Agriculture, Ecosystems and Environment 109 (2005) 310322 www.elsevier.

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Long-term impact of irrigation with sewage efuents on heavy metal content in soils, crops and groundwatera case study
R.K. Rattan a,*, S.P. Datta a, P.K. Chhonkar a, K. Suribabu a, A.K. Singh b
a

Division of Soil Science and Agricultural Chemistry, Indian Agricultural Research Institute, New Delhi 110012, India b Water Technology Centre, Indian Agricultural Research Institute, New Delhi 110012, India Received 15 September 2004; received in revised form 3 February 2005; accepted 22 February 2005

Abstract There is a gradual decline in availability of fresh water to be used for irrigation in India. As a consequence, the use of sewage and other industrial efuents for irrigating agricultural lands is on the rise particularly in peri-urban areas of developing countries. On the other hand, there is increasing concern regarding the exceedance of statutory and advisory food standards for trace metals throughout the world. Hence, a case study was undertaken to assess the long-term effect of sewage irrigation on heavy metal content in soils, plants and groundwater. For this purpose, peri-urban agricultural lands under Keshopur Efuent Irrigation Scheme (KEIS) of Delhi, India were selected where various cereals, millets, vegetable and fodder crops have successfully been grown. Sewage efuents, ground water, soil and plant samples were collected and analysed mainly for metal contents. Results indicated that sewage efuents contained much higher amount of P, K, S, Zn, Cu, Fe, Mn and Ni compared to groundwater. While, there was no signicant variation in Pb and Cd concentrations in these two sources of irrigation water and metal content were within the permissible limits for its use as irrigation water. There was an increase in organic carbon content ranging from 38 to 79% in sewage-irrigated soils as compared to tubewell water-irrigated ones. On an average, the soil pH dropped by 0.4 unit as a result of sewage irrigation. Sewage irrigation for 20 years resulted into signicant build-up of DTPAextractable Zn (208%), Cu (170%), Fe (170%), Ni (63%) and Pb (29%) in sewage-irrigated soils over adjacent tubewell waterirrigated soils, whereas Mn was depleted by 31%. Soils receiving sewage irrigation for 10 years exhibited signicant increase in Zn, Fe, Ni and Pb, while only Fe in soils was positively affected by sewage irrigation for 5 years. Among these metals, only Zn in some samples exceeded the phytotoxicity limit. Fractionation study indicated relatively higher build-up of Zn, Cu, Fe and Mn in bioavailable pools of sewage-irrigated soils. By and large, tissue metal concentrations in all the crops were below the generalized critical levels of phytotoxicity. Based on the soil to plant transfer ratio (transfer factor) of metals, relative efciency of some cereals, millet and vegetable crops to absorb metals from sewage and tubewell water-irrigated soils was worked out. Risk assessment in respect of metal contents in some vegetable crops grown on these sewage-irrigated soils indicated that these vegetables can be consumed safely by human. # 2005 Elsevier B.V. All rights reserved.
Keywords: Long-term sewage irrigation; Heavy metals; Soils; Groundwater; Crops; Hazard quotient

* Corresponding author. Tel.: +91 11 25841991; fax: +91 11 25841529. E-mail address: rkrattan@yahoo.com (R.K. Rattan). 0167-8809/$ see front matter # 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.agee.2005.02.025

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1. Introduction India supports more than 16% of the worlds population with only 4% of the worlds fresh water resources (Singh, 2003). Although agriculture sector in this country has been major user of water, share of water allocated to irrigation is likely to be decreased by 1015% in next two decades (CWC, 2000). In this changing scenario, reuse of domestic and industrial waste water in agriculture for irrigating crops appears to be a lucrative option. Besides being source of irrigation water, these waste waters contain appreciable amounts of plant nutrients. In India, total waste water generated per annum from 200 cities is about 2600 Mm3 (Kaul et al., 1989) and also the use of sewage efuents for irrigating agricultural lands is on the rise especially in the peri-urban area. These waste waters carry appreciable amounts of trace toxic metals (Feign et al., 1991; Pescod, 1992; Som et al., 1994; Gupta et al., 1998; Brar et al., 2000; Yadav et al., 2002) and concentrations of trace metals in sewage efuents vary from city to city (Rattan et al., 2002). Although the concentration of heavy metals in sewage efuents are low, long-term use of these waste waters on agricultural lands often results in the build-up of the elevated levels of these metals in soils (Rattan et al., 2002). Extent of build-up of metals in waste water-irrigated soils depends on the period of its application (Bansal et al., 1992; Palaniswami and Sree Ramulu, 1994). Crops raised on the metal-contaminated soils accumulate metals in quantities excessive enough to cause clinical problems both to animals and human beings consuming these metal rich plants (Tiller, 1986). Since food chain contamination is one of the major routes for entry of metals into the animal system, monitoring the bioavailabile pools of metals in contaminated soils has generated a lot of interest (Datta et al., 2000; Yadav et al., 2002). Also information on the fractionation of trace metals in soils is potentially valuable in predicting bioavailability, metal leaching rates, and transformation between chemical forms in agricultural and polluted soils (Jenne and Louma, 1977; McBride, 1981; Miller et al., 1986). But such information on agricultural lands receiving sewage irrigation for quite a long time is meagre. Crop species exercise differentiality in accumulating metals in their tissue (Lepp, 1981; Datta et al., 2000) and efciency of different crops in absorption of

metals is judged either by plant metal uptake or by transfer factor of metals from soil to plants. Uptake of metals by plants may be a good indicator of efciency of metal absorption of different crop species grown on soils having uniform metal levels under controlled conditions. Whereas, transfer factor of metal from soil to plants indicates the efciency of crop species better where crops are grown on soils having variable metal contents, e.g. farmers elds. Generally, soil to plant transfer factor of metals is computed based on total metal contents of soils (Hooda et al., 1997). However, total metal content in soils does not take into account the other soil factors that modify the bioavailability of metals. Hence, computation of soil to plant transfer factor of metals should be based on available soil metal pools. We attempted to study some of the abovementioned aspects in sewage-irrigated peri-urban agricultural lands under Keshopur Efuent Irrigation Scheme (KEIS) of the Delhi Government, India. Under this scheme, sewage irrigation has been provided to the farmers elds for more than two decades. Various cereals, millet, leafy vegetables and fodder crops have successfully been grown thereon. No investigation has been carried out in sewage-irrigated soils of this periurban area except one where we reported the build-up of some of major and secondary plant nutrients in soils as a result of sewage irrigation (Rattan et al., 2001). The objectives of this study were: (i) to study the chemical composition of sewage efuents emanating from KEIS and groundwater; (ii) to assess the effects of long-term irrigation with sewage efuents on metal contents in soils and plants; and (iii) to assess the risk of consuming leafy green vegetables in respect of their heavy metal contents grown on sewage-irrigated soils to human beings.

2. Materials and methods 2.1. Study area and collection of samples The study area is located in the western Delhi, India, where sewage efuents originating from Keshopur Sewage Treatment Plant have been used for irrigation purposes since 1979 (Fig. 1). Our study conned to six villages, viz. Nilothi, Mundka, Ranhola, Bakarwala, Hirankudna and Dichaonkalan covering 123, 233, 196,

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Fig. 1. Map showing the area under Keshopur Efuent Irrigation System commissioned in 1979.

775, 183 and 98 acres of agricultural lands, respectively. Agricultural lands of rst four villages have been under sewage irrigation for 20 years, while in Hirankudna and Dichaokalan, crops have been irrigating with sewage efuents for 10 and 5 years, respectively. Sewage efuents were collected periodically from 13 locations spread over these six villages under study. Similarly, groundwater samples were also collected from eight tubewells located in these villages. First sampling was done on 17 January 2002 and subsequently three more samplings were carried out each at two months interval. With active support of the Revenue Ofcials of the Delhi government and local farmers, land in each village was divided into two categories, viz. sewage and tubewell water-irrigated. Tubewell water-irrigated lands were the ones inaccessible for sewage irrigation because of their slight higher elevation. In all, 431 and 106 soil samples (015 cm) were collected from sewage and adjacent tubewell water-irrigated lands, respectively. From

sewage-irrigated sites of Nilothi, Ranhola, Mundka, Bakarwala, Hirankudna and Dichaokalan 37, 62, 57, 213, 39 and 23 soil samples were collected, respectively, the corresponding number of soil samples collected from adjacent tubewell water-irrigated sites were 11, 12, 6, 51, 10 and 16. Plant samples of crops grown on sewage and tubewell water-irrigated lands were also collected from the soil sampling sites wherever available. 2.2. Chemical analysis of sewage efuents, groundwater, soil and plant samples An aliquot of 500 mL of sewage efuents and groundwater samples with 15 mL of HNO3 was evaporated to near dryness on a hot plate. Then contents were digested with 15 mL of HNO3 and 20 mL HClO4 (70%) (Brar et al., 2000). The residue was taken in 15 mL of 6N HCl and made to the volume (50 mL) and contents were ltered. The ltrate was

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analyzed for P, K, S, Zn, Cu, Fe, Mn, Ni, Pb and Cd using inductively coupled plasma-atomic emission spectrophotometer (ICP-AES). Sewage efuent samples were analyzed for pH and electrical conductivity using pH meter and solu-bridge, respectively. Carbonates and bicarbonates were estimated by titrating an aliquot of efuent samples with H2SO4. Soil samples were dried, ground and passed through 2 mm sieve. Soil pH was measured in suspension (soil:water::1:2) according to Datta et al. (1997). Organic carbon contents in soil were determined by the wet digestion method (Walkley and Black, 1934). Further, 30 soil samples across the villages were selected and analysed for texture by hydrometer method (Day, 1965). For heavy metal analysis, the soil samples were extracted with 0.005 M DTPA according to Lindsay and Norvell (1978) and metals in the extract were determined with help of atomic absorption spectrophotometer (AAS; GBC 932). In all, nine surface (015 cm) soil samples were selected from sewage efuent-irrigated lands receiving efuent irrigation for last 20 years and three soil samples were also selected from adjacent tubewell water-irrigated lands. These soil samples were used for sequential extraction of Zn, Cu, Fe and Mn according to the scheme of Iwasaki and Yoshikawa (1990) which is modied form of fractionation scheme of Miller et al. (1986). Plant samples were dried at 60 8C in hot air oven, ground and digested in a diacid mixture (HNO3:HClO4::9:4) (Jackson, 1973). Metal contents in the plant digests were determined on AAS. 2.3. Metal transfer factor Soil to plant metal transfer factor was computed as ratio of the concentration of metal in plants (on dry weight basis) to its DTPA-extractable metal contents in soil. 2.4. Risk assessment Risk to human health (Hazard Quotient, HQ) for intake of Zn, Cu and Ni through consumption spinach (Brassica oleraceae), gobhi sarson (Brassica napus) and Indian rape (Brassica campestris) as green leafy vegetables grown on sewage-irrigated soils was calculated using the following relationship (Pierzynski et al., 2000):

HQgv = (add/RfD), where HQgv is the hazard quotient to a human from consumption of green vegetables, add: the average daily dose (mg metal/kg body weight/day) and RfD the reference dose. The values of RfD for Zn and Ni were used as 0.3 and 0.02 mg/kg bw/day, respectively (IRIS, 2003). For Cu, value of provisional maximum tolerable daily intake is 0.5 mg/kg bw/day (WHO, 1982) and the same is used as RfD (Alam et al., 2003). Daily intake of green vegetable was considered as 200 g/person/day which is recommended amount from nutritional point of view (Hassan and Ahmed, 2000). A factor of 0.085 was used to convert the fresh to dry weight of these green vegetables. Average body weight for an adult was considered as 70 kg. Average daily dose (add) was computed using following relationship: add mc cf di bw

where mc is the metal concentrations in plant (mg kg1) on dry weight basis, cf the fresh to dry weight conversion factor, di the daily intake of green vegetable (kg) and bw the body weight (kg). Assessment of risk as computed here is not complete since, metal accumulation to soil organisms, groundwater, surface water, direct uptake of soil by human and animal are some of the other risks which have not been considered here. 2.5. Statistical analysis The differences between DTPA-extractable metal contents in sewage and tubewell water-irrigated soils were statistically evaluated by applying t-test according to Snedecor and Cochran (1967). Simple correlation and multiple regression analyses were also carried out to assess the relationships of DTPA-extractable metal with plant metal concentration, soil pH and organic carbon.

3. Results and discussion 3.1. Physico-chemical properties of sewage efuents and groundwater Plant nutrients and heavy metal contents in sewage efuents and groundwater samples of rst sampling

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Table 1 Plant nutrients and heavy metals content in sewage efuents and groundwater collected at rst sampling Element P (mg L1) K (mg L1) S (mg L1) Zn (mg L1) Cu (mg L1) Fe (mg L1) Mn (mg L1) Ni (mg L1) Pb (mg L1) Cd (mg L1) Sewage efuents 0.565.91 (2.57) 9.3323.1 (11.7) 7.7122.9 (15.9) 6151 (61) 9116 (29) 6393793 (1464) 24122 (64) 3967 (49) 2267 (33) 1.172.44 (1.53) Groundwater 0.110.36 (0.22) 0.845.03 (3.58) 9.8519.4 (14.3) 338 (11) 79 (8) 100745 (557) 115 (10) 955 (37) 2241 (30) 1.071.76 (1.42)

Figures in parenthesis indicate the mean values.

are presented in Table 1. Data for second, third and fourth sampling were not shown, since similar values of these elements were obtained except S. In rst sampling, on an average, P, K, and S contents were 0.22, 3.58 and 14.3 mg L1, respectively in groundwater samples, whereas, corresponding values for sewage efuents were 2.57, 11.7 and 15.9 mg L1. Among these plant nutrients, sewage efuents contained about 12 and 3 times more P and K, respectively compared to ground water. Sulphur contents in sewage efuents in second, third and fourth sampling were about two- to three-folds higher than that of groundwater. On an average, sewage efuents contained 5.5, 3.6, 2.6, 6.4 and 1.3 times higher amounts of Zn, Cu, Fe, Mn and Ni, respectively compared to groundwater. There were no appreciable variations between these two sources of irrigation water in respect of Pb and Cd. The sewage efuents contain appreciable amounts of useful major plant nutrients, viz. P, K and S, which was also reected in the appreciable build-up of these nutrients in sewage-irrigated soils of this study area (Rattan et al., 2001). According to Pescod (1992), threshold values of heavy metals in irrigation water leading to crop damage are 2000 mg L1 for Zn, 200 mg L1 for Cu, 5000 mg L1 for Fe, 200 mg L1 for Mn, 200 mg L1 for Ni, 5000 mg L1 for Pb and 10 mg L1 for Cd. Although sewage efuents had elevated concentrations of some of the metals compared to groundwater, the concentrations of these metals in these two sources of irrigation water were within the permissible limits for their use as irrigation water. Some additional physico-chemical parameters were determined in sewage efuent samples. Results

indicate that sewage efuents were acidic in reaction with pH values ranging from 5.8 to 6.5 (data not shown). The tolerance limit of pH for irrigation water ranged from 6.0 to 9.0 (Patel et al., 1990). Thus, pH of all the efuent samples is within the permissible limit. Electrical conductivity of sewage efuents in all samples exceeded 1 dS m1 (1.362.88 dS m1) indicating that these efuents were saline in nature. The carbonate and bicarbonate contents in efuent samples varied from traces to 0.8 and 4.4 to 9.8 me L1, respectively. Carbonate concentrations in all the samples were much lower as compared to bicarbonate concentrations, which is also reected in acidic reaction of efuents. The values of residual sodium carbonate (RSC) varied from traces to 1.2, i.e. RSC in all the samples were below 1.25 me L1 (safe limit for irrigation water). These efuents can safely be used for irrigation purpose as far as RSC is concerned. 3.2. Soil texture Mechanical analysis of soil samples indicated that sand and silt contents ranged from 56 to 86 and 8 to 28%, respectively, while maximum 18% clay was recoded. Out of 30 samples analysed, 7 samples belong to loamy sand and 23 samples were classied as sandy loam. Thus, it is obvious that soils of this study area are coarse to moderately coarse in texture. 3.3. Effect of long-term use of sewage efuents 3.3.1. Soil pH and organic carbon Across the villages, soil pH varied from 5.1 to 9.9 and 6.2 to 9.1 in sewage and tubewell water-irrigated soils, respectively with the corresponding average values of 7.5 and 7.9 (data not shown). On an average, soil pH was dropped by 0.4 unit. The organic carbon content varied from 0.14 to 3.71% (average 0.65%) in sewage-irrigated soils, the corresponding values for tubewell water-irrigated soils were 0.140.76 (average 0.39%) (data not shown). Thus, organic carbon was increased by 59% as result of long-term sewage irrigation. These results concurred the ndings of Singh and Verloo (1996). After pH, soil organic carbon (SOC) is the most important indicator of soil quality and in addition to acting as a store-house of the plant nutrients, plays a major role in nutrient cycling. Besides, some estimates show that increase in the SOC

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content by 0.01% could lead to the carbon sequestration equal to the annual increase in the atmospheric CO2-C (Lal et al., 1998). Such a long-term application of the sewage efuents is a carbon-building/sequestering and soil quality sustaining practice. Farmers of the area have expressed that over a period of time, the soils, which were not productive (because of the problems of Kallarsodicity) had started giving improved yields. Such an observation could be explained on the basis of counteraction of alkalinity through sewage-induced acidication and improvement in soil organic carbon status. 3.3.2. Heavy metals in soils In Nilothi, Ranhola, Mundka and Bakarwala, there were substantial build-up of DTPA-extractable Zn, Cu, Fe, Pb and Ni in sewage-irrigated soils over tubewell water-irrigated ones (Table 2). Whereas, Mn contents in soils of Nilothi, Mundka, Bakarwala were declined by 44, 18 and 51%, respectively, as a result of sewage irrigation. In Hirankudna, on an average, sewage irrigation resulted in 113, 117, 29 and 81% increase Zn, Fe, Pb and Ni, respectively, however, Cu, Mn and Cd did not show any signicant change. Signicant effect of irrigation through sewage water was only observed in case of Fe, where 254% increase was recorded over the tubewell water-irrigated soils of Dichaonkalan. Cadmium content was not affected by sewage irrigation except in soils of Mundka. To assess the impact of duration under sewage irrigation, build-up of heavy metals in soils was computed separately for villages receiving irrigation for 20, 10 and 5 years (Fig. 2). In soils of Dichaokalan, which has been under sewage irrigation for 5 years, on average 254% build-up in Fe content was recorded and corresponding values for Hirankudna which has been receiving sewage irrigation for 10 years was 117%. Whereas, as a result of sewage irrigation for 20 years, Fe increased by 170% in soils of Nilothi, Ranhola, Mundka and Bakarwala. Zinc was not affected by sewage irrigation for 5 years, while 113 and 208% increases were observed in soils under sewage irrigation for 10 and 20 years, respectively. Signicant build-up in Cu was recorded under sewage irrigation of 20 years only, value being 170%. Sewage irrigation for 10 and 20 years increased the Ni contents in soils by 81 and 63%, respectively and corresponding values for Pb in both the cases was 29%. However, sewage

irrigation for 5 years could not change the available pool of both of these metals. Although 5 and 10 years of sewage irrigation could not change the Mn content in soil signicantly, on an average 31% decline was recorded in soil which has been receiving sewage irrigation for 20 years. In case of Nilothi and Dichaonkalan, average DTPA-extractable Fe content in the tubewell-irrigated soils is below the critical limit of deciency of 4.5 mg kg1 (as suggested by Lindsay and Norvell, 1978 and used extensively in India for delineating Fedecient soil), increased more than three to ve times in the sewage-irrigated soils. It leads one to logically conclude that the enhancement of crop productivity in the sewage-irrigated soils of this village could partly be due to alleviation of Fe-deciency syndrome. In other four villages, i.e. Mundka, Ranhola, Bakarwala and Hirankudna, there has been an enormous build-up in the available Fe content in the sewage-irrigated soils. Since Fe does not cause phytotoxicity in neutral to alkaline soils of this area, the build-up of available Fe is not likely to limit the use of sewage efuents for irrigation purpose. The sewage-irrigated soils are still maintaining higher levels of DTPA-Mn than the critical limit of Mn deciency of 2.0 mg kg1 (being used currently in this country for separating the Mndecient soils from the non-decient ones); however, this is a cause of concern and steps need to be undertaken to monitor Mn deciency and include Mn in the fertilization schedule. All the soils, both under tubewell and sewage irrigation are well supplied with Zn and Cu as their levels are generally higher than their critical levels of deciency of 0.6 and 0.20.5 mg kg1, respectively. In case of the sewage-irrigated soils, some of the soils have accumulated more than 10 mg kg1 DTPA-Zn, which has been listed as critical level of phytotoxicity (Rattan and Shukla, 1984). Accumulation of Zn and Cu in soils coupled with decrease in soil pH has a potential of aggravating the nutritional disorders associated with toxicity of these metals in the long run. 3.3.3. Fractionation In view of appreciable build-up in DTPAextractable Zn, Cu and Fe and depletion in Mn, distribution of these metals in different soil pools were studied and presented in Table 3. In tubewell water-irrigated soils, lower proportions of Zn were

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Table 2 Effect of long-term irrigation with sewage efuent on the DTPA-extractable heavy metal status of soil (mg kg1) Metals Sewage-irrigated Range Nilothi Zn Cu Fe Mn Cd Pb Ni Ranhola Zn Cu Fe Mn Cd Pb Ni Mundka Zn Cu Fe Mn Cd Pb Ni Bakarwala Zn Cu Fe Mn Cd Pb Ni Hirankudna Zn Cu Fe Mn Cd Pb Ni Dichaonkala Zn Cu Fe Mn Cd Pb Ni 2.5218.6 1.9411.9 8.4841.6 1.308.26 0.110.37 1.252.58 0.062.46 1.5636.9 2.2632.3 8.6576.8 1.5810.7 0.050.41 0.917.09 0.0083.98 0.5716.17 1.4117.03 9.96115.5 4.7314.7 0.020.46 1.123.79 0.051.83 1.018.9 1.539.7 10.2113 2.6918.4 0.040.85 0.507.92 0.159.76 0.819.18 0.494.94 1.8028.5 1.0923.3 0.010.90 0.761.46 0.010.67 1.1212.2 0.528.59 2.8642.9 1.0320.5 0.040.26 0.572.17 0.011.34 Mean 7.31** 4.91** 20.1** 3.29** 0.20 1.91** 1.19** 9.28** 7.04** 43.1** 4.19 0.15 2.37** 1.04** 3.68** 4.39** 50.2** 7.46** 0.11* 2.60** 0.58** 6.38** 6.53** 62.2** 8.43** 0.22 2.64** 1.29** 2.72* 1.71 11.3** 5.67 0.14 1.21** 0.29* 5.02 2.65 15.6** 6.92 0.14 1.11 0.36 S.D. 4.14 2.60 9.13 1.45 0.06 0.38 0.70 9.27 4.96 18.57 1.87 0.07 0.99 0.77 4.22 3.29 24.3 2.05 0.07 0.67 0.40 5.29 5.53 23.1 3.03 0.12 0.99 1.22 2.00 0.94 6.67 4.90 0.18 0.16 0.19 4.06 2.47 12.2 5.98 0.06 0.37 0.42 # (%) 638 416 554 44 46 284 189 162 214 25 131 247 181 341 18 38 44 123 186 158 144 51 19 14 113 117 29 81 254 Tubewell-irrigated Range 0.531.84 0.651.23 1.784.04 4.596.95 0.070.44 0.661.96 0.090.67 1.107.50 1.364.13 4.8534.2 1.524.79 0.080.24 1.532.37 0.160.86 0.691.49 1.232.19 9.2017.1 7.7610.1 0.050.11 1.472.29 0.070.39 0.757.73 1.184.28 7.2876.2 4.121.2 0.070.85 1.183.62 0.061.58 0.981.51 1.101.79 2.439.75 1.9113.1 0.010.23 0.661.10 0.010.35 2.3118.8 0.995.78 1.7818.6 1.0612.8 0.090.39 0.932.02 0.010.91 Mean 0.99 0.95 3.08 5.87 0.14 1.31 0.31 3.21 2.69 13.7 3.82 0.16 1.90 0.45 1.06 1.56 11.4 9.10 0.08 1.81 0.26 2.23 2.53 25.4 12.7 0.19 2.22 0.54 1.28 1.41 5.22 6.47 0.09 0.94 0.16 6.46 3.04 4.42 3.76 0.17 1.30 0.27 S.D. 0.34 0.18 0.63 0.99 0.10 0.44 0.20 2.01 1.16 9.08 1.05 0.04 0.24 0.17 0.26 0.36 2.99 0.92 0.02 0.44 0.12 1.04 0.57 16.1 4.3 0.11 0.48 0.29 0.20 0.18 2.58 3.08 0.06 0.12 0.13 4.74 1.67 3.98 2.98 0.08 0.30 0.23

#(%), increase or decrease over tubewell-irrigated soils; S.D., standard deviation; (*) and (**) indicate that differences between means of sewage and tubewell water-irrigated soils are signicant at 5 and 1% probability levels, respectively.

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Fig. 2. Effect of period of sewage irrigation on the build-up/depletion of DTPA-extractable metals (%) over tubewell water-irrigated soil.

recorded in all the fractions except residual compared to that of efuent-irrigated soils. Labile pool of Zn, i.e. adsorbed fractions [(water soluble + exchangeable) + Pb displaceable (specically adsorbed) + acid soluble] constituted higher share of total Zn (38.3%) in sewage-irrigated soils than that in tubewell water-irrigated ones (22.1%). Unlike Zn, share of adsorbed Cu was more 61.2% of total Cu for tubewell water-irrigated soils compared to efuentirrigated soils. However, immediately bioavailable pools, i.e. water soluble + exchangeable Cu (Mathur and Levesque, 1983) was much higher 23.8% in sewage-irrigated soils than that in tubewell waterirrigated ones (1.16%). Generally, less than 10% of total soil micronutrients are present in water soluble and exchangeable forms (Lake et al., 1984).

Relatively higher amount of Zn and Cu in bioavailable forms in our study may be attributed to reduction in soil pH as well as increase in organic carbon as a result of long-term use of sewage efuents which may be a cause of concern in future. Residual fraction of Fe constituted major share of total soil Fe in both the categories of soils, followed by crystalline Fe-oxide occluded and amorphous Feoxide occluded fractions. Contribution of remaining fractions to total soil Fe was meagre, ranging from 0.01 to 2.34%. Various researchers also reported that most of the Fe resides in the amorphous Fe-oxide, crystalline Fe-oxide occluded and residual fractions (Hoffman and Fletcher, 1978; Shuman, 1985). Nevertheless, build-up of Fe was relatively more in rst ve fractions in efuent irrigated soils indicating relatively more lability of Fe in sewage-irrigated soils compared to tubewell water-irrigated ones. More or less similar pattern of distribution of Mn in different fractions was observed in both the categories of soils, except water soluble + exchangeable and residual fractions. Sewage-irrigated soils exhibited comparatively higher share of water soluble + exchangeable Mn than that in tubewell water-irrigated ones, while trend was reverse for residual fractions. This may be attributed to the decrease in pH associated with increase in organic carbon as a result of long-term use of sewage efuents, which might have remobilized the Mn from structural pools to more labile fractions. This probably can explain the reason for depletion of Mn in these sewage-irrigated light textured soils due to leaching over the years. Takkar and Nayyar (1981) also

Table 3 Mean values of Zn, Cu, Fe and Mn fractions in sewage and tubewell water-irrigated soils Fractions Zn Sewage Water soluble + exchangeable Pb-displaceable Acid soluble Mn-occluded Organically bound Amorphous Fe-oxide occluded Crystalline Fe-oxide occluded Residual 2.91 (3.8) 16.9 (22.2) 9.32 (12.3) 2.64 (3.47) 22.6 (29.7) 6.84 (8.99) Tubewell 1.77 (3.4) Cu Sewage 9.69 (23.8) Tubewell 0.30 (1.16) Fe Sewage 7.27 (0.07) Tubewell 1.8 (0.01) Mn Sewage 44.9 (12.1) Tubewell 2.55 (0.77)

5.92 (11.3) 7.34 3.88 (7.4) 6.12 0.46 (0.88) ND 19.1 (36.6) 1.72 4.68 (9.0) 3.96

(18.04) 11.7 (45.3) (15.04) 3.81 (14.7) ND (4.22) 0.35 (1.33) (9.73) 0.73 (2.82)

5.48 (0.06) 4.33 (0.04) 42.1 (11.3) 43.2 (13.1) 27.4 (0.30) 18.9 (0.18) 47.8 (12.8) 40.7 (12.3) 33.4 (0.37) 23.6 (0.23) 31.5 (8.46) 26.4 (8.0) 215 (2.34) 128 (1.26) 8.87 (2.38) 6.04 (1.83) 566 (6.16) 396 (3.9) 5.78 (1.55) 5.82 (1.76) 1071 (10.6) 8492 (83.8) 18.3 (4.91) 173 (46.5) 17.5 (5.31) 187 (56.9)

8.20 (10.7) 4.74 (9.1) 6.63 (8.7) 11.5 (22.0)

0.94 (2.31) 10.9 (26.8)

0.053 (0.20) 1000 (10.9) 8.90 (34.4) 7304 (79.7)

Figures in parenthesis indicate percentage of total metal content in soils; ND: not detectable in ame AAS.

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Table 4 Heavy metal contents in crops grown on sewage efuents and tubewell water-irrigated soils Crops Metal contents (mg kg1) Zn S Rice (Oryza sativa L.) Grain Straw Wheat (Triticum aestivum L.) Sorghum (Sorghum vulgare Pers.) Maize (Zea mays L.) Oats (Avena sativa L.) Gobhi sarson (Brassica napus) Spinach (Spinacea oleraceae L.) Indian rape (Brassica campestris var. toria Dutch) Cauliower (Brassica oleracea L.) Cucumber (Cucumis sativus L.) Radish (Raphanus sativus L.) Leaf Root Egyptian clover (Trifolium alexandrinum L.) 49.6 58.9 65.3 54.2 78.8 59.0 66.9 77.1 52.5 (27) (27) (88) (38) (15) (7) (17) (17) (10) T 29.6 61.9 47.5 73.4 67.6 44.3 38.7 38.4 (4) (4) (27) (9) (1) (2) (3) (2) Cu S 51.6 57.2 9.39 16.9 14.9 8.71 23.1 20.6 5.42 10.8 19.3 14.6 10.4 18.3 T 23.0 59.8 7.45 115.5 13.3 6.35 14.1 16.1 Fe S 122 233 404 526 531 458 454 711 475 328 932 358 166 623 T 186 202 336 485 99.0 400 401 734 Mn S 53.3 208 15.3 40.6 26.0 23.8 69.0 39.3 42.6 31.8 19.9 41.9 16.7 20.7 T 88.1 229 13.6 44.8 15.3 29.2 104 87.8 Ni S 10.1 10.4 20.0 14.8 16.5 18.3 12.0 18.4 8.78 14.4 21.5 9.26 11.5 20.6 T 9.85 5.27 19.7 11.6 5.20 37.3 3.73 13.2

46.7 (11) 79.4 (5) 60.8 (7) 58.9 (7) 91.9 (15)

Figures in parenthesis indicate number of samples analysed; S: sewage-irrigated; T: tubewell water-irrigated.

reported Mn deciency in some light textured soils of Punjab because of the leaching losses of Mn from the surface soil layer. 3.3.4. Metal contents in plants Mean contents of metals in the dry matter of various crops grown on sewage efuent and tubewell water-irrigated soils are summarized in Table 4. Rice grain accumulated much higher amount of Zn and Cu grown on sewage-irrigated soils compared to tubewell water-irrigated soils, while slight increase in Ni content was recorded. Manganese content in rice grain for sewage-irrigated soils was much lower than that for tubewell water-irrigated soils. In general, this trend is in concurrence with the levels DTPA-extractable Mn in both categories of soils. Although sewage efuent-irrigated soils exhibited much higher amount of DTPA-Fe, it was not reected in Fe content of rice grain. From this study, it is difcult to elucidate the reasons for this anomaly. Iron content in rice straw to some extent reected the variations in DTPA-Fe between sewage and tubewell water-irrigated soils. Rice straw accumulated almost two times more Ni produced with sewage water over that of tubewell water irrigation. However, Zn and Cu contents in the

rice straw produced on the sewage-irrigated soils appeared to be rather marginally lower than its background level. Wheat had elevated contents of Zn, Cu, Fe, Mn and Ni grown on sewage-irrigated soils compared to that produced with tubewell irrigation. Sorghum accumulated higher amount of Fe, Cu and Ni on sewage efuent irrigated soils, while Zn and Mn contents were lower than its background level. Maize showed higher accumulation of all the elements on sewage efuent irrigated soils. Similar trends were observed in gobhi sarson and oats with only exception of Mn, where plant contents of Mn conformed to the DTPA-Mn in both the categories of soils. Spinach grown on sewage-irrigated soils accumulated higher amount of Zn, Cu and Ni than those grown on tubewell water-irrigated soils, whereas reverse were the trends for Fe and Mn. Comparison of metal contents in Indian rape, cauliower, cucumber, Egyptian clover and radish for both of these soils could not be made as these crops were not grown with tubewell irrigation in this study area at the time of sampling. Cadmium and lead contents in tissue of all the crops under study, were below the analytical detection limits, hence no data were reported. Similar were the observations of Datta et al. (2000) and Yadav et al. (2002) for some

R.K. Rattan et al. / Agriculture, Ecosystems and Environment 109 (2005) 310322 Table 5 Simple correlation coefcients (r) between DTPA-extractable metals and metal contents in crops Crops Metal contents in crops Zn Rice (Oryza sativa L.) Grain Straw Wheat (Triticum aestivum L.) Sorghum (Sorghum vulgare Pers.) Gobhi sarson (Brassica napus) Spinach (Spinacea oleraceae L.) Indian rape (Brassica campestris var. toria Dutch) Cauliower (Brassica oleracea L.) Egyptian clover (Trifolium alexandrinum L.) 0.58** 0.58** 0.35** 0.25 0.45* 0.51* 0.86** 0.72* 0.57* Cu 0.05 0.06 0.43** 0.38** 0.12 0.43 0.21 0.67* 0.28 Fe 0.04 0.25 0.14 0.25 0.26 0.03 0.25 0.41 0.01 Mn 0.38** 0.02 0.04 0.04 0.27 0.09 0.35 0.34 0.027 Ni

319

0.20 0.15 0.12 0.28* 0.38 0.03 0.61** 0.66* 0.03

(*) and (**) signicant at 5 and 1% probability levels, respectively.

sewage-irrigated soils of India. By and large, concentrations of metals in all the crops grown on sewage efuent-irrigated soils were below the generalized critical levels of phytotoxicity (as summarized by Datta et al., 2000) except Fe. Although no toxicity symptoms were noticed, Fe contents in sorghum, maize, spinach, cucumber and Egyptian clover exceeded the phytotoxicity limit (> 500 mg kg1; on dry weight basis). Crop species exercised differentiality in accumulating metals in their tissues. Similar were the observations of Lepp (1981), Sauerback (1991), Smith (1994), Hooda et al. (1997), Datta et al. (2000) and Yadav et al. (2002). Since DTPA is the most commonly used soil test for assessing bioavailability of metals in contaminated soils (Hooda et al., 1997; Datta et al., 2000; Yadav et al., 2002; Patel et al., 2004), simple correlation coefcients were worked out between plant metal concentrations and DTPA-extractable metals in soil. Results indicate that DTPA-Zn had most consistent positive relationships with tissue metal concentrations of all the crops as listed in Table 5, except sorghum. DTPA-extractable Cu positively contributed to the tissue concentration of Cu in case of wheat, sorghum and cucumber. DTPA-extractable Fe contents were not related to the Fe contents in any of the crops. Manganese contents in plants did not exhibit any relationship with soil Mn, except rice grain. Nickel contents in sorghum, Indian rape and cauliower were positively related with DTPA-Ni in soils. Failure of DTPA extractant in some cases in the present study may be attributed lesser number of observations and variations in the management practices among the

farmers of the study area. Even under controlled conditions, ability of extractants to predict plant available metals depends on the crop species, the metal and extractant used (Hooda et al., 1997). In several studies, it is established that solubility of metals in soils mainly depends on soil pH and organic carbon (Ma and Lindsay, 1993; Jopony and Young, 1994; Hough et al., 2003; Tye et al., 2003). Hence, in the present investigation, effect of these two important soil properties on the lability of metals was studied (Table 6). Results show that soil pH had negative inuence on the extractability of metals from soils by DTPA. While increase in soil organic carbon content enhanced the DTPA-extractable metals, except Mn. However, inclusion of pH and organic carbon in multiple regression equation along with DTPAextractable metals as predictor variables to predict plant metal concentrations, could not improve the values of prediction coefcients except spinach (data not shown). It appears that available metal content in soils is the principal factor predicting its concentration
Table 6 Simple correlation coefcients of DTPA-extractable metals with soil pH and organic carbon Metals Zn Cu Fe Mn Ni Pb Cd pH 0.37 0.37** 0.50** 0.31** 0.46** 0.09** 0.29**
**

Organic carbon 0.55** 0.71** 0.54** 0.02 0.73** 0.32** 0.42**

(**) signicant at 1% probability level.

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Table 7 Transfer factor (TF) for crops grown on sewage efuents and tubewell water-irrigated soils Crops Transfer factor of metals Zn S Rice (Oryza sativa L.) Grain Straw Wheat (Triticum aestivum L.) Sorghum (Sorghum vulgare Pers.) Maize (Zea mays L.) Oats (Avena sativa L.) Gobhi sarson (Brassica napus) Spinach (Spinacea oleraceae L.) Indian rape (Brassica campestris var. toria Dutch) Cauliower (Brassica oleracea L.) Cucumber (Cucumis sativus L.) Radish (Raphanus sativus L.) Leaf Root Egyptian clover (Trifolium alexandrinum L.) 16.5 20.8 18.3 23.7 14.4 15.5 16.1 24.6 19.1 7.25 13.1 9.55 15.0 25.1 T 21.2 47.5 22.6 33.4 32.0 29.6 43.5 27.7 55.6 Cu S 12.9 15.2 2.35 8.48 2.81 1.69 5.57 6.18 5.42 1.91 3.16 3.05 2.32 4.71 T 7.46 21.9 16.7 6.80 8.59 2.48 14.3 16.1 18.1 Fe S 2.30 4.46 7.91 57.8 11.8 7.17 25.6 26.0 15.8 14.7 22.5 22.4 6.00 11.8 T 4.43 5.92 16.2 104 19.6 15.3 123 255 200 Mn S 8.69 31.5 1.93 10.9 3.58 2.65 21.2 9.07 15.6 8.59 3.98 13.7 4.77 2.60 T 10.9 26.8 1.27 16.3 3.85 1.90 23.2 15.3 20.2 Ni S 15.9 23.1 24.3 145 18.9 15.2 16.0 32.3 22.1 15.6 37.3 9.00 19.7 22.5 T 20.2 12.1 47.8 457 11.4 37.3 31.7 52.2 94.3

S: sewage-irrigated; T: tubewell water-irrigated.

in plants. Regression analysis according to Snedecor and Cochran (1967) revealed that DTPA-Zn, soil pH and organic carbon could explain the variability in Zn content in spinach to the extent of 79% [Zn content in spinach (mg kg1) = 241 + 2.11 (DTPA-Zn mg kg1) 25.9 (pH) + 54.7 (organic carbon %); R2 = 0.79; signicant at 1% probability level]. Transfer factors (TF), i.e. the ratio of metal concentration in plants to DTPA-extractable metal in soil, varied considerably among the crops (Table 7). In case of Zn and Fe, TFs for all the crops grown on sewage efuent-irrigated soils were lower than that for crops produced with tubewell water irrigation. However, for other metals, such consistent variations in TFs were not obtained. This indicates that uptake of metals by crops does not increase linearly with increasing concentrations of metals in soils. This is in concurrence with the ndings of Hooda et al. (1997). The apparent advantage of this phenomenon is that although long-term sewage irrigation resulted into elevated concentration of metal in soil, the same would not be proportionately transferred to food chain. Taking all the crops together, relative orders of transfer of metals from soil to plants grown on sewageirrigated soils were Ni > Zn > Fe > Mn > Cu. These

results show that as far as entry of these metals to food chain plants is concerned, Ni has the greatest potential, followed by Zn, Fe, Mn and Cu. Based on the TFs, relative efciency of crops to absorb metals from sewage-irrigated soil could be arranged in the following order: Zinc: Egyptian clover > spinach > sorghum > rice leaf > Indian rape > wheat > rice grain > gobhi sarson > oats > radish root > maize > cucumber > radradish leaf. Copper: Rice leaf > rice grain > sorghum > spispinach > gobhi sarson > Indian rape > Egyptian clover > cucumber > radish leaf > maize > wheat > radish root > cauliower > oats. Iron: Sorghum > spinach > gobhi sarson > cucumber > radish leaf > Indian rape > cauliower > maize > Egyptian clover > wheat > oat > radish root > rice leaf > rice grain. Manganese: Rice leaf > gobhi sarson > Indian rape > radish leaf > sorghum > spinach > rice grain > cauliower > radish root > cucumber > maize > oats > Egyptian clover > wheat. Nickel: Sorghum > cucumber > spinach > wheat > rice leaf > Egyptian clover > Indian rape > radish

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321

root > maize > gobhi sarson > rice grain > cauliower > oats > radish leaf. This information will be very useful in selecting the suitable crops to be grown on metal-contaminated soils. 3.4. Risk assessment In this study area, spinach, gobhi sarson and Indian rape are produced and marketed as leafy green vegetables. Also there was a substantial build-up of Zn, Cu and Ni sewage-irrigated soils. Hence, hazard quotients (HQgv), i.e. the ratio of average daily dose to the reference dose (Pierzynski et al., 2000) for intake of metals by human through the consumption of these leafy green vegetables were worked out. The values of HQgv for gobhi sarson varied from 0.040 to 0.068 for Zn, 0.004 to 0.021 for Cu and 0.027 to 0.442 for Ni (data not shown). In case of spinach, HQgv varied from 0.035 to 0.152, 0.008 to 0.015 and 0.046 to 0.502 for Zn, Cu and Ni, respectively. The values of HQgv for Indian rape ranged from 0.027 to 0.053, 0.004 to 0.014 and 0.016 to 0.429 for Zn, Cu and Ni, respectively. Although, Ni exhibited relatively higher HQ for all the crops compared to other two metals, most of the values were far less than 1. Hence, these green vegetables are not likely to induce any health hazard to consumers (human) as far as its metal contents are concerned.

vegetables grown on these sewage-irrigated soils are still safe to be consumed by human beings.

Acknowledgement Authors would like to place on record their sincere thanks to Indian Council of Agricultural Research, New Delhi, India for funding this study as a part of AP Cess Fund project.

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