Contrasting sorption behaviours affecting groundwater arsenic concentration in Kandal Province,Cambodia

Natural arsenic(As)contamination of groundwater which provides drinking water and/or irrigation supplies remains a major public health issue,particularly in South and Southeast Asia.A number of studies have evaluated various aspects of the biogeochemical controls on As mobilization in aquifers typical to this region,however many are predicated on the assumption that key biogeochemical processes may be deduced by sampled water chemistry.The validity of this assumption has not been clearly established even though the role of sorption/desorption of As and other heavy metals onto Fe/Mn(hydr)oxides is an important control in As mobilization.Here,selective chemical extractions of sand-rich and clay-rich sediments from an As-affected aquifer in Kandal Province,Cambodia,were undertaken to explore the potential role of partial re-equilibrium through sorption/desorption reactions of As and related solutes(Fe,Mn and P)between groundwater and the associated solid aquifer matrix.In general,groundwater As is strongly affected by both pH and Eh throughout the study area.However,contrasting sorption behaviour is observed in two distinct sand-dominated(T-Sand)and clay dominated(T-Clay)transects,and plausibly attributed to differing dominant lithologies,biogeochemical and/or hydrogeological conditions.Sorption/desorption processes appear to be re-setting groundwater As concentrations in both transects,but to varying extents and in different ways.In T-Sand,which is typically highly reducing,correlations suggest that dissolved As may be sequestered by sorption/re-adsorption to Fe-bearing mineral phases and/or sedimentary organic matter;in T-Clay Eh is a major control on As mobilization although binding/occlusion of Fe-bearing minerals to sedimentary organic matter may also occur.Multiple linear regression analysis was conducted with groups categorised by transect and by Eh,and the output correlations support the contrasting sorption behaviours encountered in this study area.Irrespective of transect,however,the key biogeochemical processes which initially control As mobilization in such aquifers,may be "masked" by the re-setting of As concentrations through in-aquifer sorption/desorption processes.     

Groundwater chemistry and redox processes: Depth dependent arsenic release mechanism

Patchy occurrences of elevated As are often encountered in groundwater from the shallow aquifers (<50 m) of the Bengal Delta Plain (BDP). A clear understanding of various biogeochemical processes, responsible for As mobilization, is very important to explain this patchy occurrence and thus to mitigate the problem. The present study deals with the periodical monitoring of groundwater quality of five nested piezometeric wells between December 2008 and July 2009 to investigate the temporal changes in groundwater chemistry vis-a-vis the prevalent redox processes in the aquifer. Geochemical modeling has been carried out to identify key phases present in groundwater. A correlation study among different aqueous redox parameters has also been performed to evaluate prevailing redox processes in the aquifer. The long term monitoring of hydrochemical parameters in the multilevel wells together with hydrogeochemical equilibrium modeling has shown more subtle differences in the geochemical environment of the aquifer, which control the occurrence of high dissolved As in BDP groundwater. The groundwater is generally of Ca-HCO₃ type. The dissolved As concentration in groundwater exceeded both WHO and National drinking water standard (Bureau of Indian Standards; BIS, 10 μg L⁻¹) throughout the sampling period. The speciation of As and Fe indicate persistent reducing conditions within the aquifer [As(III): 87-97% of As_T and Fe(II): 76-96% of Fe_T]. The concentration of major aqueous solutes is relatively high in the shallow aquifer (wells A and B) and gradually decreases with increasing depth in most cases. The calculation of SI indicates that groundwater in the shallow aquifer is also relatively more saturated with carbonate minerals. This suggests that carbonate mineral dissolution is possibly influencing the groundwater chemistry and thereby controlling the mobilization of As in the monitored shallow aquifer. Hydrogeochemical investigation further suggests that Fe and/or Mn oxyhydroxide reduction is the principal process of As release in groundwater from deeper screened piezometric wells. The positive correlations of U and V with As, Fe and Mn indicate redox processes responsible for mobilization of As in the deeper screened piezometric wells are possibly microbially mediated. Thus, the study advocates that mobilization of As is depth dependent and concentrations of As in groundwater depends on single/combined release mechanisms.     

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.     

Factor and cluster analysis of water quality data of the groundwater wells of Kushtia, Bangladesh: Implication for arsenic enrichment and mobilization

The study area is located in the southwestern part of Bangladesh. Twenty-six groundwater samples were collected from both shallow and deep tube wells ranging in depth from 20 to 60 m. Multivariate statistical analyses including factor analysis, cluster analysis and multidimensional scaling were applied to the hydrogeochemical data. The results show that a few factors adequately represent the traits that define water chemistry. The first factor of Fe and HCO₃ is strongly influenced by bacterial Fe (III) reduction which would raise both Fe and HCO₃ concentrations in water. Na, Cl, Ca, Mg and PO₄ are grouped under the second factor representing the salinity sources of waters. The third factor, represented by As, Mn, SO₄ and K is related to As mobilization processes. Cluster analysis has been applied for the interpretation of the groundwater quality data. Initially Piper methods have been employed to obtain a first idea on the water types in the study area. Hierarchical cluster analysis was carried out for further classification of water types in the study area. Twelve components, namely, pH, Fe, Mn, As, Ca, Mg, Na, K, HCO₃, Cl, SO₄ and NO₃ have been used for this purpose. With hierarchical clustering analysis the water samples have been classified into 3 clusters. They are very high, high and moderately As-enriched groundwater as well as groundwater with elevated SO₄.     

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.     

Effects of desferrioxamine-B on the release of arsenic from volcanic rocks

Microorganisms play an important role in As mobilization into groundwater by directly influencing As speciation or indirectly inducing solubilisation from As-bearing phases, such as Fe, Mn and Al oxides. Iron oxide dissolution could also be induced by siderophores, small-molecule compounds produced by microorganisms to favour Fe uptake. Well waters exceeding the potable water limit of 10 μg As L⁻¹ (0.133 μM) have been widely reported in geothermal areas. Mechanisms responsible for these high As concentrations have not yet been thoroughly elucidated and the complexity of As mobilization in volcanic aquifers is still open to multiple interpretations. The present study was based on batch release experiments aimed at verifying and quantifying the effect of siderophores on As mobilization from volcanic rocks (lava, tuff, peperino and fallout deposit) at different pH and ligand concentration. In the experiments the siderophore trihydroxamate desferroxamine B (Dfob) was used and its effect on As release from volcanic rocks was manifest after the first days. The most favourable pH for As release was pH 6 while concentrations above 250 μM Dfob considerably enhanced As and Fe concentrations in solution. The As release from rocks was between 2.0–10% at pH 6 and 2.4–8.8% at pH 8. The As/Fe ratio in solution changed with time suggesting different release mechanisms and higher mobility of As compared to Fe during the first phase of the experiment. The presence of siderophore increased Fe dissolution rates up to 10 orders of magnitude. The As release correlated with Al, Mn, Fe, Si, V, Ga and Sb and the release of all these elements increased with increasing Dfob concentration. In alkaline environments also Cu, Zn and Pb were mobilized. The presence of siderophores represents a possible trigger for As mobilization from iron binding minerals to the water phase, with interesting implications for groundwater quality, plant uptake and bacterial communities.     

Comparison of arsenic geochemical evolution in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), China

Insightful knowledge of geochemical processes controlling As mobility is fundamental to understanding the occurrence of elevated As in groundwater. A comparative study of As geochemistry was conducted in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), two strongly As-enriched areas in China. The results show that As concentrations ranged from <1–1160 μg L⁻¹ (n = 37) in the Datong Basin and <1–804 μg L⁻¹ (n = 62) in the Hetao Basin. The groundwater is of the Na-HCO₃ type in the Datong Basin and Na-Cl-HCO₃ type in the Hetao Basin. Silicate mineral weathering and cation exchange processes dominated the groundwater geochemistry in the two study areas. Principal component analysis of 99 groundwater samples using 12 geochemical parameters indicated positive correlations between concentrations of As and Fe/Mn in the Datong Basin, but no correlation of As and Fe/Mn in the Hetao Basin. Phosphate correlated well with As in the Datong Basin and Hetao Basin, suggesting phosphate competition might be another process affecting As concentrations in groundwater. High concentrations of As, Fe, and Mn occurred in the pe range −2 to −4. The results of this study further understanding of the similarities and differences of As occurrence and mobility at various locations in China.     

Hydrochemical characterization,mechanism of mobilization,and natural background level evaluation of arsenic in the aquifers of upper Gangetic plain,India

Although arsenic (As) contamination has been extensively investigated in the aquifers of the lower and middle Gangetic plains, less attention has been given to the distribution and fate of As in the groundwater of the upper Gangetic plain, India. In the current study, groundwater samples (n = 40) were collected from Moradabad district in the upper Gangetic plain and analyzed for several physicochemical parameters to characterize the groundwater chemistry and evaluate various geogenic and anthropogenic factors controlling the occurrence, mobilization, and fate of As in the plain. Arsenic concentrations in groundwater ranged from 0.17 μg/L to 139 μg/L, with the majority of high-As groundwater associated with high Fe, Mn, and HCO₃⁻ and low NO₃⁻, SO₄²⁻, and negative Eh values, implying that As was released via reductive dissolution of Fe and Mn oxyhydroxides in reducing conditions under the influence of organic matter degradation. Interrelationships between various geochemical variables and the natural background level (NBL) quantification of As suggested the influence of anthropogenic processes on the mobility of As in groundwater. Piper and Gibbs diagrams and various bivariate plots revealed that the majority of groundwater was of the Ca²⁺ − Mg²⁺ − HCO₃⁻ type and that the major ions in groundwater were derived from carbonate and silicate weathering, cation exchange and reverse ion exchange processes, and anthropogenic activities. Moreover, the results of principal component analysis (PCA), and hierarchical cluster analysis (HCA) also suggested geogenic and anthropogenic sources for the ion concentration in groundwater. The health risk assessment showed a higher non-carcinogenic risk for children and a higher carcinogenic risk for adults, respectively, due to the daily intake of As contaminated groundwater. Overall, this study represents the first systematic investigation of the distribution, geochemical behavior, and release process of As in groundwater in the study area and provides a strong base for future research in the alluvial aquifers of the upper Gangetic plain.     

Arsenic distribution and hydrochemical factors in urban groundwater,Foshan City,South China

The distribution of arsenic （As） in shallow groundwater of eastern Chancheng District in Foshan City as a function of season and water table was investigated, and the influence of hydrochemical factors on the As distribution was discussed. The groundwater samples were collected from 20 sites in dry season and 9 sites in wet season. As concentrations in 20% groundwater samples exceeded value of the WHO guideline （10 μg/L）, and the highest As concentration of 23.5 μg/L occurred in dry season. It is observed that groundwater As concentration decreased with the increase of depth of water table in dry season, and were generally higher in wet season than that in dry season, indicating that ground surface As might be one of the main sources for shallow groundwater As in study area, especially in wet season. Groundwater As concentration in study area had significantly positive correlation with the concentration of Fe, Mn, NH4, F, and COD, and was positively correlated to pH, but negatively correlated to Eh and K, indicating that reductive dissolution of Fe and Mn （oxy）hydroxides might be one of the main control mechanisms for groundwater As mobilization, while pH and F also played an important role in controlling the groundwater As mobilization in study area.     

贵德盆地三河流域高砷地下水中溶解性有机物三维荧光特性及其指示意义

溶解性有机物(dissolved organic matter, DOM)可以通过多种方式控制含水层中砷的迁移转化。贵德盆地承压含水层地下水砷含量显著高于潜水含水层。为查明承压水中溶解性有机物对砷浓度的影响,对研究区地表水、潜水以及承压水进行吸光度和三维荧光光谱的分析,利用平行因子分析法确定了水样中有机物成分及荧光特征。结果表明,贵德盆地水体中DOM包含陆源类腐殖质(C1)、受人为影响的腐殖质(C2)、类醌化合物(C3)和微生物来源的腐殖质(C4)4种组分。陆源类腐殖质C1可在地下水中富集,占总有机质的40%~55%。相比于地下水,C2和C3则在地表水中占据较高的比例。高砷承压水中C2、C3所占比例高于低砷潜水。其中,C1可以通过络合作用促进溶解性砷浓度的提高,C3作为电子穿梭体可以促进含砷铁氧化物或氢氧化物的还原性溶解从而释放砷。微生物降解有机质生成的HCO-3可以与砷竞争吸附,促进砷的解吸附。此外,还原性溶解产生的Fe(II)与HCO-3形成FeCO3固定一部分的砷。该研究表明,地下水中的天然有机物通过络合作用和作为电子穿梭体促进铁氧化物还原导致地下水砷的富集,为分析黄河上游地区高砷地下水的成因提供理论依据。     

Microbial sulfidogenesis in ferrihydrite-rich environments: Effects on iron mineralogy and arsenic mobility

Microbial sulfidogenesis plays a potentially important role in Fe and As biogeochemistry within wetland soils, sediments and aquifers. This study investigates the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (pH 8) advective-flow environments. A series of experiments were conducted using advective-flow columns, with an initial solid-phase comprising As(III)-bearing ferrihydrite-coated quartz sand. Columns for each pH treatment were inoculated with the sulfate-reducing bacteria Desulfovibrio vulgaris, and were compared to additional abiotic control columns. Over a period of 28 days, microbial sulfidogenesis (as coupled to the incomplete oxidation of lactate) caused major changes in Fe mineralogy, including replacement of ferrihydrite by mackinawite and magnetite at the in-flow end of the inoculated columns. At pH 8, the Fe²⁺ produced by electron transfer between sulfide and ferrihydrite was mainly retained near its zone of formation. In contrast, at pH 6, much of the produced Fe²⁺ was transported with advecting groundwater, facilitating the downstream Fe²⁺-catalyzed transformation of ferrihydrite to goethite. At both pH 6 and pH 8, the sulfide-driven reductive dissolution of ferrihydrite and its replacement by mackinawite at the in-flow end of the inoculated columns resulted in substantial mobilization of As into the pore-water. At pH 8, this caused the downstream As concentrations within the inoculated columns to be greater than the corresponding abiotic column. However, the opposite occurred under pH 6 conditions, with the Fe²⁺-catalyzed transformation of ferrihydrite to goethite in the inoculated columns causing a decrease in downstream As concentrations compared to the abiotic column. Although thermodynamically favorable at intermediate times and depth intervals within the inoculated columns, solid As sulfide phases were undetectable by As XANES spectroscopy. Our findings show that microbial sulfidogenesis can trigger significant As mobilization in subsurface environments with advective groundwater flow. The results also demonstrate that formation of mackinawite by sulfidization of ferric (hydr)oxides is not effective for the immobilization of As, whereas the Fe²⁺-catalyzed transformation of ferrihydrite to goethite under mildly acidic conditions may mitigate As mobility.     

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.     

Effect of indigenous bacteria on geochemical behavior of arsenic in aquifer sediments from the Hetao Basin, Inner Mongolia: Evidence from sediment incubations

Incubation studies were carried out using 5 freshly collected sediments from shallow aquifers of the Hetao Basin, Inner Mongolia. The aquifer sediments covering a range of redox conditions, as indicated by their deep grey to yellow color were mixed with degassed artificial As solution or degassed deionized water at a ratio of solid to water of about 1:10 (wt./wt.). Suspensions which were either amended with glucose or autoclaved, were incubated in parallel with unamended suspensions. Five microcosm cultures of unamended sediments gradually release the equivalent of 0.03–0.30 μg/g As to the dissolved phase. The addition of glucose as a potential electron donor results in a marked stimulation in the mobilization of As (0.71–3.81 μg/g) in the amended incubations for all sediments. The quantity of As released accounts for 60–70% of As bound to Fe/Mn oxides in the original sediments. The microbially mediated mobilization of As with the organic nutrient as an electron donor is strongly associated with the As bound to Fe/Mn oxides, as well as the exchangeable As. During the incubations amended with glucose, 2–4% of the sediment Fe is released. The results suggest that the introduction of labile dissolved organic C into the yellowish sediment aquifers with As-free groundwater would reduce a significant proportion of the Fe(III) oxyhydroxides mediated by anaerobic bacteria respiration and increase groundwater As concentrations.     

河水入渗过程中近岸带地下水中砷的形成与影响因素研究

沈阳黄家水源地是我国北方地区典型的傍河地下水水源地,近岸带地下水中铁(Fe)、锰(Mn)、砷(As)含量严重超标。为查明地下水中As的来源与影响因素,对研究区河水、地下水以及土壤样品进行采集与测试,分析了水样常规指标与碳硫稳定同位素、土样中典型矿物、砷的含量及赋存形态。结果表明,研究区河水中As含量很低,而地下水中As含量普遍超标。河水入渗初期,氧化性河水使部分含As矿物发生氧化而释放As;随着河水入渗,地下水向还原环境转变,含As的Fe/Mn矿物发生还原性溶解,地下水中As含量逐渐升高。研究区典型矿物有黄铁矿、菱铁矿、软锰矿、赤铁矿、针铁矿、菱锰矿等,通过可交换态砷解吸、有机质结合态砷氧化、铁锰氧化物结合态砷还原性溶解等,介质中的As释放至地下水中。地下水中As含量与酸碱度(pH)、氧化还原电位(Eh)呈一定负相关,与溶解有机碳(DOC)、 {\mathrm{HCO}}_3^{-}、Fe、Mn含量呈正相关。     

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.     

Geochemical and hydrologic controls on the mobilization of arsenic derived from herbicide application

The fate and transport of As was examined at an industrial site where soil- and groundwater contamination are derived from the application of As₂O₃ as a herbicide. Application of arsenical herbicides was discontinued in the 1970s and soils in the source area were partially excavated in 2003. Arsenic contamination (up to 280 mg/kg) remains in the source area soils and a plume of As-contaminated groundwater persists in the surficial aquifer downgradient of the source area with maximum observed As concentrations of 1200 μg/L near the source area. The spatial extent of As contamination as defined by the 10 μg/L contour appears to have remained relatively stable over the period 1996–2006; the boundary of the 1000 μg/L contour has retreated over the same time period indicating a decrease in total As mass in the surficial groundwater.In column experiments conducted with source area soil, the As concentrations in the column effluent were comparable to those observed in groundwater near the source area. A substantial fraction of the As could be leached from the source area soil with ammonium sulfate and ammonium phosphate. Exhaustive extraction with background groundwater removed most of the total As. These results indicate that As in the source area soils is geochemically labile. Source area soils are low in extractable Fe, Mn and Al, and characterization by X-ray absorption spectroscopy and electron microscopy indicated that As is present primarily as arsenate sorbed to (alumino)silicate minerals. Batch sorption experiments showed much less sorption on surficial aquifer sediments than on sediments from the Jackson Bluff Formation (JBF), a presumed confining layer. This limited capacity of the surficial aquifer sediments for As sorption is consistent with the similar As contents observed for these sediments within and upgradient of the As plume. The apparent stability of the As plume cannot be explained by sequestration of As within the surficial aquifer. Sorption to JBF sediments may contribute to As sequestration, but As enrichment in JBF sediments within the plume (i.e., as compared with JBF sediments upgradient) was not observed. These results indicate that neither the persistence of As in the source area soils or the apparent stability of the plume of As-contaminated groundwater at this site can be explained by geochemical controls on As mobility. The absence of demonstrable geochemical bases for such observations suggests that possible hydrologic controls should be further investigated at this site.     

Deeper groundwater chemistry and geochemical modeling of the arsenic affected western Bengal basin,West Bengal,India

A regional scale hydrogeochemical study of a ∼21,000-km² area in the western Bengal basin shows the presence of hydrochemically distinct water bodies in the main semiconfined aquifer and deeper isolated aquifers. Spatial trends of solutes and geochemical modeling indicate that carbonate dissolution, silicate weathering, and cation exchange control the major-ion chemistry of groundwater and river water. The main aquifer water has also evolved by mixing with seawater from the Bay of Bengal and connate water. The isolated aquifers contain diagenetically altered water of probable marine origin. The postoxic main aquifer water exhibits overlapping redox zones (metal-reducing, sulfidic and methanogenic), indicative of partial redox equilibrium, with the possibility of oxidation in micro-scale environments. The redox processes are depth-dependent and hydrostratigraphically variable. Elevated dissolved As in the groundwater is possibly related to Fe(III) reduction, but is strongly influenced by coupled Fe–S–C redox cycles. Arsenic does not show good correlations with most solutes, suggesting involvement of multiple processes in As mobilization. The main river in the area, the Bhagirathi–Hoogly, is chemically distinctive from other streams in the vicinity and probably has little or no influence on deep groundwater chemistry. Arsenic in water of smaller streams (Jalangi and Ichamati) is probably introduced by groundwater discharge during the dry season.     

Influences of groundwater extraction on flow dynamics and arsenic levels in the western Hetao Basin,Inner Mongolia,China

Data on spatiotemporal variations in groundwater levels are crucial for understanding arsenic (As) behavior and dynamics in groundwater systems. Little is known about the influences of groundwater extraction on the transport and mobilization of As in the Hetao Basin, Inner Mongolia (China), so groundwater levels were recorded in five monitoring wells from 2011 to 2016 and in 57 irrigation wells and two multilevel wells in 2016. Results showed that groundwater level in the groundwater irrigation area had two troughs each year, induced by extensive groundwater extraction, while groundwater levels in the river-diverted (Yellow River) water irrigation area had two peaks each year, resulting from surface-water irrigation. From 2011 to 2016, groundwater levels in the groundwater irrigation area presented a decreasing trend due to the overextraction. Groundwater samples were taken for geochemical analysis each year in July from 2011 to 2016. Increasing trends were observed in groundwater total dissolved solids (TDS) and As. Owing to the reverse groundwater flow direction, the Shahai Lake acts as a new groundwater recharge source. Lake water had flushed the near-surface sediments, which contain abundant soluble components, and increased groundwater salinity. In addition, groundwater extraction induced strong downward hydraulic gradients, which led to leakage recharge from shallow high-TDS groundwater to the deep semiconfined aquifer. The most plausible explanation for similar variations among As, Fe(II) and total organic carbon (TOC) concentrations is the expected dissimilatory reduction of Fe(III) oxyhydroxides.