Arsenic Levels in Groundwater from Quaternary Alluvium in the Ganga Plain and the Bengal Basin, Indian Subcontinent: Insights into Influence of Stratigraphy

Late Quaternary stratigraphy and sedimentation in the Ganga Alluvial Plain and the Bengal Basin have influenced arsenic contamination of groundwater. Arsenic contaminated aquifers are pervasive within lowland organic rich, clayey deltaic sediments in the Bengal Basin and locally within similar facies in narrow, entrenched river valleys within the Ganga Alluvial Plain. These were mainly deposited during early-mid Holocene sea level rise. Arsenic was transported from disseminated sources as adsorbed on dispersed phases of hydrated-iron-oxide. These were preferentially entrapped as sediment coatings on organic-rich, fine-grained deltaic and floodplain sediments. Arsenic was released later to groundwater mainly by reductive dissolution of hydrated-iron-oxide and corresponding oxidation of sediment organic matter. Strong reducing nature of groundwater in the Bengal Basin and parts of affected middle Ganga floodplains is indicated by high concentration of dissolved iron (maximum 9-35 mg/l). Groundwater being virtually stagnant under these settings, released arsenic accumulates and contaminates groundwater. The upland terraces in the Bengal Basin and in the Central Ganga Alluvial Plain, made up of the Pleistocene sediments are free of arsenic contamination in groundwater. These sediments are weakly oxidised in nature and associated groundwater is mildly reducing in general with low concentration of iron (<1 mg/l), and thus incapable to release arsenic. These sediments are also flushed free of arsenic, released if any, by groundwater flow due to high hydraulic head, because of their initial low-stand setting and later upland terraced position.     

Arsenic-contaminated groundwater from parts of Damodar fan-delta and west of Bhagirathi River,West Bengal,India: influence of fluvial geomorphology and Quaternary morphostratigraphy

Arsenic contamination in groundwater affecting West Bengal (India) and Bangladesh is a serious environmental problem. Contamination is extensive in the low-lying areas of Bhagirathi–Ganga delta, located mainly to the east of the Bhagirathi River. A few isolated As-contaminated areas occur west of the Bhagirathi River and over the lower parts of the Damodar river fan-delta. The Damodar being a Peninsular Indian river, the arsenic problem is not restricted to Himalayan rivers alone. Arsenic contamination in the Bengal Delta is confined to the Holocene Younger Delta Plain and the alluvium that was deposited around 10,000–7,000 years bp, under combined influence of the Holocene sea-level rise and rapid erosion in the Himalaya. Further, contaminated areas are often located close to distribution of abandoned or existing channels, swamps, which are areas of surface water and biomass accumulation. Extensive extraction of groundwater mainly from shallow aquifers cause recharge from nearby surface water bodies. Infiltration of recharge water enriched in dissolved organic matter derived either from recently accumulated biomass and/or from sediment organic matter enhanced reductive dissolution of hydrated iron oxide that are present mainly as sediment grain coatings in the aquifers enhancing release of sorbed arsenic to groundwater.     

Arsenic solubilization and redistribution under anoxic conditions in three aquifer sediments from a basin-fill aquifer in Northern Utah: The role of natural organic carbon and carbonate minerals

The basin-fill aquifers of the Western U.S. contain elevated concentrations of arsenic in the groundwater due to ancient volcanic deposits that host arsenic minerals. Microcosms were constructed using two oxidized sediments and, by contrast, a reduced sediment collected from a shallow basin-fill aquifer in the Cache Valley Basin, Northern Utah to evaluate the fate of geologic arsenic under anoxic conditions. Sequential extractions indicated the primary arsenic host mineral was amorphous iron oxides, but 13%–17% of the total arsenic was associated with carbonate minerals. Arsenic was solubilized from the sediments when incubated with groundwater in the presence of native organic carbon. Arsenic solubilization occurred prior to iron reduction rather than the commonly observed co-reactivity. Arsenic(V) associated with carbonate minerals was the main source of arsenic released to solution and redistributed onto less soluble minerals, including FeS and siderite as defined by chemical extraction. Arsenic reduction occurred only in the site-oxidized sediments. The addition of a carbon and energy source, glucose, resulted in enhanced arsenic solubilization, which was coupled with iron reduction from the site-oxidized sediments. Adding glucose promoted iron reduction that masked the role of carbonate minerals in arsenic solubilization and retention as observed with incubation with groundwater only.     

Mineralogical and geomicrobiological investigations on groundwater arsenic enrichment in Bangladesh

Sources of As in the Ganges sediments and microbial mechanisms of its release in groundwater were examined in the present study, where the authors have systematically examined the pertinent mineral species present in the sediments using XRD, TEM-EDS and EPMA techniques. The results show several As-bearing minerals in the Ganges sediments, in western Bangladesh. Iron-sulfide minerals consist of near-amorphous and/or crystalline precursors of framboidal pyrite and pyrite both of which contain As. Several types of Fe oxyhydroxides (oxides), which contain variable amounts of As were also found in muddy sediments. The content of As increases from Fe-oxides to the precursors of framboidal pyrite and pyrite. Four different chemical forms of As from the core sediments were determined. The sequentially extracted chemical forms are as follows: (1) acid soluble form (As mainly fixed in carbonates), (2) reducible form (As fixed in Fe- and/or Mn-oxides), (3) organic form, (4) insoluble form (As fixed mainly in sulfide and rarely in silicate minerals). Arsenic is dominantly sorbed on to Fe- and/or Mn-oxides, organic forms and sulfide minerals in most samples, although their relative abundances differ in different samples. Geomicrobial culture experiments were carried out to test the hypothesis that microbial processes play a key role in the release of As in groundwater. Batch culture and circulating water system experiments were designed using the sediments from Bangladesh. In the batch experiments, As was released at low Eh values a few days after adding nutrients containing glucose, polypepton and yeast extract, urea and fertilizer under a dominantly N₂ atmosphere. This contrasts with the control experiments without nutrients. Circulating water experiments with sand layer in a N₂ atmosphere showed similar results. These results support the hypothesis that microbial processes mediate the release of As into groundwater under reducing conditions. Glucose and polypepton used in the experiments may correspond to C and N sources, respectively. Younger sediments contain abundant organic matter, which is easily used by bacteria. So, the enhanced bacterial activity may correspond to simulation of accelerated natural diagenetic process using organic matter, or some fertilizer/wastewater effects.     

Holocene estuarine sediments as a source of arsenic in Pleistocene groundwater in suburbs of Hanoi,Vietnam

Groundwater pollution by arsenic is a major health threat in suburban areas of Hanoi, Vietnam. The present study evaluates the effect of the sedimentary environments of the Pleistocene and Holocene deposits, and the recharge systems, on the groundwater arsenic pollution in Hanoi suburbs distant from the Red River. At two study sites (Linh Dam and Tai Mo communes), undisturbed soil cores identified a Pleistocene confined aquifer (PCA) and Holocene unconfined aquifer (HUA) as major aquifers, and Holocene estuarine and deltaic sediments as an aquitard layer between the two aquifers. The Holocene estuarine sediments (approximately 25–40 m depth, 9.6–4.8 cal ka BP) contained notably high concentrations of arsenic and organic matter, both likely to have been accumulated by mangroves during the Holocene sea-level highstand. The pore waters in these particular sediments exhibited elevated levels of arsenic and dissolved organic carbon. Arsenic in groundwater was higher in the PCA (25–94 μg/L) than in the HUA (5.2–42 μg/L), in both the monitoring wells and neighboring household tubewells. Elevated arsenic concentration in the PCA groundwater was likely due to vertical infiltration through the arsenic-rich and organic-matter-rich overlying Holocene estuarine sediments, caused by massive groundwater abstraction from the PCA. Countermeasures to prevent arsenic pollution of the PCA groundwater may include seeking alternative water resources, reducing water consumption, and/or appropriate choice of aquifers for groundwater supply.     

Nature and origin of arsenic carriers in shallow aquifer sediments of Bengal Delta,India

Sediments from shallow aquifers in Bengal Delta, India have been found to contain arsenic. Rivers of Ganga-Brahmaputra system, responsible for depositing these sediments in the delta, have created a store of arsenic. Geomorphological domains with different depositional styles regulate the pattern of distribution of zones with widely different content of groundwater arsenic. The high arsenic zones occur as narrow sinuous strips confined to channel deposits. A few iron-bearing clastic minerals and two post-depositional secondary products are arsenic carriers. Secondary siderite concretions have grown on the surface of the clastic carriers in variable intensity. The quantity of arsenic in all clastic carriers is in excess of what is generally expected. Excess arsenic is contributed by the element adsorbed on the concretion grown on the surface of the carriers, which adds up to the arsenic in the structure of the minerals. Variable abundance of concretions is responsible for the variable quantity of arsenic in the carriers and the sediment samples. Fe²⁺ for the growth of siderite concretions is obtained from the iron-bearing clastic carriers. The reaction involves reduction of trivalent iron to bivalent and the required electron is obtained by transformation of As³⁺ to As⁵⁺. It is suggested that oxidation of As³⁺ to As⁵⁺ is microbially mediated. In the Safe zone arsenic is retained in the carriers and groundwater arsenic is maintained below 0.05 mg/l. In the Unsafe zone sorbed arsenic is released from the carriers in the water through desorption and dissolution of concretion, thereby elevating the groundwater arsenic level to above 0.05 mg/l.     

Riddle of arsenic in groundwater of Bengal Delta Plain—role of non-inland source and redox traps

In the Bengal Delta Plain (BDP) the primary arsenic sourcing appears to be different from the global scenario. Here, the Terminal Pleistocene–Holocene depositional platform, the interactive early Holocene depositional morphology with fluvio-estuarine and marine incursions played a crucial role for arsenic sourcing and enrichment. The lenticular silt-fine sand layer between anoxic clay beds favoured entrapment of dissolved organic carbon with decayed phyto-planktons debris. The Terminal Pleistocene–Holocene transgression and regression processes may have acted as major events in the BDP. Interestingly, at the end of the last glacial maxima, the Pleistocene delta had undergone block movements, wherein some parts of the platform were raised above the level of Holocene deposition. Those blocks were found to be free from arsenic in the groundwater. The sea, during re-emerging inundation (10–7 ka BP), has witnessed a monsoon-induced environment in the BDP with the resultant oscillation of sea level leading to higher upsurge towards the north. This might have resulted in the marine incursion and inundation in pre-existing land depressions. Meanwhile arsenic entrapments through marine incursion as well as enrichment in the presence of organic carbon/DOC and/or Fe/Mn/Al catalytic agents could have developed into localised redox traps. It may be of relevance that due to the repetitive transgressive–regressive phases in Holocene, resulting in periodic exposure and weathering of iron-bearing minerals and consequent iron enrichment in the aquifer system. The iron, thus present, had free charge to host arsenic as a sink. It appears that arsenic, wherever found, would likely be of atypical localised exhaustible phenomenon, both in horizontal and vertical context. It also rationalises the cause of the absence of arsenic in the other nearby Pleistocene platform, which has not come across Holocene interaction and marine incursion, as to the likely limiting condition for the search for arsenic in the BDP or beyond.     

Role of Quaternary stratigraphy on arsenic-contaminated groundwater from parts of Middle Ganga Plain,UP–Bihar,India

Late Quaternary stratigraphy and sedimentation in the Middle Ganga Plain (MGP) (Uttar Pradesh–Bihar) have influenced groundwater arsenic contamination. Arsenic contaminated aquifers are pervasive within narrow entrenched channels and flood plains (T₀-Surface) of fine-grained grey to black coloured argillaceous organic rich Holocene sediments (Newer Alluvium). Contaminated aquifers are often located close to distribution of abandoned or existing channels and swamps. The Pleistocene Older Alluvium upland terraces (T₂-Surface) made up of oxidized yellowish brown sediments with calcareous and ferruginous concretions and the aquifers within it are free of arsenic contamination. MGP sediments are mainly derived from the Himalaya with minor inputs from the Peninsular India. The potential source of arsenic in MGP is mainly from the Himalaya. The contaminated aquifers in the Terai belt of Nepal are closely comparable in nature and age to those of the MGP. Arsenic was transported from disseminated sources as adsorbed on dispersed phases of hydrated-iron-oxidea and later on released to groundwater mainly by reductive dissolution of hydrated-iron-oxide and corresponding oxidation of organic matter in aquifer. Strong reducing nature of groundwater is indicated by high concentration of dissolved iron (11.06 mg/l). Even within the arsenic-affected areas, dugwells are found to be arsenic safe due to oxyginated nature.     

Hydrogeochemical contrast between two study areas of Bengal delta,India: A comparative insight to understand arsenic mobilization process in shallow aquifers

A comparative hydrogeochemical study evaluated arsenic release mechanism and differences in contamination levels in the shallow groundwater of two areas within the deltaic environment of West Bengal (i.e. Karimpur and Tehatta blocks of Nadia district) in India. Groundwaters from both the areas are Ca-Na(K)-Cl-HCO₃ type with highly reducing character (−110.16 ± 16.85 to −60.77 ± 16.93 mV). Low correlations among As, Fe, and Mn and the higher association between As and DOC are indicative of microbial decomposition of organic matter enhancing the weathering of shallow aquifer materials. Arsenic contamination in groundwater is higher in Karimpur (95 ± 81.17 μg/L) than that in Tehatta (43.05 ± 41.06 μg/L). The release mechanism of arsenic into groundwater is very complex. Low Fe (0.27–4.78 mg/L and 0.81–4.13 mg/L), Mn (0.08–0.2 mg/L and 0.03–0.22 mg/L), and SO₄²⁻ (3.82 ± 0.31 and 2.78 ± 0.40 mg/L) suggest that the mechanism of arsenic release is not a single mechanistic pathway. Clustering of redox-active parameters in the principal component planes indicate that the reductive dissolution, and/or weathering/co-precipitation of Fe/Mn-bearing minerals in the shallow aquifer sediments control the dominant mechanistic pathway of arsenic release.     

Source and Formation of the Arsenic in Ground Water in Hanoi,Vietnam

The problem of Arsenic source in groundwater has yet been addressed thoroughly. From the results of the analysis of samples, this article gives the statement that the Arsenic in groundwater of Quaternary sediments in Hanoi has mainly natural source, with the impact of man-made factors (industrial waste water, use of crop protection products, etc.). The article also explains the formation of Arsenic in groundwater in Hanoi area is closely related to the reduction by two main mechanisms, reducing mechanism of oxyhydroxit (Fe3 + OHAs) As liberation by microorganisms and reducing mechanism of As adsorbed on iron oxide or oxyhydroxit replaced by bicarbonate. The process of oxidation of minerals containing As is needed to be researched more.     

Study of subsurface geology in locating arsenic-free groundwater in Bengal delta,West Bengal,India

Over a large area of the Bengal delta in West Bengal, India, arsenic distribution patterns in groundwater were studied. One hundred and ten boreholes at different target locations were made, subsurface sediments were logged and analysed, and arsenic values in sediments vis-à-vis groundwater were compared. The study elucidates the subsurface geology of the western part of Bengal delta and characterises the sediments that were intersected in different boreholes with contrasting values of arsenic in groundwater. It reveals an existence of multiple aquifers stacked over each other. Depending on the color and nature of aquifer-sands and their overlying clay beds six aquifer types (Type-1 to Type-6) are classified and described. Sediment-arsenic for all the varieties of aquifer sands are near similar but the groundwater-arsenic of these six aquifers varies widely. Type-2 and Type-5 aquifers host arsenic-contaminated groundwater whereas the other four aquifers are arsenic-free. Type-2 and Type-5 aquifers are capped by a grey to dark grey soft organic matter-rich clay unit which makes these aquifers semi-confined to leaky-confined. These contribute in releasing arsenic from the sediments. The results of this study are employed in a proposed georemedial measure against this hazardous toxic element.     

Texture and mineralogy of sediments from the Ganges-Brahmaputra-Meghna river system in the Bengal Basin, Bangladesh and their environmental implications

 The Bengal basin, Bangladesh, represents one of the most densely populated recent floodplains of the world. The sediment flux through the basin is one of the highest on a global scale. A significant portion of this sediment load find its sink in the basin itself because of its lower elevation and frequent flooding. The textural, mineralogical and chemical nature of the sediments thus have an important bearing on the environmental quality of the basin as well as for the Bay of Bengal. The sediment load of the Ganges-Brahmaputra-Meghna (GBM) river system consists exclusively of fine sand, silt and clay at their lower reaches within the Bengal basin, Bangladesh, and is deposited under uniformly fluctuating, unidirectional energy conditions. The sediments have a close simitarity in grain size with the sediments of the surrounding floodplain. The mineral assemblage is dominated by quartz and feldspars. Illite and kaolinite are the major clay minerals, and occur in almost equal proportion in bed sediments. The heavy mineral assemblage is dominated by unstable minerals which are mostly derived from high-rank metamorphic rocks. The characteristic smaller grain-size, i.e. having large surface-to-mass ratios, and the mineralogy of sediments suggests that they are susceptible to large chemical adsorptive reactions and thus could serve as a potential trap for contaminants. However, the sediments of the GBM river system in the Bengal basin, Bangladesh, shows lower concentration of Pb, Hg and As, and a marginally higher value for Cd as compared to that of standard shale. Considering population density and extensive agricultural practice in the basin, the sediments can in the long run become contaminated. Received: 9 November 1994 · Accepted: 18 June 1996     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Contamination of shallow aquifers by arsenic in upper reaches of Tista river at Siliguri–Jalpaiguri area of West Bengal, India

Arsenic is present in groundwater at Siliguri–Jalpaiguri area, West Bengal, India. This is the place where Tista river descending from the Himalayas meets the alluvial plain. The area represents alluvial fan and floodplains of Tista, Mahananda-Balasan, Jaladhaka and its tributaries. In the river sediment samples, para- and ferro-magnetic minerals within 0.3–0.05 mm fraction contain 9–80 ppm of arsenic. The study indicates that iron bearing minerals viz. biotite, hornblende as well as iron coated grains of the sediment are major contributors towards arsenic budget. Though magnetite as a mineral shows maximum arsenic content (22 ppm), it is volumetrically not of much significance. Measurement of groundwater collected from tube wells shows up to 0.05 ppm of arsenic. These arsenic contaminated tube wells occur in a linear fashion along the course of the rivers. Moreover, localization of contaminated tube wells coincides with the change of channel gradient as observed in longitudinal section. The study enumerates a cause–effect relationship of arsenic occurrence with river gradient and fluvial sedimentation.     

Distribution and fractionation of heavy metals in the surface sediments of the Ganges- Brahmaputra-Meghna river system in the Bengal basin

 The lower Ganges-Brahmaputra-Meghna (G-B-M) drainage basin occupies the total Bengal Basin, which is one of the unique basins of the world because of its location and size, density of population, and catastrophic deposition of sediments. The increased heavy metal concentration in the 63 m fraction of surface sediments shows similarity among major segments of the G-B-M system in the basin, which reflects the homogenization of lithologic and chemical diversity of the greater denudation regime by the river processes. The differences in heavy metal concentation in the lower G-B-M system with that of its upper and middle counterpart is mainly related to the contrast between Himalayan rivers and the other major South Asian rivers, and may be due to the geological differences of their denudation regime. Heavy metals in the Lower G-B-M system have an affinity towards the clay fraction of the sediments. The correlation matix of heavy metals in the lower Brahmaputra and Meghna suggests the importance of Fe-Mn oxyhydroxides in their accumulations. Iron, Ti and Mn are higher in the Meghna main channel, Zn is higher in the Meghna tributaries, and Cr is higher in both the Brahmaputra and Meghna compared to the value for standard shale. The enrichment factor is ≤1 for most of the metals except Mn which is relatively higher in the Meghna and lower Ganges main channels. The geoaccumulation index (I_geo) for most of the heavy metals lies below grade zero, suggesting unpolluted sediment quality. The lower Ganges system shows relatively higher concentration in the nondetrital fraction of heavy metals, probably due to the presence of petroleum refinery, industrial and mining effluents, and agricultural runoff in the drainage basin. The relative uniformity in concentration of heavy metals in vertical profiles may be due to the uniformity in sediment grain size and catastrophic deposition of sediments, where the time period represented by the vertical sediment column is not enough to reflect the cultural accumulation of heavy metals. The Bengal basin thus represents a relatively unperturbed alluvial basin with regards to heavy metal pollution. Received: 21 July 1997 · Accepted: 13 October 1997     

Arsenic exposure through groundwater in the middle Ganga plain in the Varanasi environs,India: A future threat

The study area covers an about 100 km² of the middle Ganga plain in Uttar Pradesh, experiencing intensive groundwater extraction. In order to recognize the arsenic contamination zones of the Varanasi environs, sixty eight groundwater samples have been collected and analyzed for major ions, iron and arsenic. Twenty one sediment samples in the four boreholes were also collected to deduce the source of arsenic in the groundwater. The preliminary survey reports for the first time indicates that part of rural and urban population of Varanasi environs are drinking and using for irrigation arsenic contaminated water mostly from hand tube wells (<70 m). The study area is a part of middle Ganga plain which comprises of Quaternary alluvium consists of an alternating succession of clay, clayey silt and sand deposits. The high arsenic content in groundwater samples of the study area indicates that 14% of the samples are exceeding the 10 μg/l and 5% of the samples are exceeding 50 μg/l. The high arsenic concentration is found in the villages such as Bahadurpur, Madhiya, Bhojpur, Ratanpur, Semra, Jalilpur, Kateswar, Bhakhara and Kodupur (eastern side of Ganga River in Varanasi), situated within the newer alluvium deposited during middle Holocene to Recent. The older alluvial aquifers situated in the western side of the Ganga River are arsenic safe (maximum As concentration of 9 μg/l) though the borehole sediments shows high arsenic (mean 5.2 mg/kg) and iron content (529 mg/kg) in shallow and medium depths. This may be due to lack of reducing conditions (i.e organic content) for releasing arsenic into the groundwater. Rainfall infiltration, organic matter from recently accumulated biomass from flood prone belt in the newer alluvium plays a critical role in releasing arsenic and iron present in sediments. The main mechanism for the release of As into groundwater in the Holocene sandy aquifer sediments of Varanasi environs may be due to the reductive dissolution of Fe oxyhydroxide present as coatings on sand grains as well as altered mica content. The high societal problems of this study will help to mitigate the severity of arsenic contamination by providing alternate drinking water resources to the people in middle Ganga plain and to arrange permanent arsenic safe drinking water source by the authorities.     

Environmental mercury and arsenic sources in fossil hydrothermal systems, Northland, New Zealand

 Northland, New Zealand has been affected by natural hot water spring systems depositing elevated concentrations of mercury and arsenic over the past 5 million years. Due to the different erosion levels of these hot water systems, four principal types of mercury and arsenic occurrences are found: active hot springs; layered surface deposits (sinters) deposited by hot springs; highly fractured rock zones formed immediately beneath hot springs; and chemically altered and mineralized rock from the deeper roots of hot spring systems. Mercury occurs principally as cinnabar and as a minor impurity (<1 wt%) in phosphate minerals and iron sulfides, particularly marcasite. Mercury is irregularly distributed through limonitic cements formed during oxidation. Arsenic occurs as a minor impurity (<1 wt%) in phosphate minerals and iron sulfides, particularly marcasite. Arsenic is also variably dispersed through limonite, but not necessarily with mercury. Decomposition of marcasite constitutes the most significant source of mercury and arsenic pollution from the studied sites. Release of mercury and arsenic into the environment from marcasite, phosphates and limonite is enhanced by acidification of the sites (down to pH of 2), caused by oxidation of iron sulfides. Mercury and arsenic concentrations of up to 100 parts per billion should be expected in waters near the deposits; these concentrations are in excess of recommended drinking water levels. Received: 9 April 1999 · Accepted: 2 August 1999     

Speciation and natural attenuation of arsenic and iron in a tidally influenced shallow aquifer

The mobility of subsurface arsenic is controlled by sorption, precipitation, and dissolution processes that are tied directly to coupled redox reactions with more abundant, but spatially and temporally variable, iron and sulfur species. Adjacent to the site of a former pesticide manufacturing facility near San Francisco Bay (California, USA), soil and groundwater arsenic concentrations are elevated in sediments near the prior source, but decrease to background levels downgradient where shallow groundwater mixes with infiltrating tidal waters at the plume periphery, which has not migrated appreciably in over two decades of monitoring. We used synchrotron X-ray absorption spectroscopy, together with supporting characterizations and sequential chemical extractions, to directly determine the oxidation state of arsenic and iron as a function of depth in sediments from cores recovered from the unsaturated and saturated zones of a shallow aquifer (to 3.5 m below the surface). Arsenic oxidation state and local bonding in sediments, as As-sulfide, As(III)-oxide, or As(V)-oxide, were related to lithologic redox horizons and depth to groundwater. Based on arsenic and iron speciation, three subsurface zones were identified: (i) a shallow reduced zone in which sulfide phases were found in either the arsenic spectra (realgar-like or orpiment-like local structure), the iron spectra (presence of pyrite), or both, with and without As(III) or As(V) coordinated by oxygen; (ii) a middle transitional zone with mixed arsenic oxidation states (As(III)–O and As(V)–O) but no evidence for sulfide phases in either the arsenic or iron spectra; and (iii) a lower oxidized zone in the saturated freshwater aquifer in which sediments contained only oxidized As(V) and Fe(III) in labile (non-detrital) phases. The zone of transition between the presence and absence of sulfide phases corresponded to the approximate seasonal fluctuation in water level associated with shallow groundwater in the sand-dominated, lower oxic zone. Total sediment arsenic concentrations showed a minimum in the transition zone and an increase in the oxic zone, particularly in core samples nearest the former source. Equilibrium and reaction progress modeling of aqueous-sediment reactions in response to decreasing oxidation potential were used to illustrate the dynamics of arsenic uptake and release in the shallow subsurface. Arsenic attenuation was controlled by two mechanisms, precipitation as sulfide phases under sulfate-reducing conditions in the unsaturated zone, and adsorption of oxidized arsenic to iron hydroxide phases under oxidizing conditions in saturated groundwaters. This study demonstrates that both realgar-type and orpiment-type phases can form in sulfate-reducing sediments at ambient temperatures, with realgar predicted as the thermodynamically stable phase in the presence of pyrite and As(III) under more reduced conditions than orpiment. Field and modeling results indicate that the potential for release of arsenite to solution is maximized in the transition between sulfate-reduced and iron-oxidized conditions when concentrations of labile iron are low relative to arsenic, pH-controlled arsenic sorption is the primary attenuation mechanism, and mixed Fe(II,III)-oxide phases do not form and generate new sorption sites.     

Arsenic contamination in groundwater and its proposed remedial measures

Arsenic contamination occurs in groundwater of Bangladesh mainly from the alluvial and deltaic sediments. Arsenic contamination of groundwater in Bangladesh was first detected more than a decade ago and the ’shallow tubewells’ were reported as the main source of arsenic contaminated water. From the nutritional and metabolic points of view, arsenic is likely to adversely affect human health and nutrition. Up to now, several studies have been carried out on this context; however, inadequate knowledge on arsenic sources, mobilization and transport still remains as a constraint due to lack of data, information and technological advances. Thus, a review study has been undertaken on the sources of arsenic, its causes, mobilization, transport, effects on human health, arsenic test procedures and removal methods, in the context of groundwater contamination in Bangladesh, and finally sustainable remedial measures of arsenic have been proposed. This study suggests that laboratory facilities for testing of arsenic and effects of enhanced groundwater pumping, phosphate fertilizer etc., need to be updated, expanded and studied. This review work is significant to further knowledge improvement, as the topic is general and worldwide. It can be concluded that the integration of the proposed remedial measures with the national geographic information system interface database relating to arsenic for analysis, production of hazard maps, and dissemination on television show for the planners, engineers, managers, field supervisors and affected people, can reach at the sustainable solution for mitigating arsenic and associated problems successfully in Bangladesh.     

Arsenic-enriched aquifers: Occurrences and mobilization of arsenic in groundwater of Ganges Delta Plain, Barasat, West Bengal, India

Hydrogeochemical characteristics and elemental features of groundwater and core sediments have been studied to better understand the sources and mobilization process responsible for As-enrichment in part of the Gangetic plain (Barasat, West Bengal, India). Analysis of water samples from shallow tubewells (depth 24.3–48.5 m) and piezometer wells (depth 12.2–79.2 m) demonstrate that the groundwater is mostly the Ca-HCO₃ type and anoxic in nature (mean Eh_SHE = 34 mV). Arsenic concentrations ranged from <10–538 μg/L, with high concentrations only present in the shallow to medium depth (30–50 m) of the aquifer along with high Fe (0.07–9.8 mg/L) and relatively low Mn (0.15–3.38 mg/L) as also evidenced in core sediments. Most groundwater samples contained both As(III) and As(V) species in which the concentration of As(III) was generally higher than that of As(V), exhibiting the reducing condition. Results show lower concentrations of NO₃, SO₄ and NO₂ along with higher values of DOC and HCO₃, indicating the reducing nature of the aquifer with abundant organic matter that can promote the release of As from sediments into groundwater. Positive correlations of As with Fe and DOC were also observed. The presence of DOC may actively drive the redox processes. This study revealed that reduction processes of FeOOH was the dominant mechanism for the release of As into the groundwater in this part of the Ganges Delta plain.