Food and Chemical Toxicology 46 (2008) 28562864

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Food and Chemical Toxicology

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Impact of sedimentary arsenic through irrigated groundwater on soil, plant, crops and human continuum from Bengal delta: Special reference to raw and cooked rice
Tarit Roychowdhury *
Geo-Environment Management Division, National Environmental Engineering Research Institute, Nehru Marg, Nagpur 440 020, Maharasthra, India

a r t i c l e

i n f o

a b s t r a c t
Existence of arsenic-rich (exceeds 2000 mg/kg) iron pyrite in Bengal delta sediments is responsible for arsenic release in aquifer. Ingestion of contaminated drinking water is not the only elevated source of arsenic to the diet. Irrigation of agricultural elds with arsenic-contaminated groundwater has led to arsenic build-up in soil, with subsequent elevation of arsenic in crops grown on these soils. About 50.7 and 11.2 kg of arsenic are withdrawn per year from 23 and 18 shallow tubewells, used for agricultural irrigation in the studied two districts Murshidabad and Nadia, respectively and deposited on lands throughout the year. Considerable higher amounts of arsenic are accumulated in paddy plants. Mean arsenic concentration in food categories is 107 lg/kg. Arsenic concentrations are high in cooked food and skin of the vegetables. Arsenic concentration in cooked rice increases with water arsenic concentration. About 70.2% of arsenic is recovered by using the analytical speciation extraction method. Inorganic arsenic and DMA contribute 89.5% and 10.5% of the total content of arsenic in food, respectively. About 0.081% and 1.57% of arsenic are accumulated in rice grain from arsenic-deposited lands and contaminated soils. The daily dietary intake of inorganic arsenic (lg/kg body wt./day) by an adult from rice grain itself (2.32) is higher than the WHO recommended PTDI value of inorganic arsenic (2.1) and inorganic arsenic contributes 96.8% of the total dietary intakes of arsenic. Population exposed to arsenic toxicity has been identied. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 11 January 2008 Accepted 20 May 2008

Keywords: Arsenic-rich sediment Agricultural irrigation Soil, plant and crops Total arsenic and its species Raw and cooked rice Human exposures from arsenic toxicity

1. Introduction Natural groundwater arsenic-contamination, and the sufferings of people as a result, has become a crucial water quality problem in many parts of the world, particularly in Bengal delta, Bangladesh and West Bengal, India (Chowdhury et al., 2000; Smith et al., 2000; Chakraborti et al., 2002). A large part of the Ganga-Meghna-Brahmaputra plain (GMB) with an area 569,749 km2 and population over 500 million is at risk (Chakraborti et al., 2004). The situation is at its worst in the Bengal delta, with over 100 million people living in zones with arsenic above 0.05 mg/L (Chowdhury et al., 2000; Chakraborti et al., 2002). Fifty districts in Bangladesh (out of a total of 64 districts) and nine districts in West Bengal (out of a total of 18 districts) including 85 blocks (police stations) and approximately 3500 villages have been identied where groundwater contains arsenic above 0.05 mg/L (Chakraborti et al., 2002; Rahman et al., 2005). The source of arsenic in groundwater is geologic (Roychowdhury et al., 1999; Nickson et al., 2000; Chakraborti et al., 2001).

* Tel./fax: +91 712 2249756. E-mail address: t_roychowdhury@neeri.res.in 0278-6915/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.fct.2008.05.019

The relationships between the amount of arsenic in soil, plant growth and arsenic toxicity have been investigated (Walsh et al., 1977). Arsenic is a naturally occurring element and levels of arsenic in foods generally reect normal accumulation from the environment. It is becoming apparent that ingestion of drinking water is not the only elevated source of arsenic to the diet in Bengal delta. Irrigation of agricultural elds with arsenic-contaminated groundwater has led to arsenic build-up in soil (Roychowdhury et al., 2002a, 2005; Meharg and Rahman, 2003), with subsequent elevation of arsenic in crops grown on these soils (Roychowdhury et al., 2002b, 2003; Alam et al., 2003). The arsenic species reported in groundwater from Bengal delta is inorganic (Chatterjee et al., 1995; Rasul et al., 2002; Tokunaga et al., 2005). Inorganic arsenic contributed more than 90% of the total content of arsenic in crops, grown on arsenic-contaminated soil (Chowdhury et al., 2001). Knowledge of the level of human exposure to arsenic is considered an integral part of the health protection programs in Canada and the world community (Joint FAO/WHO, 1989). The toxicity and bioavailability of arsenic depend on its chemical form (Cullen and Reimer, 1989; National Research Council, 1999). Inorganic arsenic species are believed to be more toxic than methylated species (Cullen and Reimer, 1989) and have been established as human

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2857

carcinogens (USEPA, 1988; National Research Council, 1999). Intake of 1.0 mg of inorganic arsenic per day may give rise to skin lesions within a few years (WHO, 1981). The Food and Agriculture Organization/World Health Organization provisional tolerable daily intake (PTDI) value of inorganic arsenic is 2.1 lg/kg body wt./day (Joint FAO/WHO, 1989). Ingestion of excessive inorganic arsenic may cause cancer of skin, urinary bladder, kidney, lung, and liver as well as with disorders of the circulatory and nervous system (USEPA, 1988; Bates et al., 1992; Chen et al., 1992; National Research Council, 1999). The present study is centered on several arsenic-affected areas of Murshidabad and Nadia districts in West Bengal. Murshidabad and Nadia are two, out of the nine arsenic-affected districts in West Bengal, where groundwater contains arsenic above 0.05 mg/L (Chowdhury et al., 2000; Chakraborti et al., 2002). Both the districts form a part of the deltaic alluvial plain of the modern Ganga-Brahmaputra delta and are underlain by uvial sediments of Quaternary age. The studied areas are two adjacent districts in West Bengal and located in the Bangladesh border. The geo-environmental distribution (groundwater, sediment, soil, agricultural land), agricultural system (irrigated groundwater, shallow, large-diameter tubewells, nature of agricultural plants and crops) and the socio-economic condition of the villagers of the two districts are similar. Besides domestic use, groundwater is widely used for irrigation during dry season (DecemberApril), particularly for growing of the dry season rice called boro which requires about 1 m of irrigation water each year (Hossain et al., 2003). To meet the food demands of the increasing population in Bengal delta, the growing season has been expanded from one to four or ve crops per year. Rainwater alone can no longer meet the water demand of such intensive agriculture, since only limited rainfall occurs during the dry season. Therefore, agriculture has shifted to using groundwater to supplement the rainwater supplies. Approximately, tens of thousands of shallow large-diameter tubewells are used for agricultural irrigation in West Bengal (Mandal et al., 1996). A total of 925,152 shallow and 24,718 deep tubewells were used for irrigation during the 2004 dry season in Bangladesh (BADC, 2005) and groundwater irrigation covered about 75% of the total irrigated area. Boro cultivation and irrigation have together increased since 1970, and from 1980 until present, the area under groundwater irrigation has increased by almost an order of magnitude (Harvey et al., 2005). During 2003 dry season, about 87% of the total irrigated area of about 4 million hectare (about 28% of the total area in Bangladesh) was under boro cultivation and boro accounted for about 49% of the total rice production (MoA, 2004). Many millions of cubic meters of underground water are used for agricultural irrigation. Much of this groundwater is contaminated with arsenic, which is deposited in the soil in contact with the irrigation water throughout the year (Mandal et al., 1996). Except in the rainy season (JuneOctober), the agricultural land soils have been exposed to irrigated groundwater round the year. Sometimes, the farmers used to run the shallow tubewells in the rainy season due to insufcient rain. As a result, groundwater exploitation goes on unchecked. The status of aquifer exploitation was as high as 79.4% from a single district, North 24Parganas in West Bengal (Directorate of Agricultural Engineering, 1991). The heavy withdrawal of groundwater may be the reason why iron pyrite decomposes and releases arsenic in groundwater (Roychowdhury et al., 1999; Chakraborti et al., 2001). A single Rural Water Supply Scheme (RWSS) in Maldah district (another arsenicaffected district in West Bengal) was alone withdrawing 147 kg of arsenic from groundwater in a year (Mandal et al., 1996). About 6.4 tons of arsenic was withdrawing in a year from the shallow large-diameter tubewells in use for agricultural irrigation in Deganga block, North 24-Parganas district (Chakraborti et al., 2001). Due to its afnity for metal oxides/hydroxides in soil, the accumulation of arsenic in irrigated surface soils is expected and a

number of studies (Alam and Sattar, 2000; Roychowdhury et al., 2002a, 2005; Meharg and Rahman, 2003; Saha and Ali, 2007) have reported elevated concentrations of arsenic in agricultural eld soils irrigated with arsenic-contaminated groundwater. Crops grown on these soils are expected a major unrecognized route for arsenic exposure (Roychowdhury et al., 2002b, 2003; Alam et al., 2003). The main objective of this study is to clarify the arsenic-bearing sediments in the studied areas, and to locate the magnitude of soil contamination by arsenic, follows by the plant and food contamination, due to the huge withdrawal of irrigated groundwater in these areas. Further investigations are carried on total and speciated arsenic present in food composites, contribution of water arsenic concentration in cooked rice and the accumulation of arsenic in rice grain (which is the staple food in the studied areas), from arsenic-contaminated irrigated water and soil, and nally, the human exposure from arsenic toxicity in the studied areas.

2. Materials and methods 2.1. Sample collection and preparation Borehole sediment, groundwater (both drinking water and irrigated water), soil, plant and food samples were collected from several arsenic-affected blocks of Murshidabad district (Jalangi, Domkal, Hariharpara and Raninagar II blocks) and Nadia district (Tehatta I, Tehatta II and Karimpur II blocks) in West Bengal. The sediment samples were collected during 19932000 and all the other samples were collected during 20032005. Sediment samples were collected during drilling of wells. The collection, preservation, processing, digestion and instrumental analysis of the sediments were described elsewhere (Roychowdhury, 1999; Chakraborti et al., 2001). The sediment samples were divided into three parts:  Parent sample (P); the samples were collected at every 3.03 m or 6.06 m interval, up to a depth of 250 m.  Homogenized sample (H); parent sample was powdered using mortar and pestle.  Selected particle (S); these particles were opaque, soft or hard, reddish/brown/ grayish in nature and were picked from the parent sample with naked eye or pocket lens. Water samples were collected from the hand tubewells, used for drinking, cooking and other household purposes by the villagers and shallow large-diameter tubewells, used for agricultural irrigation. The collection and preservation of water samples were described elsewhere (Chatterjee et al., 1993; Roychowdhury et al., 2002a, 2003). Agricultural land soils were collected from the (i) upper surface of the land (ii) root after pick off of the plants, and (iii) below ground level (up to a maximum depth of 50 cm and at every 5 cm interval from the upper surface). The plants cultivated in several plots of the agricultural land during eld survey, were paddy, cabbage, cauliower, gram, garlic, radish, lentil, wheat, mustard, egg plant, onion, potato, coriander, tomato, spinach, peas, beans etc. The shallow large-diameter tubewells (710 cm in diameter), used for agricultural irrigation (ran 7 h a day and 7 months per year) had a discharge rate of about 20 m3/h. The tubewells ran with the help of an electric/diesel pump (average 5 HP). Other than the irrigation water, the soils had been exposed to rainwater, especially in the rainy season or sometimes had been exposed to ooded river or pond water during the heavy rain in the rainy season. The plants collected in this survey were 3035 days old. The collection, preservation, and processing of agricultural land soils and plants were described elsewhere (Queirolo et al., 2000; Roychowdhury et al., 2002a, 2005). Rice plants with full-grown paddy were studied before harvesting and related information was collected from the local farmers. Tubewell waters and food samples were collected from 49 families in the surveyed areas. The food samples were divided into three main categories:  Vegetables (potato, onion, garlic, chili, arum, beans, spinach, radish, egg plant, bitter gourd, leaf of vegetables, etc.).  Cereals (rice grain, wheat, wheat our, lentil, other pulses).  Spices (cumin, turmeric powder, coriander, chili powder, aniseed, mustard, etc.). Cooked food samples like cooked rice, potato curry, fried potato, mixed vegetables curry and cooked edible herbs were also collected. The collection and preservation of the food samples were described elsewhere (Roychowdhury et al., 2002b, 2003). Only the raw vegetables (contained approximately 80% moisture)

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T. Roychowdhury / Food and Chemical Toxicology 46 (2008) 28562864

and cereals (such as rice grain, wheat grain and pulse grain; contained approximately 5% moisture) were washed with deionized water in an ultrasonic cleaner (50/60 Hz, Model No. B-220, Branson, USA) (Queirolo et al., 2000; Roychowdhury et al., 2002b). The food samples were dried in open air under diffused sunlight until complete dryness. The samples were manually ground to a ne powder of less than 30 mesh particle size using a mortar.

3. Results and discussions The observed values of arsenic in standard reference materials (SRMs) are for rice our (1568a): 0.28 0.05 mg/kg (certied value 0.29 0.03 mg/kg), wheat our (1567a): 0.006 mg/kg (certied value 0.006 0.001 mg/kg), apple leaves (SRM 1515): 0.032 0.004 mg/kg (certied value 0.038 0.007 mg/kg), tomato leaves (1573a): 0.098 0.007 mg/kg (certied value 0.112 0.004 mg/ kg), San Joaquin soil (2709): 17.3 0.9 mg/kg (certied value 17.7 0.8 mg/kg) and River sediment: 60 4 mg/kg (certied value 66 mg/kg), respectively. The observed values are in good agreement with the certied values. 3.1. Arsenic in sediments Twenty-nine arsenic-bearing sediments (above 10 mg/kg in homogenized form of parent sediment) including three arsenicrich selected particles in parent sediments from nine boreholes in the studied areas are shown in Table 1. The arsenic-rich particles (mean: 2382 mg/kg) are also iron-rich (mean: 26.8%) and there is existence of sulfur isotope. Arsenic concentration in the parent sediment or its homogenized form may differ, but the selected opaque particles always contain an elevated level of arsenic. Arsenic concentration in sediment is not also depth dependent. Higher concentration may be found at any depth and mainly in coarse grain sand. Identical value of the As/Fe ratios (mean: 0.0089, range: 0.00820.0100) has been observed in the arsenic-rich selected particles. Petrologic and chemical studies of these arsenic-rich selected particles identied the presence of iron pyrite (FeS2) with arsenic (Roychowdhury et al., 1999; Chakraborti et al., 2001). The existence of arsenic-rich pyrite in the Bengal basin sediments was reported from other study also (Nickson et al., 2000). Both pyrite-oxidation (Roychowdhury et al., 1999; Chakraborti et al., 2001) and iron oxyhydroxide-reduction (Nickson et al., 2000) hypotheses are mainly responsible to groundwater contaminated by arsenic in Bengal delta. 3.2. Soil and plant contamination About 50.7 kg and 11.2 kg of arsenic are withdrawn per year from 23 and 18 shallow tubewells and deposited on the agricultural and paddy lands having an area of 6.67 ha and 6.30 ha, in Murshidabad and Nadia district, respectively (Table 2). Thus, the soils and plants are contaminated. Addition of arsenic compounds to soils might be toxic to plants directly or may accumulate in plants and enter the animal and human food chain (National Research Council, 1999). Mean arsenic concentrations in all kind of soils and plants (root, stem and leaf) from the agricultural and paddy lands are 14 mg/kg (range: 3.3431.6 mg/kg), 12.1 mg/kg (range: 4.5995.3 mg/kg), and 0.51 mg/kg (range: <0.042.9 mg/ kg), 102 mg/kg (range: 1.681238 mg/kg), respectively (Table 3). In this study, the mean arsenic concentrations in agricultural land soils are higher than the mean arsenic concentration in fallow land soils (mean: 5.31 mg/kg, range: 2.686.79 mg/kg), studied earlier from Murshidabad district (Roychowdhury et al., 2002a). It has been observed that the higher the arsenic in irrigated groundwater, the higher the arsenic in agricultural land soil and different parts of plants. Soil and plant arsenic levels were correlated with local well water concentrations, suggested that those had become contaminated through irrigation with arsenic-contaminated water in West Bengal and Bangladesh (Alam et al., 2003; Meharg and Rahman, 2003; Roychowdhury et al., 2005). High concentration of arsenic was reported in branch (2.814.3 mg/kg), leaf (2.19.5 mg/kg), trunk (0.355 mg/kg) and root (45130 mg/kg) of the plants, grown up in arsenic-contaminated soil (Jenkins, 1980). The higher

2.2. Chemicals and reagents All reagents were of analytical grade. MilliQ water was used throughout. Sodium arsenite and sodium arsenate were purchased from Wako Pure Chemical Industries (Osaka, Japan). Monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) were purchased from Tri Chemical Laboratory (Yamanashi, Japan). Other chemicals were also from Wako Pure Chemical Industries (Osaka, Japan). Sample digestions were carried out with concentrated nitric acid and high-purity hydrogen peroxide (3035.5%). Stock standard solutions of arsenic species, each of 1000 mg/L, were obtained by weighing accurate amounts, followed by dissolving in MilliQ water. These stock standard solutions were kept in a refrigerator at 4 C until required. Mixed standard solutions, containing 30 lg/L and 150 lg/L of each arsenic species were prepared daily from the stock standard solutions, by appropriate dilution. San Joaquin soil (SRM 2709) from the National Institute of Standards and Technology (Gaithersburg, MD 20899, USA), River sediment (SRM 1645) from the National Bureau of Standards (Washington, DC 20234), Rice our (SRM 1568a) and wheat our (SRM 1567a) from the National Bureau of Standards (Gaithersburg, MD, USA), Apple leaves (SRM 1515) and tomato leaves (SRM 1573a) from the National Institute of Standards and Technology (Gaithersburg, MD, USA) were used as Standard Reference Materials (SRMs). Details of the reagents and standard reference materials were described elsewhere (Roychowdhury et al., 2002a,b; Tokunaga et al., 2002).

2.3. Digestion A microwave digestion system (MARS 5) from CEM Corporation, Matthews, North Carolina 28106, USA with a rotor for 14 Teon digestion vessels HP-500, was used for sample (soil, plant and foodstuff) digestion. Details of the digestion procedures and microwave condition for digestion were described elsewhere (Roychowdhury et al., 2002a,b). To check whether the analytical results of the samples agree with standard reference materials, the SRM samples were analyzed after utilizing the same digestion and analytical procedures as that of samples. 2.4. Analytical procedure for extraction of arsenic species in food sample About 0.51.0 g of the dry, nely powdered sample was taken in a 10 mL centrifuge tube. Five mL of methanol/water mixture (1:1, v/v) was added. The tube was then sonicated for 10 min and centrifuged for 5 min at 3000 rpm (g force was about 2500). The supernatant liquid was collected in a 25 mL volumetric ask. The extraction procedure was repeated twice and the extracts were combined. The extracted solution was then rotoevaporated to dryness at 35 C and taken up by addition of 10 mL MilliQ water. It was ltered through a millipore membrane (0.45 lm) and stored in a freezer until analysis. 2.5. Analysis An inductively coupled plasma mass spectrophotometer (Hewlett-Packard 4500) was used as a chromatographic detector for total arsenic analysis. The ICPMS system was equipped with a Shimadzu LC-10ADVP liquid chromatograph solvent delivery pump, Shimadzu DGU-12A degasser, and double-pass, scott-type spray chamber (water cooled, 2 C, ORION, RKS-1500V-C). The instrumental conditions for ICP-MS system were described elsewhere (Roychowdhury et al., 2002b). The detection limit of arsenic in the system was 0.04 lg/L. Off-line data from the ICP-MS were processed with special chromatographic software (HP ChemStation). Arsenic speciation was carried out using HPLC coupled with ICP-MS system (Agilent 7500, DE, USA). The instrumental conditions were described elsewhere (Tokunaga et al., 2002). The HPLC system consisted of a Shimadzu 10AC liquid chromatograph solvent delivery pump, STM-10A system controller, Shimadzu SIL-10A auto sampler and Shimadzu CTO-10AC column oven. The analytical column was a Gel PAK GL-ICA15 (4.6 mm i.d. 150 mm) packed with anion-exchange resin (Hitachi Kasei Co. Ltd., Tokyo, Japan). HPLC was performed under the following conditions: mobile phase, 10 mmol/L phosphate buffer (pH 6.0), ow rate 1 mL/min, column temperature 35 C and injection volume 20 lL. The outlet from the separation column was connected directly to the nebulizer of the ICP-MS using a polyethylene tube of 0.3 mm i.d. After injection of 20 lL of liquid sample into the HPLC column, the peak areas of the arsenic species were measured by ICP-MS for 8 min. The amounts of arsenic species were calculated using working curves prepared by 0, 30, and 150 lg/L solutions of mixed arsenic species. The detection limit of mixture of arsenic species in the system was 0.2 lg/L.

T. Roychowdhury / Food and Chemical Toxicology 46 (2008) 28562864 Table 1 Concentration of arsenic, iron and sulfur isotope in borehole sediments Location Borehole (BH) Depth rangea (m) As (mg/kg) P Murshidabad BH 1 BH 2 BH 3 BH 4 Nadia BH 1 BH 2 136152 155194 06.06 6.0612.1 109112 010 90.993.9 215218 221224 22427 233236 245248 65.467.3 67.369.1 73.980.3 124127 145148 103106 112115 115118 118121 121124 124127 127130 130133 133136 136139 139142 142145
b

2859

Selected particle (S) H

c

As (mg/kg) 2117 2251

Fe (%) 20.7 27.3

As/Fe ratio 0.0100 0.0082

Sulfur isotope (Permit V-CDT)d 4.3 4.3

77.6 15.2 10.3 10.4 28.4 11.2 14.5 17.5 13.1 52 59.7 57.2 20.7 15.7 16 23.1 20.1 57.2 27 8.94 22.7 6.50 59.4 42.2 42.9 74.5 374 103 24.2

31.2 15.8 16.6 11.7 11.3 21.4 17.6 22.7 19.6 16.2 36 16.6 64.4 114 19.6 25.8 22.2 24.1 69.7 36.9 41.1 156 71.6 96.8 27.6 52.7 197 181 141

BH 3

BH 4 BH 5

2778

32.3

0.0086

18.4

Depth range at which arsenic was found above 10 mg/kg in homogenized sample. Parent sediment sample. c Homogenized sample (from parent sediment). d V-CDT (Vienna-Canyon Diablo Troilite) is a FeS meteorite used as the accepted zero point for expression of sulphur-34 in delta units. V-CDT is thought to have a sulphur34 value close to the universal mean.
b

Table 2 Arsenic withdrawn and deposition on land by the shallow tubewells in the studied areas Location (land) Land area (ha) n Mean Range As in shallow water (mg/L) Discharge rate of As withdrawn by the wells per yearb (kg) As deposition per land per year (kg ha1) watera (m3 h1) n Mean Range Mean Range Mean Range 0.075 0.021 0.0180.20 0.0040.082 20 20 2.20 0.62 0.535.88 0.1182.41 7.52 1.96 1.6616.8 0.328.03

Murshidabad 23 0.29 (agricultural) Nadia (paddy) 18 0.35

0.220.36 23 0.300.39 18

Notes: aDischarge rate of water = 20 m3 h1 = 20 7 210 m3 year1 (each tubewell ran average 7 h per day and 7 months per year) = 20 7 210 1000 l year1 = 2.94 107 l year1. P P Arsenic withdrawn by the wells per yearb = (arsenic withdrawn by each well per year) = (discharge rate of well watera arsenic concentration in each shallow tubewell water).

arsenic concentrations in paddy plants is due to the fact that the paddy elds are covered with irrigated groundwater and the roots absorb arsenic from contaminated water for at least 1 month. A considerable amount of arsenic has been found in irrigated soils (mean: 44.7 mg/kg, range: 6.92132 mg/kg, n = 4) from the paddy elds. The mean arsenic concentration is in the root > stem > leaf. That means arsenic is translocated from the root into the aerial organs in amounts decreasing from the stem to leaf. The distribution of arsenic in plants, in general is in descending order from root to stem and leaf to edible parts (Liu et al., 1985; Roychowdhury et al., 2005). Approximately 7.07%, 2.14% and 1.78% of arsenic is taken up by root, stem and leaf of agricultural plants from the soil, respectively. The uptake of arsenic in different parts of paddy plants is not reected correctly from the soil. Because the paddy plants absorb a considerable amount of arsenic from the irrigated groundwater that is directly in touch with the root for at least 1 month.

External contamination of arsenic could not be ignored also. The farmers sometimes used to spray arsenic-contaminated groundwater onto the plants. As a result, water on the leaves dries up, leaving a residue of arsenic that, with time, accumulates on the leaf (mean: 20.5 lg/kg, range: <0.0462 lg/kg, n = 128). 3.3. Arsenic levels in food categories The summary of arsenic levels and concentration of arsenic species in food categories are shown in Table 4. The mean arsenic concentrations in vegetables, cereals and spices are 78.4 lg/kg (range: 21690 lg/kg, n = 174), 139 lg/kg (range: 21662 lg/kg, n = 108), and 127 lg/kg (range: 40481 lg/kg, n = 82) respectively. The food samples containing the highest mean arsenic concentrations are potato skin (mean: 335 lg/kg, range: 59792 lg/kg, n = 27), leaf of vegetable (mean: 268 lg/kg, range: 87690 lg/kg, n = 22), rice

2860 <0.041.6 1.8031.8

T. Roychowdhury / Food and Chemical Toxicology 46 (2008) 28562864

Murshidabad (030 cm); Nadia (1550 cm). Plants of cabbage, cauliower, gram, garlic, radish, lentil, wheat, mustard, egg plant, onion, potato, coriander, tomato, spinach, peas, beans, etc.

Soil from root of plant

grain (mean: 214 lg/kg, range: 43662 lg/kg, n = 52), wheat grain (61.2 lg/kg, range: 34362 lg/kg, n = 9), wheat our (mean: 54.3 lg/kg, range: 21119 lg/kg, n = 19), cumin seed (mean: 107 lg/kg, range: 49259 lg/kg, n = 11) and turmeric powder (mean: 289 lg/kg, range: 131481 lg/kg, n = 19). The shallow tubewells used for agricultural irrigation in Nadia district contain less amount of arsenic (mean: 0.021 mg/L, range: 0.004 0.082 mg/L, n = 18). But an appreciable amount of arsenic is found in different parts of plants and crops, cultivated in this district. It was reported that only 0.018 mg/L of arsenic in the shallow tubewell water of Bakshipur agricultural land, Domkal block contaminated the food chain from crops cultivated in that area and the arsenic concentrations in foodstuffs were rice grain (183 lg/kg), wheat our (80 lg/kg), turmeric powder (335 lg/kg), beans (200 lg/kg), green chili (130 lg/kg) and ve spices (247 lg/kg) (Roychowdhury et al., 2002b). The rice grain (up to 1.7 mg/kg) and vegetables grown in Bangladesh using the arsenic-contaminated irrigation water contained a considerable amount of arsenic (Alam et al., 2003; Meharg and Rahman, 2003). The mean arsenic concentrations in rice grain (72 10 lg/kg) and edible herbs (91 30 lg/kg) were reported from arsenic-affected areas of South 24-Parganas district, West Bengal (Mandal et al., 1998). The mean arsenic concentrations in rice grain and vegetables were 358 and 34 lg/kg, respectively in North 24-Parganas district, West Bengal (Chowdhury et al., 2001). The average arsenic concentrations in rice and yams from Taiwan were 150 and 110 lg/kg, respectively for samples collected in 1995 and 1993 (Schoof et al., 1998). About 95% of the crops in Taiwan were found to contain detectable amounts of total arsenic, mainly in the range of 100700 lg/kg (Li et al., 1979). All these values agree the study results. A signicant amount of arsenic is absorbed by skin from most of the vegetables. The arsenic concentration in eshy vegetable material is low (mean: 18 lg/kg, range: <0.0459 lg/kg, n = 61). In another study, arsenic could not be detected (<2 lg/kg) in the extract of the eshy material of vegetables by a FI-HG-AAS system (Mandal et al., 1998). Higher levels of arsenic are observed in cooked food samples compared with raw. Mean arsenic concentrations in cooked rice and cooked vegetables are 518 lg/kg (range: 105 1030 lg/kg, n = 22) and 369 lg/kg (range: 186617 lg/kg, n = 6), respectively. The villagers usually wash rice/vegetables and cook using arsenic-contaminated water that certainly increases the arsenic level. 3.3.1. Cooked rice: contribution of water arsenic concentration The traditional method of cooking rice still used by more than 90% of the villagers in Bengal delta is: raw rice is washed till the washings become clear (46 times), washings are discarded, and then the rice is boiled in excess water (approximately 5 times the weight of raw rice) till cooked, nally discarding the remaining water by tilting the pan against the lid before serving the rice. By following the method, the weight of cooked rice in this survey is approximately 4 times higher than that of raw rice, which means, water content of cooked rice is about 75%. Mass balance study for cooked rice preparation from Murshidabad district is shown by a simple calculation (Table 5). The experimental value shows that the arsenic concentration in cooked rice is approximately 2.1 times higher than that of raw rice. The mean arsenic concentration in studied cooked rice from Murshidabad district is 569 lg/kg (range: 1981030 lg/kg, n = 18) and it is 2.4 times higher than that of raw rice grain (mean: 239 lg/kg, range: 43662 lg/kg, n = 34) in the district (studied randomly) (Table 4). Similarly, the mean arsenic concentration in studied cooked rice from Nadia district is 290 lg/kg (range: 105410 lg/kg, n = 4) and it is 1.5 times higher than that of raw rice grain (mean: 190 lg/kg, range: 45386 lg/ kg, n = 18) in the district (studied randomly) (Table 4). The mean arsenic concentrations in cooking water (the same water used for

Mean Leaf n Mean Stem n Mean Root n Mean n Mean n Mean n Range Surface soil As in soil Location (land) Range Range Soil below ground levela Range As in plants Table 3 Arsenic levels (mg/kg) in soils and plants in the studied areas Range

Range

Murshidabad (agriculturalb) Nadia (paddy)

279 162

14.3 16.7

3.3431.6 595.3

99 162

13.7 11

7.5620.7 5.6723.2

102 282

14.8 10.1

8.6921 4.5924.4

99 162

0.99 279

<0.042.9 60.31238
b a

99 162

0.30 15.9

<0.042.9 1.6866

99 162

0.25 10.3

T. Roychowdhury / Food and Chemical Toxicology 46 (2008) 28562864 Table 4 Summary of arsenic levels and concentration of arsenic species (lg/kg) in food categories from the studied areas Location Food category Concentration of As n Murshidabad Vegetable Cereals Raw Cooked veg. Raw, all typesa Rice grain Cooked rice Raw Raw Raw, all typesa Rice grain Cooked rice Raw 126 6 70 34 18 66 48 38 18 4 16 Mean 85 369 150 239 569 136 61 118 190 290 90 Range 43690 186617 85662 43662 1981030 74481 21108 21386 45386 105410 40321 Rice Rice Rice Rice Rice Rice LV LV LV LV 1 2 3 4 1 2 3 4 5 6 120 150 244 210 116 85 158 175 290 126 8.03 13.5 51.8 45.4 10.2 7.6 34.3 36.8 48.7 16.9 2.68 20 23.9 17 4.14 3.95 5.96 11.7 35.5 9.09 75 72 88.7 80 70.4 50.4 68.6 74 111 67 Food sample Total As As (III) DMA As (V) Inorganic As/total species (%) 96.9 81 85.5 88.1 95.1 92.9 94.5 90.4 81.8 90.2

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Recovery (%)

Spices Nadia Vegetable Cereals

71.4 70.3 67.4 67.8 73 72.9 68.9 70 67.3 73.8

Spices
a

Rice grain, wheat, wheat our, lentil, other pulses; LV: leaf of vegetable.

Table 5 Mass balance study for cooked rice preparation from Murshidabad district Item no. (i) (ii) (iii) (iv) (v) (vi) (vii) (viii) (ix) (x) (xi) (xii) (xiii) Item Arsenic concentration in rice grain Weight of rice grain Total arsenic in rice grain Arsenic concentration in cooking water Weight of cooking watera Total arsenic in cooking water Arsenic concentration in discarded water Weight of discarded waterb Total arsenic in discarded water Total arsenic concentration in cooked rice Weight of cooked ricec Arsenic in cooked rice (wet) Arsenic in cooked rice (dry) Quantity 239 lg/kg (mean value) m g (suppose) (i) (ii) = 0.239 m lg 110 lg/l (mean value) 5mg (iv) (v) = 0.55 m lg 96.9 lg/kg 3mg (vii) (viii) = 0.29 m lg [(iii) + (vi)] (ix) = 0.499 m lg 4mg (x)/(xi) = 125 lg/kg (x)/(ii) = 499 lg/kg

a Weight of cooking water is approximately 5 times higher than the weight of rice grain. b Weight of discarded water is approximately 3 times higher than the weight of rice grain. c Weight of cooked rice is approximately 4 times higher than the weight of rice grain.

drinking purposes also by the studied families) from Murshidabad district (mean: 110 lg/L, range: 6200 lg/L, n = 44) is twice than that of Nadia district (mean: 52 lg/L, range: 1192 lg/L, n = 19), respectively. Thus, arsenic concentration in cooked rice increases with water arsenic concentration. Few other reports also showed an increase in the arsenic content after cooking rice in contaminated water (Bae et al., 2002; Misbahuddin, 2003; Sengupta et al., 2006). 3.3.2. Arsenic species in food categories HPLC chromatograms of standard 30 lg/L mixture solution of arsenic species, Rice 2, Rice 3 and Leaf of Vegetable 1 (from Table 4) are shown in Fig. 1ad, respectively). The retention times (tR) of As (III), DMA, MMA and As (V) for standard 30 lg/L arsenic solutions (sample analysis was done on two different days) are 109, 146, 206 and 395 s (Fig. 1a) and 109, 141, 212 and 371 s, respectively (not shown in gure). Inorganic arsenic (arsenite and arsenate) contributes 89.9% and 89.2% of the total content of arsenic, in rice grain and leaf of vegetables, respectively. DMA contributes the rest of the total content of arsenic. There is no evidence of MMA in these samples. About 70.2% of arsenic is recovered by using the analytical speciation extraction method

in this study. Other than the seafood, inorganic arsenic may be the major contribution of arsenic in many foods. Seafood contains mainly non-toxic organic forms of arsenic and rapidly excreted through urine (Francesconi and Edmonds, 1997). The Canadian diet study reported that 65% of the total content of arsenic in food composites was inorganic (Dabeka et al., 1993). Inorganic arsenic contributed 95% and 96% of total content of arsenic in rice grain and vegetables, respectively in West Bengal (Chowdhury et al., 2001). Douglas et al. (2001) reported that the percentage of inorganic arsenic and DMA in rice (n = 6) were 43.8% and 56.2%, respectively. FDA total diet study (Tao and Bolger, 1998) reported that 10% of the arsenic in seafood was inorganic and that 100% of the arsenic in rest of the food was inorganic. About 64 1% (n = 7), 80 3% (n = 15), 81 4% (n = 11) and 42 5% (n = 12), of the arsenic was found to be inorganic in rice extract from Europe, Bangladesh, India and USA, respectively (Williams et al., 2005). Inorganic arsenic calculated as arsenite and arsenate made up 87% of the total arsenic measured in rice, and 96% of the total arsenic in vegetables from Bangladesh (Smith et al., 2006). Other than the total inorganic arsenic concentration (arsenite and arsenate) in rice/other food sample from Bengal delta, separate existence of the two species is not available in literature. A high variation in concentration has been observed between the two inorganic arsenic species (arsenite and arsenate) in this study. The mean ratio of As (V)/ As (III) for rice (n = 6) and leaf of vegetable (n = 4) are 3.2 and 2.3, respectively (Table 4). Although, a least possibility of oxidation (arsenite to arsenate) during sample processing could not be dismissed. 3.3.3. Accumulation of arsenic in rice grain Rice grain plays a major role for arsenic exposure. A number of studies have been reported on impact of irrigating rice paddies with groundwater containing arsenic (Norra et al., 2005; van Geen et al., 2006; Roberts et al., 2007). It was calculated that, even at background levels (0.10.2 lg As/g), the arsenic in rice contributed considerably to arsenic ingestion in affected areas of Bangladesh (Meharg and Rahman, 2003). In this study, approximately 0.081% and 1.57% of arsenic are accumulated in rice grain from arsenic-deposited land and contaminated soil and about 0.029 and 0.133 mg of arsenic are accumulated in rice grain per kg of plant and kg of paddy, respectively in Nadia district (Table 6). Daily intake of inorganic arsenic from rice grain is 2.32 lg/kg body wt./day (Table 6) and this value is higher than WHO recommended PTDI (provisional tolerable daily intake) value of inorganic arsenic (2.1 lg/kg body wt./day) (Joint FAO/ WHO, 1989).

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T. Roychowdhury / Food and Chemical Toxicology 46 (2008) 28562864

Fig. 1. HPLC chromatogram of As (III), DMA, MMA and As (V) species in (a) standard 30 ppb solution; (b) rice 2; (3) rice 3 and (d) leaf of vegetable 1.

3.4. Population exposed to arsenic toxicity Water and rice are the main sources of arsenic to the diet in the arsenic-affected areas of Bengal delta. Vegetables grown on arsenic-contaminated soil also contribute some amount of arsenic. The average daily intake of water, rice and vegetables by an adult (both male and female) in this study are 5 L (4 L as drinking water and 1 L during food preparation), 712 g (dry weight, wet weight:

750 g) and 100 g (dry wt., wet wt.: 500 g), respectively (approximately, 5% and 80% moisture are contained in rice grain and vegetables, respectively). Then, the average daily dietary intakes of arsenic by an adult from these three sources in Murshidabad and Nadia district are 729 lg (110 lg/L 5 L + 239 lg/kg 712 g + 85 lg/kg 100 g) and 401 lg (52 lg/L 5 L + 190 lg/kg 712 g + 61 lg/kg 100 g), respectively. Water contributes about 70% of arsenic, with respect to the total dietary intakes of arsenic in the

T. Roychowdhury / Food and Chemical Toxicology 46 (2008) 28562864 Table 6 Accumulation of arsenic in rice grain and daily dietary intake from Nadia district Item Production of paddy per land Production of rice grain per landa Arsenic concentration in rice grain Total arsenic in rice grain per land per yearb Arsenic deposition per land per year Arsenic in rice grain, accumulated from deposited land Arsenic in soil Arsenic in rice grain, accumulated from soil Production of paddy per plantc Production of rice grain per plant Total arsenic in rice grain per paddy plant Total arsenic in rice grain per paddy Daily intake of inorganic arsenic by an adult from rice graind Quantity

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20 Mon/Bigha = 20 40 kg/Bigha = 800 7.5 kg ha1 = 6000 kg ha1 6000 28/40 = 4200 kg ha1 0.19 mg/kg 4200 0.19 2 = 1.60 g ha1 1.96 kg ha1 (1.60 g ha1/1.96 kg ha1) x 100 = 0.081% 12.1 mg/kg (0.19 mg/kg/12.1 mg/kg) 100 = 1.57% 222 g/kg of plant 222 28/40 = 155 g/kg of plant 155 0.19/1000 = 0.029 mg/kg of plant 0.19 155/222 = 0.133 mg/kg of paddy 0.19 mg/kg 89.9% 712.5 g/52.5 kg= 2.32 lg/kg body wt./day

Mon is the unit of measurement of weight of crops, commonly used in rural Bengal, where 1 Mon = 40 kg. Bigha is the unit of measurement of area of land, commonly used in rural Bengal, where 1 ha = 7.5 Bigha. Twenty Mon paddies are produced from 1 Bigha land. a Twenty-eight kilograms of rice grain is produced from 1 Mon (40 kg) of paddy. b Two times rice production per year from the same land. c Average value of produced paddy per plant, collected from 15 different spots from paddy eld during survey. d Inorganic arsenic contributes 89.9% of total content of arsenic in rice and an adult (male/female) having an average weight of 52.5 kg, consumes 712 g of rice (dry wt.) per day.

two districts. Rice grain contributes about 95% of arsenic, with respect to the dietary intakes of arsenic from the food samples only. The average daily dietary intakes of inorganic arsenic by an adult in the two districts are 710 lg (97.4% of total) and 386 lg (96.3% of total), respectively, considering inorganic arsenic contributes 89.5% of total arsenic in foods from this study and arsenic species reported in groundwater from Bengal delta is inorganic (Chatterjee et al., 1995; Rasul et al., 2002; Tokunaga et al., 2005). The dietary intakes of inorganic arsenic (lg/kg body wt./day) by an adult from three main sources (water, rice and vegetables) in the two districts are: for males (11.8 and 6.43), and females (15.8 and 8.58), respectively (average weights for adult males and females in this study are 60 and 45, respectively). These values are much higher than WHO recommended PTDI value of inorganic arsenic (2.1 lg/kg body wt./day) (Joint FAO/WHO, 1989). So, there could be an increased risk of suffering from arsenical skin lesion. Approximately 48.7 (n = 41) and 33.3% (n = 33) of adult females suffer from arsenical skin lesions, compared to 76.7 (n = 43) and 86.4% (n = 22) of adult males in Murshidabad and Nadia districts, respectively. The children in this survey do not suffer from arsenical skin lesions. Infants and children are considered to be more susceptible to the adverse effect of toxic substances (National Research Council, 1993). A report from USEPA indicates that estimated mean per capita ingestion rates (per kg of body wt.) of babies, younger than 1 year are three to four times higher than the mean rates for the population as a whole (USEPA, 2000). Normally children below the age of 11 years do not exhibit arsenical skin lesions. However, there were exceptions (Roychowdhury et al., 1997; Chowdhury et al., 2000; Rahman et al., 2005). Another important factor is nutritional status. It was reported that people with healthy nutrition suffered less from arsenic toxicity compared with undernourished people (Harrington et al., 1978; Das et al., 1995). Literature surveys indicate arsenic resistance and its relation with nourishment (Calabrese, 1980; Harding-Barlow, 1983; USEPA, 1988). The families in this survey are poor and have a poor nutrition, therefore they suffer more from arsenic toxicity. The children and few adults, who had no arsenical skin lesions during the survey, still have high arsenic body burden in their urine and hair (Tokunaga et al., 2002, 2005; Uchino et al., 2006). So they are sub-clinically affected by arsenic. Conict of interest statement The authors declared that there are no conicts of interest.

Acknowledgements The author acknowledges the help of Division of Environmental Chemistry, National Institute of Health Sciences, Japan and School of Environmental Studies, Jadavpur University, India during the study. Financial supports from JSPS, Ministry of Education, Japan and CSIR, New Delhi is highly acknowledged. References
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