Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

Vertical distribution of bacterial populations associated with arsenic mobilization in aquifer sediments from the Hetao plain, Inner Mongolia

To understand the mechanism of arsenic mobilization from sediment to groundwater mediated by microorganism, vertical distribution of bacterial populations in aquifer sediments of the Hetao plain, Inner Mongolia was investigated by a two-step nested PCR-DGGE and 16S rRNA gene clone libraries, combined with sediment geochemistry. A borehole to 30 m depth was drilled and 11 sediment samples were collected. Lithological profile and different geochemical characteristics of sediments indicated a distinct transition of oxidizing–reducing environment along the depth of the sediment core. As(III) and Fe(II) concentrations elevated progressively from 10 m, simultaneously coupling with decrease of As(V) and Fe(III) concentrations, implying that reductive dissolution of arsenic-rich Fe(III) oxyhydroxides led to arsenic release. Results of DGGE displayed that sediment samples with higher concentrations of total arsenic and total organic carbon had lower population diversity, which suggested total arsenic concentrations were important to determine the population diversity of sediments. Bacterial communities of a sediment sample with the highest diversity and ratio of As(III) to total As were dominated by aerobic and facultative anaerobic bacteria and belonged to Alpha-, Beta-, and Gammaproteobacteria and Firmicutes group. Most of the retrieved sequences were closely related to high arsenic-resistance organisms, sulfide/thiosulfate oxidizers, denitrifiers, and aromatic hydrocarbon degraders. Thiobacillus distinctly predominated in clone library, which suggested that arsenic might be released by oxidized dissolution of sulfide minerals coupled to arsenate reduction or nitrate reduction in anaerobic condition. These data have important implications for understanding the microbially mediated arsenic mobilization in aquifers.     

Occurrence and geochemistry of arsenic in the groundwater of Eastern Croatia

In order to examine the extent of the As enrichment and the factors influencing this enrichment in the groundwater of Eastern Croatia, groundwater samples were collected from 56 production wells in two counties, Osijek-Baranja and Vukovar-Srijem, suspected to be more affected. Hydrochemical analyses were performed at all locations including in situ As speciation at 32 locations. Arsenic was detected in 46 out of 56 groundwater samples with total As concentrations up to 491 μg/L. Thirty-six of the studied wells yielded groundwater with total As concentrations that exceeded the WHO Maximum Contaminant Level for arsenic in drinking water of 10 μg/L. Only inorganic As species were detected with arsenite As(III) as the predominant form. The spatial distribution of As in the groundwater was significantly linked with geological, geomorphological and hydrogeological development of the alluvial basin of the Drava and Sava rivers. The most probable groundwater As sources are deeper sediments from the Middle and Upper Pleistocene. The results obtained suggest that biogeochemical processes controlling As concentration in the groundwater are complex and location-specific. Reductive dissolution of Fe oxides, desorption of As from Fe oxides and/or clay minerals as well as competition for the sorption sites with organic matter and phosphate could be the principal mechanisms that control As mobilization. The extent of those processes vary in the different parts of the Drava and Sava depressions and could be linked to different site related parameters, such as lithology, mineralogy, local hydrology and hydrogeology; thus different processes of As mobilization have been proposed for the different types of water in relation to groundwater evolution.     

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.     

Assessment of naturally occurring arsenic contamination in the groundwater of Sarkisla Plain (Sivas/Turkey)

High arsenic levels in groundwater of the aquifers, belonging to the Pliocene terrestrial layers and Quaternary alluvial sediments, have become a significant problem for the inhabitants living in Sarkisla (Turkey). The main objective of this study was to determine the origin and arsenic contamination mechanisms of the Sarkisla drinking water aquifer systems. The highest arsenic concentrations were found in Pliocene layers and alluvial sediments with concentrations ranging from 2.1 to 155 mg/kg. These rocks are the main aquifers in the study area, and most of the drinking groundwater demand is met by these aquifers. Groundwater from the Pliocene aquifer is mainly Ca-HCO₃ and Ca-SO₄ water type with high EC values reaching up to 3,270 μS/cm, which is due to the sulfate dissolution in some parts of the alluvial aquifer. Stable isotope values showed that the groundwater was of meteoric origin. Tritium values for the groundwater were between 8.31 and 14.06 TU, representing a fast circulation in the aquifer. Arsenic concentrations in the aquifers were between 0.5 and 345 μg/L. The highest arsenic concentrations detected in the Pliocene aquifer system reached up to 345 μg/L with an average value of 60.38 μg/L. The arsenic concentrations of the wells were high, while the springs had lower arsenic concentrations. These springs are located in the upper parts of the study area where the rocks are less weathered. The hydrogeochemical properties demonstrated that the water–rock interaction processes in sulfide-bearing rocks were responsible for the remarkably high groundwater arsenic contamination in the study area. In the study area, the arsenic levels determined in groundwater exceeded the levels recommended by the WHO. Therefore, it is suggested that this water should not be used for drinking purposes and new water sources should be investigated.     

Hydrogeochemistry and arsenic contamination of groundwater in the Rayen area, southeastern Iran

High As contents in groundwater were found in Rayen area and chosen for a detailed hydrogeochemical study. A total of 121 groundwater samples were collected from existing tube wells in the study areas in January 2012 and analyzed. Hydrogeochemical data of samples suggested that the groundwater is mostly Na–Cl type; also nearly 25.62 % of samples have arsenic concentrations above WHO permissible value (10 μg/l) for drinking waters with maximum concentration of aqueous arsenic up to 25,000 μg/l. The reducing conditions prevailing in the area and high arsenic concentration correlated with high bicarbonate and pH. Results show that arsenic is released into groundwater by two major phenomena: (1) through reduction of arsenic-bearing iron oxides/oxyhydroxides and Fe may be precipitated as iron sulfide when anoxic conditions prevail in the aquifer sediments and (2) transferring of As into the water system during water–acidic volcanic rock interactions.     

长江中游河湖平原浅层地下水中砷空间异质性的同位素指示

近年来陆续有报道发现长江中游河湖平原广泛分布着高砷地下水,鄱阳湖平原与江北平原（古彭蠡泽）作为长江中游南北两岸典型的河湖平原,其地下水资源丰富,但砷的空间分布规律尚不清楚,区域供水安全存在风险.本研究在两个区域系统采集98个浅层地下水（< 40 m）样品和8个地表水样品,通过水化学、氢氧稳定同位素分析,查明地下水中砷的空间分布异质性及其影响因素.研究发现江北平原浅层地下水砷含量为0.65~956.72 μg/L（平均值210.78 μg/L）,高砷地下水集中分布于长江古河道;鄱阳湖平原浅层地下水砷含量为0.09~267.45 μg/L（平均值11.85 μg/L）,高砷地下水仅分布于赣江三角洲局部地区.江北平原地下水δD与δ18O值相对鄱阳湖平原更偏负,且与地表水的差异更大.地下水化学及主成分分析结果表明物源和含水层结构差异是影响鄱阳湖平原和江北平原砷空间分布异质性的关键因素,来自长江物源的古彭蠡泽区域沉积物为高砷含水层的形成提供了物质来源,湖相含水层中含砷铁氧化物的还原性溶解是地下水砷富集的主要过程.地下水氢氧稳定同位素指示江北平原较鄱阳湖平原地下水赋存环境更封闭,地下水循环交替速度缓慢,有利于砷的富集.      

Vertical geochemical variations and arsenic mobilization in the shallow alluvial aquifers of the Chapai-Nawabganj District, northwestern Bangladesh: implication of siderite precipitation

Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO₃ type with high concentrations of As, but low levels of Fe, Mn, NO₃ ^? and SO ₄ ^?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.     

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.     

Vertical distribution and mobilization of arsenic in shallow alluvial aquifers of Chapai-Nawabganj district, Northwestern Bangladesh

Core sediments from two boreholes and groundwater from fifty four As-contaminated well waters were collected in the Chapai-Nawabganj area of northwestern Bangladesh for geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10 to 40 m of depth) range from 2.76?C315.15 mg/l (average 48.81 mg/l). Arsenic concentration in sediments ranges from 3.26?C10 mg/kg. Vertical distribution of arsenic in both groundwater and sediments shows that maximum As concentration (462 mg/l in groundwater and 10 mg/kg in sediments) occurs at a depth of 24 m. In January 2008, 2009 and 2010, maximum As concentration occurs at the same depth. Environmental scanning electron microscope (ESEM) with EDAX was used to investigate the presence of major and trace elements in the sediments. The dominant groundwater type is Ca-HCO₃ with high concentrations of As and Fe, but with low levels of NO₃ ^? and SO₃ ^?2. Statistical analysis clearly shows that As is closely associated with Fe (R² = 0.64) and Mn (R² = 0.91) in sediments while As is not correlated with Fe and Mn in groundwater samples. Comparatively low Fe and Mn concentrations in some groundwater, suggest that probably siderite and/or rhodochrosite precipitated as secondary mineral on the surface of the sediment particles. The correlations along with results of sequential leaching experiments suggest that reductive dissolution of FeOOH and MnOOH mediated by anaerobic bacteria represents mechanism for releasing arsenic into the groundwater.     

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.     

Fluoride and arsenic hydrogeochemistry of groundwater at Yuncheng basin,Northern China

High fluoride and arsenic concentrations in groundwater have led to serious health problems to local inhabitants at Yuncheng basin, Northern China. In this study, groundwater with high fluoride and arsenic concentration at Yuncheng basin was investigated. A majority of the samples (over 60%) belong to HCO₃ type water. The predominant water type for the shallow groundwater collected from southern and eastern mountain areas was Ca/Mg-Ca-HCO₃ types. For the shallow groundwater from flow through and discharge area it is Na-HCO₃/SO₄-Cl/SO₄/Cl type. The predominant water type for the intermediate and deep groundwater is of Na/Ca/Mg-Ca-HCO₃ type. According to our field investigation, fluoride concentration in groundwater ranges between 0.31 and 14.2 mg/L, and arsenic concentration ranges between 0.243 and 153.7 μg/L. Out of seventy collected groundwater samples, there are 31 samples that exceed the World Health Organization (WHO) standard of 1.5 mg/L for fluoride, and 15 samples exceeds the WHO standard of 10 μg/L for arsenic. Over 40% of high fluoride and arsenic groundwater are related to the Na-HCO₃ type water, and the other fifty percent associated with Na-SO₄-Cl/HCO₃-SO₄-Cl type water; little relation was found in calcium bicarbonate type water. A moderate positive correlation between fluoride and arsenic with pH were found in this study. It is due to the pH-dependent adsorption characteristics of F and As onto the oxide surfaces in the sediments. The observed negative correlation between fluoride and calcium could stem from the dissolution equilibrium of fluorite. The high concentration of bicarbonate in groundwater can serve as a powerful competitor and lead to the enrichment of fluoride and arsenic in groundwater. Most of the groundwater with high fluoride or arsenic content has nitrate content about or over 10 mg/L which, together with the observed positive correlations between nitrate and fluoride/arsenic, are indicative of common source of manmade pollution and of prevailing condition of leaching in the study area.     

Influence of hydrostratigraphy and structural setting on the arsenic occurrence in groundwater of the Cimino-Vico volcanic area (central Italy)

Arsenic occurrence in groundwater near the Cimino-Vico volcanoes (central Italy) was analysed considering the hydrostratigraphy and structural setting and the shallow and deep flows interacting within the Quaternary volcanics. Groundwater is the local source of drinking water. As documented in the past, arsenic in the groundwater has become a problem, and the European maximum allowable contaminant level was recently lowered to 10 μg/L. Chemical analyses of groundwater were conducted, sampled over an area of about 900 km², from 65 wells and springs representative of the volcanic aquifer and thermal waters. Considering the type of aquifer, the nature of the aquifer formation and its substratum, the hydrochemical data highlight that the arsenic content of the groundwater is mainly connected with the hydrothermal processes in the volcanic area. Thermal waters (54–60°C) fed from deep-rising fluids show higher arsenic concentrations (176–371 μg/L). Cold waters sampled from the volcanic aquifer are characterized by a wide variability in their arsenic concentration (1.6–195 μg/L), and about 62% exceed the limit of 10 μg/L. Where the shallow volcanic aquifer is open to deep-rising thermal fluids, relatively high arsenic concentrations (20–100 μg/L) are found. This occurs close to areas of the more recent volcano-tectonic structures.     

The influence of groundwater chemistry on arsenic concentrations and speciation in a quartz sand and gravel aquifera)

We examined the chemical reactions influencing dissolved concentrations, speciation, and transport of naturally occurring arsenic (As) in a shallow, sand and gravel aquifer with distinct geochemical zones resulting from land disposal of dilute sewage effluent. The principal geochemical zones were: (1) the uncontaminated zone above the sewage plume [350 μM dissolved oxygen (DO), pH 5.9]; (2) the suboxic zone (5 μM DO, pH 6.2, elevated concentrations of sewage-derived phosphate and nitrate); and (3) the anoxic zone [dissolved iron(II) 100–300 μM, pH 6.5–6.9, elevated concentrations of sewage-derived phosphate]. Sediments are comprised of greater than 90% quartz but the surfaces of quartz and other mineral grains are coated with nanometer-size iron (Fe) and aluminum (Al) oxides and/or silicates, which control the adsorption properties of the sediments. Uncontaminated groundwater with added phosphate (620 μM) was pumped into the uncontaminated zone while samples were collected 0.3 m above the injection point. Concentrations of As(V) increased from below detection (0.005 μM) to a maximum of 0.07 μM during breakthrough of phosphate at the sampling port; As(III) concentrations remained below detection. These results are consistent with the hypothesis that naturally occurring As(V) adsorbed to constituents of the coatings on grain surfaces was desorbed by phosphate in the injected groundwater. Also consistent with this hypothesis, vertical profiles of groundwater chemistry measured prior to the tracer test showed that dissolved As(V) concentrations increased along with dissolved phosphate from below detection in the uncontaminated zone to approximately 0.07 and 70 μM, respectively, in the suboxic zone. Concentrations of As(III) were below detection in both zones. The anoxic zone had approximately 0.07 μM As(V) but also had As(III) concentrations of 0.07–0.14 μM, suggesting that release of As bound to sediment grains occurred by desorption by phosphate, reductive dissolution of Fe oxides, and reduction of As(V) to As(III), which adsorbs only weakly to the Fe-oxide-depleted material in the coatings. Results of reductive extractions of the sediments suggest that As associated with the coatings was relatively uniformly distributed at approximately 1 nmol/g of sediment (equivalent to 0.075 ppm As) and comprised 20%-50% of the total As in the sediments, determined from oxidative extractions. Quartz sand aquifers provide high-quality drinking water but can become contaminated when naturally occurring arsenic bound to Fe and Al oxides or silicates on sediment surfaces is released by desorption and dissolution of Fe oxides in response to changing chemical conditions.

     

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.     

Arsenic enrichment in groundwater in the middle Gangetic Plain of Ghazipur District in Uttar Pradesh,India

Groundwater with high geogenic arsenic (As) is extensively present in the Holocene alluvial aquifers of Ghazipur District in the middle Gangetic Plain, India. A shift in the climatic conditions, weathering of carbonate and silicate minerals, surface water interactions, ion exchange, redox processes, and anthropogenic activities are responsible for high concentrations of cations, anions and As in the groundwater. The spatial and temporal variations for As concentrations were greater in the pre-monsoon (6.4–259.5 μg/L) when compared to the post-monsoon period (5.1–205.5 µg/L). The As enrichment was encountered in the sampling sites that were close to the Ganges River (i.e. south and southeast part of Ghazipur district). The depth profile of As revealed that low concentrations of NO₃⁻ are associated with high concentration of As and that As depleted with increasing depth. The poor relationship between As and Fe indicates the As release into the groundwater, depends on several processes such as mineral weathering, O₂ consumption, and NO₃⁻ reduction and is de-coupled from Fe cycling. Correlation matrix and factor analysis were used to identify various factors influencing the gradual As enrichment in the middle Gangetic Plain. Groundwater is generally supersaturated with respect to calcite and dolomite in post-monsoon period, but not in pre-monsoon period. Saturation in both periods is reached for crystalline Fe phases such as goethite, but not with respect to poorly crystalline Fe phases and any As-bearing phase. The results indicate release of arsenic in redox processes in dry period and dilution of arsenic concentration by recharge during monsoon. Increased concentrations of bicarbonate after monsoon are caused by intense flushing of unsaturated zone, where CO₂ is formed by decomposition of organic matter and reactions with carbonate minerals in solid phase. The present study is vital considering the fact that groundwater is an exclusive source of drinking water in the region which not only makes situation alarming but also calls for the immediate attention.     

Interplay of S and As in Mekong Delta sediments during redox oscillations

The cumulative effects of periodic redox cycling on the mobility of As,Fe,and S from alluvial sediment to groundwater were investigated in bioreactor experiments.Two particular sediments from the alluvial floodplain of the Mekong Delta River were investigated:Matrix A(14 m deep)had a higher pyrite concentration than matrix B(7 m deep)sediments.Gypsum was present in matrix B but absent in matrix A.In the reactors,the sediment suspensions were supplemented with As(Ⅲ)and SO_4~(2-),and were subjected to three full-redox cycles entailing phases of nitrogen/CO_2,compressed air sparging,and cellobiose addition.Major differences in As concentration and speciation were observed upon redox cycling.Evidences support the fact that initial sediment composition is the main factor controlling arsenic release and its speciation during the redox cycles.Indeed,a high pyrite content associated with a low SO_4~(2-)content resulted in an increase in dissolved As concentrations,mainly in the form of As(Ⅲ),after anoxic half-cycles;whereas a decrease in As concentrations mainly in the form of As(Ⅴ),was instead observed after oxic half-cycles.In addition,oxic conditions were found to be responsible for pyrite and arsenian pyrite oxidation,increasing the As pool available for mobilization.The same processes seem to occur in sediment with the presence of gypsum,but,in this case,dissolved As were sequestered by biotic or abiotic redox reactions occurring in the Fe—S system,and by specific physico-chemical condition(e.g.pH).The contrasting results obtained for two sediments sampled from the same core show that many complexes and entangled factors are at work,and further refinement is needed to explain the spatial and temporal variability of As release to groundwater of the Mekong River Delta(Vietnam).     

The geochemical study of fluvio-lacustrine aquifers in the Kathmandu Basin (Nepal) and the implications for the mobilization of arsenic

The geochemical analyses of fluvial-lacustrine aquifer sediments of the Kathmandu Valley have been made as a step in assessing the environment for the mobilization of arsenic in groundwater. Elements measured by X-ray fluorescence (XRF) include 4 major oxides (Fe₂O₃, TiO₂, CaO, P₂O₅) and 14 trace elements (As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc and TS). Elution tests of 15 selected core samples were also carried out to determine the potential leaching of arsenic from the sediments. The XRF results show that average bulk concentrations of the major oxides and trace elements are similar to modern unconsolidated sediments and average upper continental crust. However, the abundance of elements varies with grain size, with higher concentrations in finer-size grades. Variations in elemental abundances within the basin are strongly controlled by sediment facies. The elution tests show that greater amounts of arsenic are generally eluted from the fine sediments, although the rates are variable. The results overall suggest that As concentrations in the bulk sediments are not a controlling factor for elevated As in the Kathmandu Basin groundwater, and the roles of other factors such as redox conditions and organic matter contents are likely to be more significant.     

High arsenic contents in groundwater of central Spain

The chemical and microbiological characteristics of groundwater from two provinces of central Spain were studied. In some zones of this area, the concentrations of As in groundwater exceed the guideline concentrations, set internationally between 10 g/l and 50 g/l, reaching levels over 100 g/l. A narrow correlation between the contents of arsenic and HCO₃^– was observed. These data suggest a possible mechanism of the As mobilization from aquifer sediments to groundwater: the bicarbonate ions could displace HAsO₄^2– adsorbed on aquifer oxyhydroxides. Sediments containing relatively high contents of adsorbed arsenic are deposited in surface water environments with low carbonate concentrations. Subsequently, the sediments become exposed to groundwater with highly dissolved carbonate content, and arsenic can be mobilized by displacement from mineral surfaces. In addition, the presence of Pseudomonas genera bacteria, which secrete siderophores (Fe chelating agents) could mobilize As adsorbed on Fe oxides through their dissolution. These combined microbiological and chemical processes might have increased the natural mobility of As.     

Geochemical characterization of arsenic-affected alluvial aquifers of the Bengal Delta (West Bengal and Bangladesh) and Chianan Plains (SW Taiwan): Implications for human health

Major ion and trace element analyses were performed on groundwater samples collected from the Bengal Delta (Chakdaha municipality, West Bengal and Manikgonj town, Bangladesh) and Chianan Plains (SW Taiwan) to compare geochemical characteristics. Results showed that concentrations of Na, K, Mg, Cl and SO₄ were generally higher in Chianan Plain (CNP) groundwaters, while high Ca was observed in Bengal Delta Plain (BDP) groundwater. Measured As concentrations in groundwaters of BDP and CNP showed large variations, with mean As concentrations of 221 μg/L (range: 1.1-476 μg/L) in Chakdaha, 60 μg/L (range: 0.30-202 μg/L) in Manikgonj, and 208 μg/L (range: 1.3-575 μg/L) in CNP groundwater. The Fe-reduction mechanism was found to be the dominant geochemical process in releasing As from sediment to groundwater in Chakdaha, West Bengal, however the Mn-reduction process was dominant in groundwaters of Manikgonj, Bangladesh. In Chianan Plain groundwater, a combination of geochemical processes (e.g., bacterial Fe-reduction, mineral precipitation and dissolution reactions) controlled release of As. Fluorescence spectral patterns of the groundwater showed low relative fluorescence intensity (RFI) of dissolved humic substances in BDP groundwater (mean: 63 and 72 QSU, Chakdaha and Manikgonj, respectively), while high RFI was observed in CNP groundwater (mean: 393 QSU). The FT-IR spectra of the extracted humic acid fractions from sediments of Chianan Plain showed a stronger aliphatic band at 2850-3000 cm⁻¹ and a higher resolved fingerprint area (from 1700 to 900 cm⁻¹) compared with BDP sediments. The geochemical differences between the study areas may play a crucial role in the clinical manifestation of Blackfoot disease observed only in Chianan Plain, SW Taiwan.