Abstract

The water quality and chemistry of the groundwater of the fluvial Bengal plains have been investigated. It has been found that shallow aquifers (< 50 m bgl) are contaminated in a few pockets, surrounded by areas with low arsenic (As)/As-free groundwater, while the deeper aquifer (> 100 m bgl) is generally free from As (< 10 g/L). It also reveals that multiple As mobilization processes are occurring simultaneously, rather than any single geochemical process. An attempt has been made to demonstrate the degree of As heterogeneity with groundwater quality, and this has been followed by a few local conditions. The study further suggests that the.As distribution (spatio-vertical) helps to identify safe shallow aquifers, and several signatures (colour of the sediments /land use pattern/ geomorphological features /local recharge events) are apparent that can be useful for formulating long-term mitigation options.
1. Introduction Drinking water has always been considered as the major ingestion route of As to the human system and recently, exposure from the food chain has also been reported. The occurrence of As in groundwater (>50 g/L) is observed in several pockets surrounded by large areas with low As/As-free water (1). The As distribution pattern is heterogeneous in nature and often shows severe anomalies with respect to spatial and vertical distribution. The influence of local conditions on As release/mobilization both spatially and vertically is reported (2). In this study we would like to document the spatial scale of As heterogeneity in a deltaic region of West Bengal. The inter-relationship between the prevailing local conditions and surveyed wells is studied carefully that often regulates the (hydro)chemical environment, notably the concentrations of redox elements. Ultimately, this helps to formulate the planning of water supply structures and better management of the affected aquifers. The study area (~ 400 km , 23.02- 23.14 o N; 88.49- 88.620 E) encompasses part of the worlds largest delta. The aquifers consist of thick (~ up to 250 m) sands overlain by a surface silty clay aquitard (~ 20 -40 m). The upper aquifer material consists of silica sand (86 %) with minor biotite, muscovite, illite and iron oxyhydroxide, while the lower aquifer passes downward into silty sand. The area lies within the active flood plain of the Hooghly-Bhagirathi River (3). 2. Methods and materials Groundwater samples were collected in acid-washed bottles. The sampling procedures have been described previously (1,3). Samples were filtered (0.45m membrane filter) and collected in three separate bottles: (i) As by AAS in HG mode (Varian 440 A), (ii) cations and trace elements (acidified with suprapure HNO3 T), and (iii) major anions. Analysis of As(III) and As(V) was made through a disposable cartridge (Metal Soft Centre, USA). Anion analyses were determined by ICP and cations by IC. Fe and Fe(II) concentrations were measured spectrophotometrically using 1, 10 phenanthroline (510 nm). DOC samples were measured by a Shimadzu 5000 TOC analyzer. Undisturbed core samples were collected in HDPE bags purged with nitrogen on-site (wash sediment colours were observed soon after their recovery from the borehole, prior to atmospheric oxidation).Sediments were analyzed by several techniques. C was analyzed with the help of a CNS analyzer (Leco) after initial dissolution in 10% HCl to remove inorganic carbon. Commercially available reference materials (NIST-STM1643e/STM 2583) were used for quality control.

3. Results and discussion 3.1. Groundwater chemistry and aquifer materials Ground waters are normally of Ca-HCO type irrespective of depth and type of aquifer sediments. In shallow and deep aquifers, groundwaters have circum-neutral pH (5.957.98) and a narrow temperature range (25.130 C). The electrical conductivities vary but are relatively high (450 1514 S/cm) in shallow aquifers and lower in the deeper aquifers (180856 S/cm). This suggests that groundwaters in the two aquifers are fresh and possibly different in age and origin (2). The Eh

values of shallow groundwater samples show highly reducing nature (down to -187 mV). These samples often contain high As T 3 (up to 340 g/L; notably as As(III)), Fe(II) (0.010.2 mmol/L), HCO 3 - (4.8310 mmol/L) and low to moderate concentrations of P (0.010.07 mmol/L) and Mn (up to 3.2 mg/L). DO, SO concentrations are low/very low, or even absent. The NH4+ and DOC concentrations are moderate to high (NH4+ up to 4.5 mg/L and DOC up to 10.53 mg/L) and are often high in those shallow wells where existing local land use (habitation/agricultural field/geomorphological features) has been noticed during the field visit. The most interesting is the conservative behaviour of Cl-which is generally low in concentration (mean 22.8 mg/L) but can be high (up to 147 mg/L) in those wells which are located near (~ 3-5 m) sanitation/ponds within habitations. The non-contaminated tube wells are generally free from As (<10 g/L) and their E h is relatively high (mean 26 mV) with high concentrations of HCO and low/very low Fe along with relatively high concentrations of nitrate and sulphate. This indicates that these wells occur under relatively oxic conditions. Surveyed contaminated wells are generally in lowland areas (present day flood basin and plain/back swamp). These are the areas where accumulation of organic matter is common and there are easily bio-available and often can be introduced into the aquifer during groundwater recharge (local recharge events). Biodegradable organics also likely play a role in regulating the redox environment in the shallow aquifers. The presence of high concentrations of DOC, HCO and redox-sensitive elements (As/Fe/Mn) is further evidence of a reducing environment associated with the highly contaminated wells. By contrast, the non-contaminated wells are generally located in the upland area (present day levee, sand bar) that is free from natural organics and relatively oxic in nature. Aquifer depths are also playing an important role and deeper levels are relatively uncontaminated where low As or As-free wells are common. XRD data indicate that quartz and micas (muscovite, biotite and chlorite) dominate the sediment mineralogy. The average C content of the sediment is relatively low (up to 0.5 %) and there is no buried peat. The limited supply of the C org indicates that the sedimentary carbon source is not an essential parameter (singular and/or sufficient) for the development of the local reducing conditions in the aquifers. The sediment colours (grey/off-white to white/orange to red) are often important to distinguish between oxidized and unoxidized aquifers (Fig. 1b). Orange/red sands (oxidized org aquifer) are generally associated with an oxidizing environment where tube wells yield As-free water whereas grey/bluish-grey/white/off-white sands yield high-As water and are associated with a reducing environment. 3.2. As spatial distribution and safe water supply The spatial distribution of As indicates that the contaminated wells are generally surrounded by the safe wells (Fig. 1a). This is more pronounced in the lowland areas (south and south-eastern parts). Safe water wells are rare in the flood basin area where sediment colour is generally grey to bluish grey. The distribution of As is a function of site characteristics and land use around monitored wells. The mean As concentration varies among the selected site characteristics where wells adjacent to agricultural fields have the highest mean value (67 g/L) followed by surface water body (60 g/L), sanitation coupled with 42 and NO3 33-surface water body (49 g/L), sanitary installations (44 g/L). The distribution of Fe with respect to As shows a strong relationship within the south-eastern part of the study area, whereas the distribution of Mn shows a relationship with As in the north-western parts. The competitive ion-exchange process is also important where local anthropogenic input is regulating the system (wells adjacent to agricultural

fields), because of the high PO4 3- input from the locally used fertilizers (PO4 3- chemistry is very similar to the As oxyanions). The concentrations of oxyanions (NO3-/SO42-) are important because they act as a terminal electron acceptor in aqueous systems. As concentration (up to 9 g/L) in groundwater is relatively low where NO3- is high (up to 12.68 mg/L). This suggests that the groundwater chemistry of the aquifer is influenced by local recharge events and becomes more oxic due to local anthropogenic input. The distribution of redox species [iAs(V)/(III)/Fe(III)/(II)/NH 4/NO] in specific sites under different land use is distinct and indicates the variation of the redox status of the aquifers under specific local conditions. This further suggests that a single mechanism (reductive dissolution of Fe/Mn-oxyhydroxides) is not sufficient to explain the heterogeneous As distribution pattern. It is likely that multiple mechanisms are operating to maintain As release and distribution. A delineation of risk free aquifers with respect to physico-chemical characteristics (base cations/E h/DOC/HCO3 3 ), generally elevated in the contaminated aquifers, can be useful for identifying groundwater as a safe resource of water. This will be further ensured by sediment colours (grey/white unfavourable; orange/red favourable), along with its depth dependence and local land use mapping. A field manual can be made and necessary skill (training of local villagers/tube well drillers/school teachers/local leaders) may be developed to supply safe groundwater rather than depending on As removal options including articulated piped water supply that often fail in remote villages. These mitigation options are less eco-friendly, user-friendly and cost effective. 4. Conclusion As-contaminated wells generally occur in small pockets (~ 50-100 m2) of Holocene reducing (grey sand) shallow aquifers which overlies an relatively oxidised unit (red sand) in a deeper aquifer notably free from As. The critical examination of the groundwater composition reveals that Fe oxyhydroxide reduction and As mobilization (widely expected reduction model) may not be the only process to explain high As groundwater in shallow aquifers. The competitive exchange of ions can also influence As distribution when the wells are located near to agricultural fields due to the PO4 3-input from the locally used fertilizers.