Applied Geochemistry

Applied Geochemistry 22 (2007) 12731292 www.elsevier.com/locate/apgeochem

Chemodynamics of an arsenic hotspot in a West Bengal aquifer: A eld and reactive transport modeling study
Laurent Charlet a,*, S. Chakraborty a,b, C.A.J. Appelo c, G. Roman-Ross d, B. Nath b,e, A.A. Ansari a, M. Lanson a, D. Chatterjee b, S. Basu Mallik e
a

LGIT CNRS/UJF, University of Grenoble-I, P.O. Box 53, F 38041 Grenoble Cedex 9, France b Department of Chemistry, University of Kalyani, Kalyani, West Bengal, India c Hydrochemical Consultant, Valeriusstraat 11, NL1071MB Amsterdam, The Netherlands d Faculty of Sciences, University of Girona, Campus de Montilivi, 17071 Girona, Spain e Department of Geological Sciences, Jadavpur University, Calcutta, West Bengal, India Received 30 March 2005; accepted 17 December 2006 Editorial handling by R.B. Wanty Available online 20 March 2007

Abstract Extremely high As concentrations in drinking water of the Ganges Delta (West Bengal and Bangladesh) has emerged as an issue of great concern in the past decade because of its serious impact on the health of millions of people. The distribution pattern of As concentrations in the Ganges Delta region is patchy and there are numerous As hotspots. The present study is perhaps the rst attempt in West Bengal to characterize such a hotspot by geophysical and geochemical methods, and to model the transport of the enrichment plume using a 1D reactive transport model (PHREEQC). The study site is located along the Hooghly River, 60 km north of Kolkota City, near the city of Chakdaha. Total As concentrations in the groundwater range from 0.5 to more than 6 lmol L1; the WHO recommended maximum drinking water concentration is 0.13 lmol L1 (i.e. 10 lg L1). Results show groundwater is in chemical equilibrium with siderite and calcite, a mineral phase previously shown to be an ecient trap for As(III). Groundwater redox potential is controlled by the Fe(OH)3(am)/Fe2+ couple. The As(III) versus As(V) distribution (42% As(III) and 58% As(V), on average) is not at equilibrium with measured Eh values. No evidence of sulde solid phases, such as As rich pyrite or arsenopyrite, was found. Although amorphous Fe dissolution is conrmed to play an important role in the release of As, selective dissolution extractions indicate that adsorption of As on carbonates and micas may also be an important component of As cycling in the sediment. Modelling results demonstrate the role of PO3 ; HCO and Fe(II) in mobilizing the As plume, thereby increasing 4 3 the threat to the 75,000 inhabitants of Chakdaha. 2007 Elsevier Ltd. All rights reserved.

1. Introduction
Corresponding author. Tel.: +33 4 7682 8020; fax: +33 4 7682 8101. E-mail address: laurent.charlet@obs.ujf-grenoble.fr (L. Charlet).
*

Arsenic enrichment in groundwater has been an issue of serious concern worldwide in recent years, particularly in the Bengal Delta Plain (BDP; West

0883-2927/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.apgeochem.2006.12.022

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Bengal and Bangladesh) where a large population relies on As-rich groundwater for drinking and agriculture purposes (Acharyya et al., 1999; Das et al., 1994; Bhattacharya et al., 1997; Dhar et al., 1997; Nickson et al., 1998; Ravenscroft et al., 2001; McArthur et al., 2001; Smedley and Kinniburgh, 2002; Charlet and Polya, 2006). Several million people in parts of the Ganges River Delta region are estimated to be at risk and exhibit symptoms of chronic As exposure (e.g., keratosis, melanosis, and fatal cancer, Das et al., 1994; Charlet and Polya, 2006). Arsenic is both highly toxic and carcinogenic (Morton and Dunnette, 1994). Assessing the risks associated with groundwater, As enrichment depends heavily on the ability to understand and predict the reactive transport of As. Not only does the reactivity and transport of As species depend on their chemical speciation, so does their toxicity. Reduced As(III) species are more toxic, and adsorb more weakly than As(V) species, which behave in many respects similarly to phosphate (Mok and Wai, 1994). Present in most waters as H2 AsO or 4 HAsO2 (pK2 = 7.0), As(V) bonds strongly to Fe 4 (and to a lesser extent Al) hydrous oxide surfaces and is therefore highly retarded. The extent of adsorption strongly depends on pH but also on the presence of background species that compete for sorption sites, and As(V) can be desorbed by PO3 and HCO anions, as well as by Fe(II) cations 4 3 (Appelo et al., 2002). In contrast, As(III) is present in most natural waters as a neutral aqueous 0 AsOH3 species (pK1 = 9.2), and its adsorption on hydrous oxides depends little on pH in the neutral pH range and is rarely complete. Both ions can adsorb on other substrates as well, such as clays, micas, mackinawite or calcite (Manning and Goldberg, 1997; Chakraborty et al., in press; RomanRoss et al., 2006). The regional distribution pattern of As enrichment in the Ganges Delta region is extremely patchy and there are numerous groundwater hotspots. Analysis of a large database of aquifers in West Bengal reveals that As concentrations decrease with depth (Acharyya et al., 1999). Three levels of aquifer systems in the upper delta plain (UDP) have been delineated within the 150 m-deep enriched horizon, where mid-level aquifers are relatively more arseniferous (Bhattacharya et al., 1997). Hotspot areas are located in low-lying areas of the young Gangetic oodplain, with the most enriched aquifers between 20 and 60 m depth. Nickson et al. (1998) and Nath et al. (2005) proposed that As-rich lenses could have

been deposited in association with paleomeanders. Indeed, the Ganges River is now primarily a meandering river, having metamorphosed from a braided to a meandering form during the Holocene (Singh, 1996). The aquifer system of West Bengal is hydrodynamically and hydro-chemically very active because of monsoonal rains and several anthropogenic activities, such as intense agriculture and groundwater exploitation for irrigation and drinking purposes (McArthur et al., 2001). The upperlevel (shallow) aquifers are often unconned, whereas the lower-level (deeper) aquifers are semiconned. The deeper aquifers are generally interconnected with shallow aquifers either by truncation of a conning silty/clayey layer or as a result of groundwater pumping (Chowdhury et al., 1999). Various factors are responsible for the chemical changes in groundwater chemistry and thus for the increasing mobility of As in aquifer systems of the Ganges Delta: biological and abiotic reductive dissolution of Fe oxides (Nickson et al., 1998; McArthur et al., 2001), oxidation of suldes (Chowdhury et al., 1999) and anion exchange (Appelo et al., 2002) (see Charlet and Polya, 2006, for a detailed discussion on these various factors). In this paper the transport of As from an apparent point source in a deep silty sand aquifer in Chakdaha, West Bengal, India, is discussed. The study site is located 65 km north of Kolkata, along the Hooghly River, the largest tributary of the Ganges in West Bengal, India. The 4 km 5 km site was fully characterized by geochemical and geophysical methods. Electrical resistivity of the aquifer sediment was measured to distinguish the silty clay-rich surface layer from the deeper productive aquifer, where most wells are extracting groundwater. A network of 44 groundwater monitoring wells were sampled for 2 a. Groundwater was monitored for pH, Eh, conductivity, dissolved O2, alkalinity, DOC, Fe(II), Mn(II), sulde, NH ; NO , As(III), 3 4 As(V), and other major dissolved species. Aquifer sediments were sampled from dierent boreholes and characterized for porosity and grain size distribution, as well as for the presence of crystalline phases using X-ray diraction. A series of selective dissolution extractions was also performed on sediment cores obtained from a single borehole. Field results show that the As hotspot develops in a HCO -rich, Fe(II)-rich anoxic environment. 3 A 1D groundwater model for the reactive transport of both As(III) and As(V) is proposed, based on

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experimental data and results obtained from the small-scale eld study. The results have important implications for the assessment of future risk to nearby populations, who may be exposed to this source of As-rich groundwater. 2. Study site and monitoring well installation Field investigations were conducted on a deep, silty sand aquifer in Chakdaha, West Bengal. The study covers an area of 20 km2 and is situated in the heart of the BDP along the Hooghly River, a main tributary of the river Ganga. The BDP encompasses an integral part of the GangaBrahmaputra, the worlds largest deltaic alluvial deposit. The combined discharge of the Ganges and Brahmaputra Rivers into the Bay of Bengal is approximately 82,000 m3/s during the monsoon season (JulySeptember). The sediment load is extremely high, reaching as much as 13 106 tons per day during the monsoon season (Coleman, 1969). The large alluvial plain, spreading southward down to the Bay of Bengal, is formed by successions

of a ning upward sequence with occasional clay layers. The Ganga has shifted from time to time to the west during the Holocene. The area is at and intersected by small rivers, backwaters, minor streams and swamps. There is a gentle hydraulic gradient generally sloping towards the SE. Geomorphologically the area occurs within the active oodplain of Hooghly and is characterized by a series of oxbow lakes and meander scars of varied wavelengths and amplitudes. Landform features, like natural levees, separate the paddy-lled oodplain from the constructed inhabited area (Fig. 1). The climate is tropical, hot and humid: temperatures range between 16 C and 42 C; average relative humidity >65%; and annual rainfall ranges between 1295 mm and 3945 mm, mostly concentrated during the monsoon (JulyOctober). Ten 30 m-deep wells were installed along a groundwater owpath from the enriched zone to the non-enriched zone close to the school (Fig. 1), i.e. at the As hotspot, a nest of four wells were drilled within a proximity of 20 m of each other, at depths from 8 to 30 m and undisturbed sediment

Fig. 1. IKONOS satellite image of the study site, Chakdaha Block, Nadia district, 65 km north of Kolkata in West Bengal, India showing various types of geomorphic features relevant to As reservoirs and source. The data were processed to emphasize in purple the presence of water in streams, ponds, and irrigated elds without vegetation. Images were fused to generate a false colour composite merged map with multispectral behavior and higher resolution (10 m). Contrasting bright areas of the IKONOS image indicate dry, presumably uncultivated elds. Green areas show the vegetation of the elds that are cultivated as well as the tree cover that identies the villages.

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Fig. 2. Water level map at the end of the dry season, and well locations located within the center of Chakdaha, West Bengal. During the wet season part of the area is ooded (see Nath et al., 2005, for a detailed description). The railway runs through the middle of the city; the railway station is located by well #9. Resistivity proles were recorded along the AA 0 transect and reactive transport modelling was performed along the BB 0 transect.

cores were obtained from one of the four hotspot wells (Borehole B-4, Fig. 2). Fourty-four additional wells (depth range: 946 m) located throughout the study site were also monitored (Fig. 2). This network extends from the river shore and nearby rice elds to the center of Chakdaha. Distinctive paleomeanders are indicated on the satellite photograph (Fig. 1) in the ooded area and particularly at the border between the oodplain and the city. A separate study is dedicated to a geochemical and geophysical study of the oodplain lying along the river (Metral et al., submitted for publication). 3. Methods 3.1. Aqueous chemical characterization 3.1.1. Sampling Groundwater was sampled in such a way as to exclude contact with the atmosphere. Whenever possible, a multiprobe (multilane P4 WTW) tted

with calibrated Pt redox and dissolved O2 electrodes was introduced directly into the groundwater. Otherwise, about 50 L of water was pumped with a hand pump before water was sampled. Samples for dissolved O2 determination were ltered from a 0.2 L amber glass sampling bottle. Samples for measurement of Fe(II) and sulde were immediately collected with a syringe and ltered through a 0.45 lm cellulose ester lter membrane directly into pre-prepared colorimetric reagent solutions (Lindsay and Baedecker, 1986). For anion and DOC measurements, a 60-mL sample was ltered into a special untreated amber glass bottle, with specically designed taps to prevent air bubbles entering the bottles. To measure major and trace elements, a ltered 60-mL sample was acidied with 0.5 mL of suprapure concentrated HNO3 acid in a polypropylene bottle. To prevent any organic growth or decay, samples were refrigerated in an icebox within minutes after collection and kept cooled (4 C) until analysis in the lab-

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oratory. Sampling, sample ltration, treatment and titration of O2 and H2S took about 23 h. 3.1.2. Major and trace element analyses Dissolved metals were determined by ICP-AES (PerkinElmer 3300 DV Optima) and anions by capillary electrophoresis (CIA Waters) at LGIT, University of Grenoble, France. Cation and anion concentrations were also in part measured at the Department of Chemistry, University of Kalyani with a Methrohm ion chromatograph except in a few cases, results of replicated water analyses in both laboratories were within 10% of each other. Redox sensitive constituents (Fe(II) and sulde ions) were measured colorimetrically with a Hach DR 2010 spectrophotometer. Dissolved Fe(II) was measured using the o-phenanthroline method (Vogel, 1989) and dissolved O2 by the Winkler method. Alkalinity and pH were measured on-site with a manual eld titrator and a WTW 197 pH meter, respectively. 3.1.3. Arsenic analysis Total As was measured by ICP-AES (Perkin Elmer 3300 DV Optima) with a detection limit of 20 lg L (0.26 lM L1) or by hydride generation atomic uorescence spectrometer (HG-AFS, Millenium Excalibur System, PS Analytical Ltd., Kent, UK) with a detection limit of 200 ng L1 (2 nM L1). All total As values were well above the detection limits. To selectively analyze for As(III), two methods were used. In the analytical speciation method (Kuhn and Sigg, 1993), aliquots from the ltered solutions were diluted at ratios between 1:500 and 1:50 into a 0.5 M Na2Hcitrate buer. As(III) is selectively converted to AsH3 under these conditions and measured by AFS. It was veried that As oxidation in the citrate buer continued only at a very slow rate. Total As values measured after preliminary KI reduction of the solution represent the sum of all toxicologically relevant species i.e. As(III), As(V), and methylated As-acids (monomethyl arsenic acid, MMAA; dimethyl arsenic acid, DMAA). In the second method (Kneebone and Hering, 2000), species were separated in the eld using an anion-exchange resin (Dowex 1 8; 100 200 mesh, acetate form). Arsenic is analyzed, as discussed above, after separation of As(III) and As(V) with the anion-exchange resin which retains As(V) but not As(III). The resin is provided in chloride form and must be converted to the acetate form

with an hydroxyl form as intermediate. For this purpose, 3 mL 1 M NaOH are rst injected into the column. After rinsing the resin with distilled water to eliminate the excess of NaOH, 5 mL 1 M acetic acid are injected. The resin is rinsed with water, and 50 mL of sample are ltered and acidied with 0.5 mL of concentrated HCl to avoid the oxidation of As(III) to As(V). Kim et al. (2000) suggested that aqueous As(III)HCO3 negatively charged complexes may form, which solubilize As and aect anionic resin based eld speciation studies. However, this was not observed in the present study, as the fraction of As not retained by the anion exchange resin (and expected to be dominated by As(OH)3 species) was identical to the As(III) fraction measured by HG-AFS. The absence of As(III)carbonate complex has been recently conrmed by ICP-MS (Wallschlager D., pers. com.). Speciation and saturation state calculations were carried out using PHREEQC (Parkhurst and Appelo, 1999). 3.2. Sampling and analysis of sediments Bulk sediment was sampled from various boreholes, including a paleomeander near the Hooghly River (Fig. 2). An undisturbed sediment core was extracted at 18 m depth from the silty/clayey layer found at this depth in Borehole B-4 (Fig. 2). The 60-cm tube was sealed, put in a sealed bag lled with N2 and transported in an ice box to Grenoble, France, where the bag and the tube were opened in a glove box. Sediments were characterized for porosity using the core method (Blake and Hartge, 1986). In this method a cylindrical metal sampler is pressed into the undisturbed sediment core and carefully removed to preserve a known volume of sample. This sample was then stored at 10 C and weighed. The material was later dried to constant weight in a freeze-dryer (Christ, Alpha Ia) in the laboratory. Samples for sequential extractions were taken at the middle of the core, in order to avoid the eect of any oxidation which may have occurred during transport, and immediately frozen and freeze-dried. Sequential extractions were performed on the <63 lm fraction following the method detailed in Table 1. Each successive extraction dissolves specic solid phases with which As may be associated (Table 1). Extractants were analyzed for total As, as well as dissolved Fe2+ (o-phenanthroline method) and total Fe (after reduction by addition of

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Table 1 Sequential chemical extraction treatments for As-bearing sediment (silty clay sediment sampled at 18 m depth, borehole B-4) solid phases Fraction F1 F2 F3 F4 F5 F6 Extractant 1 M MgCl2 pH 8, 2 h, 25 C 1 M NaH2PO4 pH 5, 16 and 24 h, 25 C 1 N HCl, 1 h, 25 C 0.1 M ascorbic acid 0.2 M C6H5Na3O7 tri-sodium citrate, 0.6 M sodium hydrogen carbonate 24 h pH 8 0.3 M sodium dithionite, 0.35 M sodium acetate, 0.2 M sodium citrate, 5 h pH 4.4, 60 C H2O235%, pH 2, 5 h, T 85 C Target phase Ionically bound As (Keon-Blute et al., 2001) As strongly adsorbed on Fe oxyhydroxides and humic acids (Keon-Blute et al., 2001, Zheng et al., 2004) As coprecipitated with AVS, carbonates Mn oxides and very amorphous Fe oxyhydroxides (Keon-Blute et al., 2001) As coprecipitated with amorphous Fe oxyhydroxides (Kotska and Luther, 1994) As coprecipitated with crystalline Fe oxyhydroxides (Kotska and Luther, 1994) Orpiment and remaining recalcitrant As minerals (Tessier et al., 1979)

hydroxylamine hydrochloride; Vogel, 1989). Crystalline phases were identied using X-ray diraction (Siemens 5000) and mineral grain-size distribution was determined by a Coulter Laser Granulometer. 3.3. Hydrological and geophysical methods Groundwater table levels were measured in 44 pre-existing tube wells using an electronic tape with an accuracy of 1 cm (Fig. 2). All wells were measured with respect to mean sea level (msl) using the GTS Bench Mark. The water levels were then used to construct a water level iso-contour map using the triangulation method included in SURFER 7.0 software. Satellite imagery was used to obtain information about geomorphological features and land use patterns, an IKONOS satellite image of the study area in Chakdaha was purchased from Space Imaging Inc. to map the area. This image provides reectance data in four wave bands at 4-m spatial resolution and panchromatic data at 1-m resolution (www.spaceimaging.com; Fig. 1). Both vertical electrical sounding (VES) and electrical imaging techniques were used to investigate resistivity in both vertical and lateral directions. In VES, the Schlumberger conguration was used, in which the distance between the two current electrodes (AB) is successively expanded, while the distance between the two potential electrodes (MN) is kept at a minimum (MN 61/5 AB). The apparent resistivity (qa) is measured using the relation qa KdV =I where K is the geometrical factor and dV and I are the measured potential dierence and current, respectively. Apparent resistivity values are plotted against AB/2 on a loglog graph to give the vertical

electrical sounding curves, which were interpreted using Resix-P software to determine the true resistivity and thickness of the geo-electric layer, dened here as the computed layer based on the electrical resistivity values of the subsurface aquifer sediments. Electrical imaging involves measuring a series of constant separation traverses along a single line as the electrode spacing is increased with each successive traverse. The Wenner array was used to obtain a reasonable resolution and moderate sensitivity relative to geological noise. The initial electrode separation was 10 m in the rst traverse, which was then successively increased to 20, 30, 40, 50 and 60 m. As electrode separation leads to greater depth penetration, the measured apparent resistivity can be used to construct a vertical contour section using RES2DINV code, which displays the variation of resistivity both laterally and vertically in the section. 3.4. Reactive transport model A 1D advective transport model was developed based on the formulation presented by Appelo and Postma (1993). Vertical ow during the monsoon season recharges the upper few meters of the aquifer, since 5 m annual uctuations of groundwater level are observed (Charlet and Polya, 2006, and discussion in Section 4.3). However, this vertical ow is neglected in the present model which describes the groundwater ow at 2535 m depth as a horizontal water ow. A 3000-m 1D column, or ow tube, was dened by a series of thirty 100m-long cells. All cells have the same physical characteristics (Table 2), and reactive mineral set up equal to 83 mg Fe per kg solid sediment in agreement with ascorbic acid selective extraction measurements. Four series of cells were distinguished based on their

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Table 2 Concentration ranges of groundwater constituents sampled at Chakadaha, Nadia district, West Bengal between April 2001 and April 2002 Range at study site pH Pe As(III) As(V) Alk (HCO 3 Cl P Ca Mg Na K Fe(II) Mn(II) Al Si 6.717.67 2.27 to 0.31 0.15.83 483010,300 302270 868 19404890 6801750 3303580 70620 10177 1.928.2 0.154.19 151334 Zone 0 (cells 05) 6.93 2.05 2.79 2.79 8710 390 27 2600 1230 1030 110 160 5.6 1.04 276 Zone 1 (cells 612) 7.36 1.66 1.52 1.52 8150 950 35 2890 1150 670 100 140 3.1 1.22 284 Zone 2 (cell 1317) 6.97 1.66 1.82 1.82 10,320 1600 27 3400 1750 1690 120 170 3.1 1.30 325 Zone 3 (cells 1830) 6.93 1.66 1.25 1.25 6.686 420 8 2320 810 730 120 90 6.2 0.15 288

The measured groundwater compositions of the four zones given below were used as initial (t = 0) concentrations in the reactive transport model. All concentrations are total concentrations, except for Fe(II) and Mn(II) and are reported in lmol L1.

solution chemistry (Table 3). The water composition in Zones 0, 1, 2, and 3 corresponds to that of 2535 m deep wells #8, 42, 28 and 30, located along the transect BB 0 B00 (Fig. 2). The groundwater composition from the four wells given in Table 3 was used and 8.95 mmol of ferrihydrite/L solid phase was initially equilibrated with this groundwater. The actual Fe oxyhydroxyde sand coatings are mixed Fe(II)/Fe(III) solid compounds (Horneman et al., 2004), but since no complexation constant is available for these poorly dened solid phases (Charlet and Polya, 2006), ferrihydrite is used here as a model sorbent. The Dzombak and Morel (1990) and Appelo et al. (2002) surface complexation constants were used for As(III) and As(V), and the surface complexation capacity was coupled to the amount of ferrihydrite in PHREEQC-2 (Appelo et al., 2002). The PHREEQC numerical simulation employed an explicit nite dierence scheme, upgradient for advective transport and central in space for dispersion, with

the spatial and temporal discretization adjusted to ensure that grid Peclet and Courant criteria were met (Pe < 3 and Cr < 1). After the initial equilibration of the solid phase with a groundwater of known composition, a pore volume of groundwater within each of the 30 cells is moved to the next respective cell. The groundwater is then equilibrated once again with the solid phase and the dissolved As composition in the ow tube is calculated. A series of six shifts was performed, and composition graphed as computed after 532 (i.e. 6 88.33) years. Residence time in one cell was obtained considering a water ow velocity of 9.27 102 m/day and a total ow path of 3000 m. 4. Results and discussion 4.1. Geomorphology and remote sensing An IKONOS satellite image of the study area in Chakdaha was purchased from Space Imaging Inc. to map the study site. This image provides reectance data in four wave bands at 4-m spatial resolution and panchromatic data at 1-m resolution. The IKONOS data were processed to emphasize in dark blue or purple the presence of water in streams and ponds, and in light purple the presence of irrigated elds without vegetation (Fig. 1). Contrasting bright areas of the IKONOS image indicate dry, presumably uncultivated elds. Green areas show the vegetation of the elds that are cultivated as well tree cover that identies villages. The largest stream

Table 3 Hydrodynamic model parameters Parameter vp E Conductivity Am. Fe oxide content Units cm day1 mg kg1 Model value 20 0.4 2.34 83 Measured range 0.40 0.42 20014,000

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meandering in a southerly direction west from the study area is the so-called Hooghly River, a branch of the Ganges which ows downstream through Kolkata City. The ood plain, located on the west side of the study area, is agricultural land with high moisture content (typical of deltaic alluvium) and no habitation. It is characterized by small elds, shown as pink or green stripes in Fig. 1, distributed perpendicular to former meanders of the Hoogly River where small streams are now owing. Irrigation is used for the newly introduced dry-season rice called Boro that now provides more yield than the traditional rice grown during the monsoon season, called amman, and boro rice cultivation and irrigation increased together from 1970 to the present day. A natural levee, marked as a dark curved line on the west edge of Fig. 1, separates this ood plain from the inhabited area and the tree cover. The village is organized along the NS railway track and around the railway station, where most streets converge. Villages and elds share the available land in roughly equal proportion in the study area, where the population density is nearly three times higher than the West Bengal state average. Throughout the village, dark blue rectangles denote local ponds, from which clay-rich building materials were exca-

vated. These ponds, which cover in some place $15% of the land, are disconnected from the rivers, but act as engineered aquifer recharge systems during the wet season, until in the dry season their bottom sediments become hydraulically disconnected from the aquifer, and their water levels remain several meters above the water table. The distribution of wells in the same area is given in Fig. 3. Responses to a questionnaire collected with the well samples indicate that the vast majority of these wells were paid for by individual households and therefore are privately owned. The survey data also indicate that half the existing wells in the study area were installed between 1995 and 2000, i.e., after the discovery of the epidemic of arsenicosis in West Bengal. Recently however, these wells have been less and less used for drinking-water supply, since four 150 m deep DPHE wells were drilled and rich families connected to their water distribution system. 4.2. The arsenic plume Total As concentrations in the groundwater are typical of a hotspot, with a maximum of 480 lg L1, surrounded by waters of lower As content (e.g. 10 lg L1) (Fig. 3). The As plume present

6.0 5.5 5.0 4.5

Zo ne
N2305'

4.0

0 Zo ne 1 Zo ne Zo ne

3.5 3.0 2.5 2.0

1.5 1.0 0.5 0.0

[As]tot mol/l E8831' Hoogly river railway E8832' Railway station School

Fig. 3. Aqueous As (total) iso-concentration map at the end of the dry season, calculated using SURFER 7.0.

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in the Chakdaha aquifer has signicantly dierent physico-chemical characteristics, compared with other analogous sites in the Bangladesh part of the BDP aquifer (Charlet and Polya, 2006). The Chakdaha aquifer has a slightly higher proportion of As(V) than As(III) species (42% As(III) versus 58% As(V)). EhpH diagrams show the oxidation potential to be controlled by the Fe2+/Fe(OH)3(s) couple (Charlet et al., 2005), and not by the sulde/sulfate couple as observed elsewhere (Harvey et al., 2002). Indeed, at sites located in Bangladesh, As(III) is the dominant thermodynamically stable form, and S is present as amorphous acid volatile suldes (AVS) and aqueous species (Harvey et al., 2002). Under these conditions, As(III), which is less strongly sorbed than As(V) on ferrihydrite, becomes adsorbed to some extent on FeS(s) (Wolthers et al., 2005), as shown to be the case in Bangladesh (Wolthers et al., 2003). 4.3. Groundwater hydrodynamics Groundwater pumping during the dry season draws more water than is being recharged, as indicated by the cone of depression below the Chakdaha city centre (Fig. 2, wells 21, 9, 10 and 11). The center of the depression cone coincides with the 150 mdeep public water supply well, located near tube well #9, which supplies a quarter of the drinking water for the 75,000 inhabitants of Chakdaha. Groundwater pumping for domestic and industrial purposes may therefore be responsible for recently drawing groundwater from the shallow aquifer into deeper aquifer levels. Groundwater recharge is composed of a mixture of C-rich surface waters which enter the aquifer all year round, and rainwater which enters the aquifer from April until ooding starts in June (Harvey et al., 2002; see Charlet and Polya, 2006, for a review). On the onset of monsoon (JuneAugust) groundwater levels rose by $2 m indicating rainand pond-water as the major source of recharge. However, outside the monsoon period groundwater is mainly recharged from surface water bodies and the Hooghly River, as indicated from the water level iso-contour map of pre- and post-monsoon times (Nath et al., submitted for publication). The result of the detailed investigation on groundwater recharge/discharge by the Hooghly River, rainfall and surface water bodies during the pre- and postmonsoon period in the study area are presented elsewhere (Nath, 2006; Nath et al., submitted for

publication). Recharge by local articial ponds used more than 30 a ago to supply drinking water (e.g. those located near wells #12 and #42, Fig. 2) also create local maxima in the water level, e.g. in June just before the monsoon started (Fig. 2). 4.4. Aquifer structure and sediment solid phase Resistivity is primarily a function of porosity, pore uid resistivity (salinity), temperature and clay content. Of all these sediment properties, the clay content and related porosity are the most important; resistivity generally increases as porosity increases. The geometry and lithology of the upper aquifer system can thus be dened by sounding and resistivity proling. The inverse model resistivity section (Fig. 4a) clearly distinguishes the silt/clay rich, low resistivity surface layer in the upper 13 m (1525 X m) from the deeper productive aquifer (1525 m depth, 2648 X m), where most wells are extracting groundwater. Iso-resistivity contours recorded at 15 and 25 m depth indicate a conductive aquifer and changes in porosity as one gets away from the river (Fig. 4b). The resistivity, and thus porosity, is high below the oodplain at both depths, and steadily decreases as one moves towards the SE, i.e. along a groundwater ow line. The deeper productive aquifer sediment material is a rather homogeneous gray, ne to mediumgrained sand, made of Fe(II)/Fe(III) oxide-coated quartz sand particles, micas, feldspars and carbonates, with the ner particles made of illite, magnetite and illmenite. No peat was found, which has been previously hypothesized to be associated with higher concentrations of dissolved As, through reductive dissolution of Fe oxyhydroxides or through adsorption of As(V) on detrital organic C (McArthur et al., 2001). Inverse resistivity proles show the occurrence of low resistivity in the upper layer (Fig. 4a) where IKONOS satellite imaged surface morphology shows the presence of channel scars and remnants of former courses of the Ganga River and its tributaries (Fig. 1). These paleomeanders and oxbow lakes were hypothesized to be the location of As deposition (Nath et al., 2005), where mangrove vegetation may have induced the precipitation of As-rich suldes (As-rich-pyrite and arsenopyrite). Various authors (Charlet and Polya, 2006, and references included therein) have suggested that As may have been recently released through sulde oxidation by O2, introduced into the aquifer by the massive increase in dry-season irrigation pumping.

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Fig. 4. Geophysical data: (a) resistivity prole along cross-section AA 0 (Fig. 2); horizontal and lateral distances are given in meters. From top to bottom: measured apparent resistivity, calculated apparent resistivity and inverse model resistivity pseudosections. (b) Isoresistivity contours at 15 and 25 m depth, respectively.

Bulk sediment samples were collected from various boreholes (Figs. 2 and 5) and core samples (silty clay layer at 18 m depth) from Borehole 4 (B-4) where it was assumed, based on geophysical results and on the IKONOS image, there were paleomeanders, but the expected clay-, sulde- and As-rich lenses were not found. Selective As extraction studies on B-4 sediment core samples are summarized in Fig. 6. The total extracted As concentration was 3.0 0.4 ppm. Two major sinks for As are the amorphous Fe(III) oxide (34% 8% of total extracted As; fraction F4) and acid volatile suldes and/or carbonates (19% 7% of total extracted As; fraction F3). The heterogeneity observed in the 30-cm-long sediment core collected at 18 m depth is high as shown in Fig. 5. Attempts to determine the bulk As speciation by X-ray adsorption near-edge spectroscopy (XANES) at the European synchrotron research facility (ESRF) in Grenoble failed, as on-line oxidation of As was observed while making the measurement. Oxidation of As was tentatively attributed to reaction with Fe(III) oxyhydroxides under the high energy beam. No evidence of crystallized or amorphous solid sulphide was observed. In conclusion

As is sorbed, i.e. adsorbed or coprecipitated (Sposito, 1986), on amorphous Fe oxyhydroxides, AVS and/or carbonates, in addition to micas (Charlet et al., 2005). 4.5. Aquifer geochemistry The groundwater chemistry changes signicantly as water ows along a BB 0 ow line (Fig. 2). The Hooghly River has a pH of 8.25 0.15 and together with irrigated elds it recharges the groundwater during post-monsoon (Nath et al., submitted for publication). Within the rst kilometer from the river shore, pH decreases rapidly to pH 6.9, the average pH value in the aquifer (Fig. 7), while at the same time alkalinity increases from 6.1 0.5 mmolc L1 in the river to 1522 mmolc L1 in the aquifer. In the recharge area, Eh is high and the groundwater is nearly free of aqueous Fe(II). Groundwater temperature is high, and remains between 26 C and 28 C, except for a few wells close by the river, where groundwater temperature reaches 29 C. Alkalinity and pH measurements, combined with carbonic acid equilibria, lead to a P CO2 ranging from 102.15 to 100.85 atm, with an

L. Charlet et al. / Applied Geochemistry 22 (2007) 12731292

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23

Resistivity contours at 20m depth

88 23

Resistivity contours at 24m depth

88
Fig. 4 (continued)

average value of 101.3 atm, i.e. a value far greater than atmospheric P CO2 . Calcium is rather constant throughout the aquifer, with an average concentration of 2.8 0.6 mmol L1. The groundwater is roughly at equilibrium with calcite, with a saturation index X ranging from 0.22 to +0.44, with an average X value of +0.14. Other major cations, in order of decreasing concentration, are Mg2+, Na+, K+, Fe2+ and Mn2+ (Table 2). The groundwater is hard, with an average hardness of 140 mg equivalent CaCO3 L1 (based on the sum of Ca2+ and Mg2+ concentrations). Bicarbonate represents up to 90% of the inorganic anion equivalent concentration. Other anions, in order of decreasing concentration, are Cl, SO2 ; NO and PO3 . No trend in Cl concentra4 3 4 tion could be used to trace the groundwater recharge or the mixing of dierent waters. Total

PO3 ranges from 8 to 68 lmol L1. Dissolved 4 SiO2 is nearly constant, ranging from 0.15 to 0.33 mmol L1 throughout the aquifer. 4.6. Anoxia and aqueous Fe(II) Surface water inltrating into the upper aquifer is heavily loaded with untreated waste from the 75,000 inhabitants of Chakdaha. Consequently, the groundwater concentration of dissolved organic C is generally high (0.97.5 mg C L1), with an average concentration of 4.4 1.9 mg C L1, similar to inltrates from organic-rich sediments (Harvey et al., 2002). Outside the paddy elds located in the ood plain recharge area along the Hooghly River (see Metral et al., submitted for publication, for a detailed study of this recharge area), Fe2+concentrations range

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Fig. 5. Vertical lithological distribution pattern along a ow path (cross-section BB 0 B00 , Fig. 2), indicating various granulometric classes. The approximate depth of the water level is shown. For example at B11, the patterns represent the following classes with increasing depth: silty clay, sandy clay, coarse sand, silty clay, sandy clay, coarse sand; ne sand is indicated in white.

between 0.010 and 0.017 mmol L1. Groundwater is at equilibrium with siderite (FeCO3), with a saturation index, X, ranging from 0.80 to +0.47, and average X value of 0.05. Dissolved O2 is always below 0.06 mg L1, the detection limit of the Winkler method. Under these conditions, Fe oxides are likely being reductively dissolved by dissolved organic matter, resulting in the groundwater recharge becoming enriched in Fe2+and HCO 3 (Appelo et al., 2002): 4FeOOH CH2 O 7H2 CO3 4Fe2 8HCO 6H2 O 3 1

4.7. Competitive sorption In addition to oxidationreduction processes, competition for adsorption sites may also act to mobilize As in groundwater. The groundwaters of this aquifer contain high amounts of HCO ; PO3 and dissolved H4SiO4 (Table 2). 3 4 Sources of PO3 in the groundwater include oxida4 tion of organic matter and fertilizer used in modern agricultural practices (McArthur et al., 2001). Aqueous silica, which results from strong weathering of the silicate minerals in Ganges sediments, could also displace As from Fe hydroxide surfaces (Appelo et al., 2002). But silicate concentrations are nearly equal throughout the groundwater in the area, which means silica displacement of adsorbed As will not vary much spatially. Thus, HCO (and to a small extent, PO3 ) anions repre3 4 sent the most important species which compete with As species for adsorption sites at mineral surfaces (e.g., Fe/Mn oxyhydroxides, clay minerals and weathered mica), consequently releasing As into the groundwater. It should be noted that anion exchange is not the only cause of high As concentrations in West Bengal groundwater. Most of the As present in

Ferrous iron concentrations shown in Fig. 8 suggest reaction (1) does not occur at the river bed, but rather at the border between the rice eld plain and the terrace where the city has been built, that is, at the location of recent paleomeanders (Fig. 1). Hence, the boundary between oxic and anoxic groundwaters may be due to: (i) intense recharge of the western part of the aquifer during the monsoon when rice elds are ooded, (ii) the presence of a former riverbed at the eld-city boundary exhibiting intense microbiological activity, or (iii) a combination of the two.

L. Charlet et al. / Applied Geochemistry 22 (2007) 12731292

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As (mg/Kg)
0 1 2 3 4 5

10

Depth (cm)

15

F1 F2 F3 F4 F5 F6

20

25

30

35
Fig. 6. Dissolved As concentrations obtained by a sequence of extractions (F1F6) which target dierent solid phases (Keon-Blute et al., 2001, see Table 1). F1 Ionically bound As; F2 Strongly adsorbed As; F3 As coprecipitated with AVS, carbonates, Mn oxides and very amorphous Fe oxyhydroxides; F4 As coprecipitated with amorphous Fe oxyhydroxides; F5 As coprecipitated with crystalline Fe oxyhydroxides; and F6 Orpiment and remaining recalcitrant As minerals. Results are reported as a function of depth.

the area is sorbed, i.e. adsorbed to, or co-precipitated with (Sposito, 2004), sediment particles. The selective extractions performed on the B-4 sediment core give insight into the various sorption processes at work in this heterogeneous medium. Arsenic sorbed to carbonate and acid volatile suldes amounts to 0.8 ppm, As sorbed to ferrihydrite and other amorphous Fe(III) oxides to 1.1 ppm and As sorbed to crystalline Fe(III) oxide to 0.4 ppm (Fig. 6). Although the amount of As sorbed to ferrihydrite in the river suspended particles is high (Appelo et al., 2002), it may contribute little to the As hotspot since reductive dissolution does not occur in the present river bed, but rather, within the sediment at the level of a paleomeander. Therefore, much of the As present in this groundwater originates from the aquifer sediment, where it may be found as outerand inner-sphere surface complexes (fractions F1 and F2, respectively). However, most of the As seems to be coprecipitated within amorphous

(fraction F4) and crystalline (fraction F5) Fe hydroxides (Waychunas et al., 1993), and within carbonate or AVS (fraction F3) minerals (Roman-Ross et al., 2003). Therefore, in order to accurately assess As behavior in these groundwaters, various sorbent phases should be ideally taken into consideration, and aqueous carbonate and Fe(II) surface complexation must also be taken into account. 4.8. Role of micas Arsenic also adsorbs strongly to clay particles, which are transported through the river system as suspended load (Ansari, 1997). At pH 67, Frost and Grin (1977), and Charlet et al. (2001), Charlet et al. (2005) observed 90100% of As(V) and 40% of As(III) adsorbs to kaolinite and montmorillonite from a US landll barrier and from a North Mortagne industrial site in France, respectively. Saifullah (1988) highlighted the complex

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CH2

N2306'

AA4

8.3 8.2
AA2

8.1 8.0
AA1

F10 CH1 AA25 F4 F5 F7 AA23 AA8 F3 F2 AA56 AA50 AA26 AA6 AA7 F8 AA27 F6 AA48 AA24

AA3

AA33

7.9 7.8 7.7

AA52 AA49 AA55 AA54 AA0 AA5 F1 AA42 AA28 AA30 AA9 AA10 AA31

7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7

N2305'

AA34 AA43 AA21

AA51

AA12

pH

E8831'
Hooghly river Hoogly river

E8832' Railway station School

railway

Fig. 7. Groundwater pH contour map at the end of the dry season, calculated using SURFER 7.0.

CH2

N2306'

AA4

0.16
AA2 F10 AA3 AA24 AA25 F4 F5 F7 AA23 AA8 F3 F2 AA56 AA50 AA26 AA6 AA7 AA43 AA21 AA12 AA34 AA51 F8 AA27 AA9 AA42 AA52 F6 AA48 AA49 AA55 AA54 AA0 AA5 AA28 AA30 AA10 AA31

0.14
AA33 AA1

0.12 0.10 0.08 0.06 0.04 0.02 0.00

N2305'

[FeII] mmol/l

E8831' Hoogly river Hooghly river railway

E8832' Railway station School

Fig. 8. Groundwater Fe(II) iso-concentration map at the end of the dry season, calculated using SURFER 7.0.

L. Charlet et al. / Applied Geochemistry 22 (2007) 12731292

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role that organic matter and clay minerals play, along with Fe and Mn oxyhydroxides, in regulating As concentrations. The Charlet et al. (2001) study also shows about 100% of both As(III) and As(V) adsorb to Black slag (organic matter) from North Mortagne, over a pH range of 38. In addition, oxidation of organic matter itself may release As during the reductive dissolution of As-rich hydroxides. About 30% of the total mineral mass in the Ganges sediments is present as micas (Ansari, 1997). Micas are transported by the Ganges River as suspended load for about 2500 km, during which time they are chemically and physically weathered (Ansari, 1997). Once buried in anoxic conditions, micas (e.g., phlogopite) can adsorb As in the presence of Fe(II) and transform As and other pollutants into less toxic forms (Charlet et al., 2002). In particular As(V) may react with surface Fe(II) to form surface nanoparticles, with a mixed AsFe composition and mixed oxidation states. A recent X-ray photoelectron spectroscopy (XPS) study of As sorbed on micas indicates that the oxidation state of As, sorbed as As(V) on weathered muscovite mica grains, may have an oxidation state of (III) or lower (Charlet et al., 2005). A more detailed study on adsorptiondesorption of As on mica from the Ganges Delta has been carried out with the oxidation status of arsenic systematically studied by XPS (Chakraborty et al., in press, submitted for publication). The silt-sized fractions of muscovite and biotite micas are eective for removal of arsenate and arsenite from solution in the groundwater pH region (6.57.5; Chakraborty et al., in press). Moreover, an X-ray photoelectron spectroscopic study of reduction of As by biotite also provides an important mechanism in the immobilization/mobilization of As in Bengal and Bangladesh groundwaters (Chakraborty et al., submitted for publication). So, micas and other phyllosilicates represent an important component of the As cycle in the aquifer sediments, although lack of surface (de)protonation data, and lack of surface complexation data with species other than As (phosphate, carbonate, silicate) prohibit the inclusion of micas in the following model. 4.9. Modeling As migration The displacing eect of HCO may oer an 3 explanation for high As concentrations in Chakdaha groundwater, given that the pH values and

alkalinities of river water and groundwater are very dierent. The Hooghly river water has a low CO2 partial pressure of 103.0 atm and a high pH. On the other hand, the hotspot and downstream groundwater has a very high alkalinity of 4.8 10.3 mmol of HCO L1 , as a result of relatively 3 high temperatures, high CO2 partial pressures in the aquifer, and presumably high microbiological activity in the paleomeander. The contribution of the various processes were calculated by rst equilibrating the groundwater in each of the dierent zones (Table 2, Fig. 3) with the model solid phase. Organic C, which reduces dissolved O2 and ferrihydrite to give aqueous Fe(II) according to Eq. (1) at the paleomeander, was assumed to be constant downstream, thus not to dissolve any more Fe(III) hydroxides and not release As upon oxidation (Starr and Gillham, 1993). Indeed, the Fe(II) concentration remains fairly constant downstream in Zones 1, 2 and 3, ranging only from 0.14 to 0.17 mM. The log K value of the reaction: H3 AsO4 2H 2e H3 AsO3 H2 O 2

was set equal to 16.0 instead of 18.89 (Parkhurst and Appelo, 1999) in order to qualitatively reproduce the As(III)/As(V) balance observed throughout the study site. Model calculations were then rst performed taking into account only the 8 rst chemical reactions given in Table 4, i.e. only As adsorption reactions and reactions of protonation/deprotonation of reactive surface groups. As the groundwater moves from one 100 m-long cell to the next (residence time in one cell:
Table 4 Surface reactions taken into account in the reactive transport model (Appelo et al., 2002) Surface complexation reactions (1) (2) (3) (4) (5) (6) >Fe OH + H = >Fe >FewOH = >FewO + H >FesOH + H+ = >Fes OH 2 >FesOH=>FesO + H+ >FewOH + Fe2+ = >FewOFe+ + H+ >FewOH + AsO3 + 3H+ = >FewH2AsO4 + H2O 4
w +

log Kint 7.29 8.93 7.29 8.93 2.98 29.31 23.51 10.58 12.56 20.61 31.29 25.39 17.72

OH 2 +

(7) >FewOH + AsO3 + 2H+ = >FewHAsO4 + H2O 4 (8) >FewOH + AsO3 = >Few H2 AsO3 + H2O 4 4 (9) >FewOH + CO2 + H+ = >Few CO2 + H2O 3 3 (10) >FewOH + CO2 + H+ = >FewHCO3 + H2O 3 (11) > Few OH PO3 3H > Few H2 PO4 H2 O 4 (12) > Few OH PO3 2H > Few HPO H2 O 4 4 (13) > Few OH PO3 H > Few HPO2 H2 O 4 4

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88.66 a) and is again equilibrated with the model mineral reactive surface, one may observe either a net removal of As from the groundwater, as for As(III) when water from Zone 1 i.e. the hotspot enters Zone 2 (Fig. 9a), or a release of previously sorbed As as observed in Zone 2 As(V) front (Fig. 9b). Model calculations were afterwards repeated, taking into consideration competition for adsorp-

tion sites by either HCO ; PO3 or Fe2+ or by 3 4 the three ions together. The eect of sorption site competition on the As concentration in West Bengal groundwater is graphed in Fig. 9a and b. Whereas Fe2+ competition does not aect signicantly the concentration prole (Fig. 9a), competition by anionic species for reactive surface sites aects the propagation of the contaminant plume in dierent ways. Phosphate ions unexpectedly

a 400
Zone 0
350

Zone 1

Zone 2

Zone 3

300 As(III) concentration (ppb) As(III) init without competition 250 effect of carbonates effect of Fe(II) phosphate effect of Phosphate Effect of all components 150

200

100

50

0 0 500 1000 1500 Distance (m) 2000 2500 3000

400

Zone 0
350

Zone 1

Zone 2

Zone 3

300 As(V) concentration (ppb)

As(V) init without competition

250

effect of carbonates effect of Fe(II) phosphate effect of Phosphate Effect of all components

200

150

100

50

0 0 500 1000 1500 Distance (m) 2000 2500 3000

Fig. 9. Results of the 1D reactive transport model predicting plume propagation: (a) As(III) and (b) As(V). The various scenarios dier depending on whether Eqs. (1)(13) (Table 4) are taken into account or not.

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have little aect on the propagation of arsenate ions but have a strong impact on the As(III) fronts: the Front in Zone 3 is accelerated, whereas it is slowed down in Zone 2. However, HCO 3 remains by far the most important competing species (Fig. 9), producing an important desorption of As in Zone 2 and thus peak As concentrations in solution which may threaten the Chakdaha City Centre. This result conrms previous studies where high As concentrations in groundwater were correlated with high HCO concentrations (Welch 3 and Lico, 1998; Nickson et al., 2000). The displacing eect of HCO on As sorbed to Fe oxyhy3 droxides in the reactive transport model has been conrmed using FTIR spectroscopy. In their experiments Voegelin and Hug (2003) oxidized surface As(III) by H2O2, and they quantitatively observed the disappearance of the HCO peak 3 as the As(V) peak developed, demonstrating that oxidative desorption of As leads to increased sorption of HCO . 3 Thus when sediments deposited from lowcarbonate river water containing large amounts of sorbed As become exposed to the high-carbonate groundwater, As may become mobilized by displacement from the sediment surface due to competitive eects of carbonate sorption. Paleohydrological studies are being performed to further quantify this contrast between deposition and present day physico-chemical conditions (Guillot and Charlet, submitted for publication). The model results suggest that this eect could lead in the future to even higher As concentrations than those observed today, and that arsenate and Fe(III)-oxide reduction is not even necessary to achieve the high As groundwater loads. This conrms previous studies which pointed out the co-occurrence of high alkalinity and high As in groundwaters in SW USA and in India (Welch and Lico, 1998; Welch et al., 2000; Nickson et al., 2000). The mobilization of As by HCO has also been used by Anawar et al. 3 (2003, 2004) to explain the high As concentrations in Bangladesh groundwaters, as well as by GarciaSanchez et al. (2005) to explain the high As concentrations in groundwater in central Spain. 5. Conclusions High levels of As in well water are causing widespread poisoning, posing the greatest threat to human health in West Bengal. To assess the origin

and mode of As mobilization, an extensive geophysical and geochemical data set was collected at an As hotspot in a typical aquifer located along the Hooghly River, 60 km north of Kolkata City, near the city of Chakdaha. Arsenic is present not only in amorphous and crystalline Fe(II)/Fe(III) hydroxides, but also in other solid phases present in this sediment such as carbonates and mica particles. Once water passes through bacterially active paleomeanders located at the border between the ood plain and the inhabited terraces, Fe hydroxides undergo reductive dissolution and release As and Fe reduced species. Carbonate may dissolve under the resulting high P CO2 , also leading to the formation of the observed hotspot. Therefore, release of redox species depends on geomorphological characteristics and land-use patterns. Total As concentrations range from 0.5 to more than 60 lmol L1. The As plume present in the West Bengal aquifer near Chakdaha has signicantly dierent physicochemical characteristics, compared with other analogous sites in the Bangladesh part of the BDP (Harvey et al., 2002). The West Bengal aquifer has a slightly higher proportion of As present as As(V) species with no observed sulde phases (As-rich pyrite or arsenopyrite) present, and redox is mostly controlled by the Fe2+/ Fe(OH)3(s) couple. Arsenic release appears to be controlled by dissolution of Fe(II/III) hydroxides and carbonates. Spatial distribution maps of As and water levels indicate the presence of a contaminant plume moving during the dry season towards a major drinking water supply well in the most densely populated area of the city, near the railway station. Results from a 1D horizontal reaction transport model show that, due to the slow horizontal groundwater velocity ($1 m a1) and to the ecient retardation created by Fe oxide sorption sites, the plume is apparently moving very slowly in the direction of Chakdaha (Fig. 9). However, this optimistic conclusion may not hold once the spatial variability (Figs. 3 and 4) of parameters such as porosity and amorphous Fe hydroxide content have been measured and fully integrated into the model. For instance, model calculations which take into account the competition between other aqueous major ions, such as HCO ; PO3 , Fe2+ and As indicate the 3 4 plume is actually moving much faster. A few decades are still necessary, however, for the plume to reach the major population center. Rather, the real

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threat for the local population may come from a vertical transfer of As from the shallow, contaminated aquifer to the 150-m-deep As-free wells recently used to distribute large quantities of high quality drinking water. Acknowledgements This research was partly funded by the Indo French Centre for the Promotion of Advanced Research (IFCPAR), Project #W1-2200, and by grants from the French Ministry of Research (ACI-Eau), CNRS (EC2CO) and the Embassy of France in New Delhi and We thank Anthony Le Beux and Anne Audrey Latscha for their eld work and Michel Dietrich for his help in geophysical data treatment. A.A. is thankful to the French Ministry of Science and Technology for a visiting scientist fellowship at LGIT. The authors acknowledge the editorial work of Victoria L. Knowles and technical assistance from Delphine Tisserand for running comparative speciation tests with HPLC-AFS. Thanks are due to Richard B. Wanty for Editorial Handling. References
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