York-Washington, DC: CRC Press LLC. 16. Kabata-Pendias, A. & Pendias, H. (1992). Trace Metals in Soils and Plants. Boca Raton, FL: CRC Press. 17. Khan, S., Lin, A., Shuzhen, Z., Qinhong, H. & Yong-Guan, Z. (2008). Accumulation of polycyclic aromatic hydrocarbons and heavy metals in lettuce grown in the soils contaminated with long-term wastewater irrigation. J. Haz. Mat. 152, 506-515. 18. Llamas, A., Ullrich, C. I. & Sanz, A. (2008). Ni2+ toxicity in rice: effect on membrane functionality and plant water content. Plant Physiol. Biochem. 46(10), 905-10. 19. Mengel, K.& Kirkby, E. A.(1987). Principles of Plant Nutrition. Berne: International Potash Institute. 20. Mortvedt, J. J., Giordano, P. M. & Lindsay, N. L.(eds).(1972). Micronutrients in agriculture. Madison, WI: Soil Science Society of America. 21. Norrish, K. (1975). The geochemistry and mineralogy of trace elements. In Trace Elements in Soil-Plant-Animal Systems, ed. D. J. D. Nicholas, and A. R. Egan, 55. New York: Academic Press. 22. Onyeike, E. N., Ogbuja, S. I. & Nwinuka, N. M. (2002). Inorganic ion levels of soils and streams in some areas of Ogniland , Nigeria as affected by crude oil spillage. Environ. Monit. Assess. 73(2),191-205. 23. Osuji, L. C. & Onojake, C. M. (2004). Trace heavy metals associated with crude oil: a case study of Ebocha-8 oilspill-polluted site in Niger Delta, Nigeria. Chem. Biodiders. 1(11), 1708-15.

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24. Pawlak, L. (1980). Trace Element Pollution of Soils and Plants in the Vicinity of the Oil Refinery Plant near Plock. PhD diss., Agricultural University, Warsaw. 25. Russell, E. W. (1973). Soil conditions and plant growth (10th edition). Longman. 26. Sauve, S. McBride, M. B.& Hendershot, W.(1997) Speciation of lead in contaminated soils. Environ. Pollut. 98:149155. 27. Saxena, P. K., Krishnaraj, S., Dan, T., Perras, M. R.& Vettakkorumakankav, N. N. (1999). Phytoremediation of Heavy Metal Contaminated and Polluted Soils. In Heavy Metal Stress in Plants From Molecules to Ecosystems, ed. M. N. V. Prasad and J. Hagemeyer, 305-329. Berlin-Heidelberg-New York: Springer Verlag. 28. Schachtschabel, P., Blume, H. P., Hartge, K. H., & Schwertmann, U. (1984). Lehrbuch der Bodenkunde. Enke, Stuttgart. 29. Stoeppler, M. (1991). Cadmium. In Metals and their compounds in the environment, ed. E. Merian, 804. Weinham: VCH. 30. Street, R. A., Kulkarni, M. G., Stirk, W. A., Southway, C.& Van Staden, J. (2008). Variation in heavy metals and microelements in South African medicinal plants obtained from street markets. Food Addit. Contam. PartA Chem. Anal. Control Expo. Risk Assess. 25(8), 953-60. 31. Suleimanov, R. A., Safonnikova, S. M., Lakhina, M. R.& Magzhanova, S. A. (1996). The effect of petrochemical and oil-refining enterprises on the sanitary state of the soil cover. Gig. Sanit.1996:May-June(3), 12-5. 32. Temminghoff, E. J. M. Van der Zee, S. E. A. T. M.& De Haan F. A. M.(1997) Copper mobility in a copper contaminated sandy soil as affected by pH, solid and dissolved organic matter. Environ. Sci. Technol. 31, 11091115 33. Tiller, K. G. & Merry, R. H. (1981). Copper pollution of agricultural soils. In Copper in Soils and Plants, ed. J. F. Loneragan, A. D. Robson and R. D. Graham, 119. New York: Academic Press. 34. VanAssche, F. & Clijsters, H. (1986). Inhibition of photosynthesis in phaseotus vulgaris by treatment with toxicconcentration of zinc: effect of ribulose-1,5-biphosphate carboxylase/oxygenase. J. Plant Physiol. 125, 355360. 35. Weng, L. Temminghoff, E. J. M. Lofts,S. Tipping,E. & Van Riemsdijk,W.E.(2002). Complexation with Dissolved Organic Matter and Solubility Control of Heavy Metals in a Sandy Soil. Environ. Sci. Technol, 36, 4804-4810 .Table 1: Metal Contents in Musa Paradisiaca (Fruit Part) Samples (in Mg/Kg Dry Weight), and Metal Contents (Mg/Kg) of Growth Soils (APlant Sample, BSoil Sample). Growth Site LGGS3(Mus.p) LGGS9(Mus.p) A1 B1 A2 B2 Cd 1.27 3.45 1.35 4.50 Cu 1.80 18.45 1.95 20.35 Zn 5.93 51.85 6.00 77.70 Fe 112 39105 114 60920 Mn 168 180.4 171 219.8 Ni 6.10 52.0 6.40 78.5 V 1.40 295.0 1.60 342.5 a BDL <0.1mg/L, bBDL <0.02mg/L Metal L(Mus.p) A3 B3 1.19 0.65 1.65 7.30 5.70 12.95 74 15470 92 55.2 5.15 aBDL 1.25 bBDL Range Contaminated Sites A B 1.27-1.35 3.45-4.50 1.80-1.95 18.45-20.35 5.93-6.00 51.85-77.70 112-114 39105-60920 168-171 180.4-219.8 6.10-6.40 52.0-78.5 1.40-1.60 295.0-342.5

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Table 2: Metal Contents in Ziziphus Jujuba Lamk (Fruit Part) Samples (in Mg/Kg Dry Weight), and Metal Contents (Mg/Kg) of Growth Soils (APlant Sample, BSoil Sample). Growth Site LGGS3(Ziz.j) LGGS9(Ziz.j) A4 B4 A5 B5 Cd 0.87 2.90 0.90 4.00 Cu 4.62 17.60 4.78 19.65 Zn 18.2 38.9 18.25 54.65 Fe 120 30045 122 43995 Mn 21.3 151.2 22.0 208.1 Ni 6.26 39.3 6.27 66.5 V 0.25 240.5 1.00 322.0 a BDL <0.1mg/L, bBDL <0.02mg/L. Metal L(Ziz.j) A6 B6 0.78 0.63 4.50 7.20 18.00 12.86 119 15560 20.0 54.8 a 6.25 BDL b 0.20 BDL Range Contaminated sites A B 0.87-0.90 2.90-4.00 4.62-4.78 17.60-19.65 18.20-18.25 38.9-54.65 120-122 30045-43995 21.3-22.0 151.2-208.1 6.26-6.27 39.3-66.5 0.25-1.00 240.5-322.0

Table 3: Metal Contents in Solanum Melongena Linn (Fruit Part) Samples (in Mg/Kg Dry Weight), and Metal Contents (Mg/Kg) of Growth Soils (APlant Sample, BSoil Sample). Growth Site LGGS3(Sol.m) LGGS9(Sol.m) A7 B7 A8 B8 Cd 1.48 3.05 1.50 4.10 Cu 12.87 18.30 13.10 20.00 Zn 4.58 45.80 4.90 66.65 Fe 129.0 33245 135.0 60785 Mn 24.0 166.6 26.0 213.9 Ni 6.77 50.85 7.12 74.3 V 0.10 256 0.20 328 a BDL <0.1mg/L, bBDL <0.02mg/L. Metal Range Contaminated Sites A B 1.48-1.50 3.05-4.10 12.87-13.10 18.30-20.00 4.58-4.90 45.80-66.65 129.0-135.0 33245-60785 24.0-26.0 166.6-213.9 6.77-7.12 50.85-74.3 0.10-0.20 256-328

L(Sol.m) A9 B9 1.40 0.67 11.65 7.24 4.10 12.81 112.0 15480 19.1 55.4 a 6.50 BDL b BDL bBDL

Table 4: Metal Contents in Brassica Juncea Hk F&Th (Leaf Part) Samples (in Mg/Kg Dry Weight), and Metal Contents (Mg/Kg) of Growth Soils (APlant Sample, BSoil Sample) Metal Cd LGGS3(Bras.j) A10 B10 a BDL 3.50 Growth Site LGGS9(Bras.j) A11 B11 a BDL 5.00 L(Bras.j) A12 B12 a BDL 0.68 Range Contaminated Sites
a

A BDL-aBDL

B 3.50-5.00

b b b b Cu BDL 18.75 BDL 22.05 BDL 7.29 BDL-bBDL 18.75-22.05 Zn 13.30 53.30 13.40 94.35 13.21 12.79 13.30-13.40 53.30-22.05 Fe 2693 39845 2762 63495 2510 15652 2693-2762 39845-63495 Mn 1185 195.4 1190 223.1 1065 55.9 1185-1190 195.4-223.1 c c c Ni BDL 63.9 BDL 171.9 BDL cBDL cBDL-cBDL 63.9-171.9 d V 7.20 320.5 7.39 352.0 7.19 BDL 7.20-7.39 320.5-352.0 a b c BDL <0.02mg/L, BDL <0.03mg/L, BDL <0.1mg/L, dBDL <0.02mg/L.