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.     

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.     

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.     

Sources of low-arsenic groundwater in the Bengal Basin: investigating the influence of the last glacial maximum palaeosol using a 115-km traverse across Bangladesh

Pollution of groundwater in the Bengal Basin (Bangladesh and West Bengal, India) by arsenic (As) puts at risk the health of more than 100 million consumers. Using 1,580 borehole lithological logs and published hydrochemistry on 2,387 wells, it was predicted that low-As (<10 μg/L) groundwater exists, in palaeo-interfluvial aquifers of brown sand capped by a protective palaeosol, beneath at least 45,000 km² of the Bengal Basin. The aquifers were predicted to be at a depth of as little as 25 m below ground level (mbgl), and typically no more than 50 mbgl. The predictions were confirmed along an east–west traverse 115 km in length (i.e. across half of Bangladesh) by drilling 28 new boreholes to 91-m depth to reveal subsurface sedimentology, and by mapping As distribution in groundwater. The aquifers identified occur at typically <40 mbgl and so are accessible with local drilling methods. A protective palaeosol that caps the palaeo-interfluvial aquifers prevents downward movement into them of As-polluted groundwater present in shallower palaeo-channel aquifers and ensures that the palaeo-interfluvial aquifers will yield low-As groundwater for the foreseeable future. Their use, in place of the shallower As-polluted palaeo-channel aquifers, would rapidly mitigate the health risks from consumption of As-polluted groundwater.     

Role of Quaternary stratigraphy on arsenic-contaminated groundwater from parts of Barak Valley, Assam, North–East India

Groundwater arsenic survey in Cachar and Karimganj districts of Barak Valley, Assam shows that people in these two districts are drinking arsenic-contaminated (max. 350 μg/l) groundwater. 66% of tubewells in these two districts have arsenic concentration above the WHO guideline value of 10 μg/l and 26% tubewells have arsenic above 50 μg/l, the Indian standards for arsenic in drinking water. 90% of installed tubewells in these two districts are shallow depth (14–40 m). Shallow tubewells were installed in Holocene Newer Alluvium aquifers are characterised by grey to black coloured fine grained organic rich argillaceous sediments and are mostly arsenic contamination in groundwater. Plio-Pleistocene Older Alluvium aquifers composed of shale, ferruginous sandstone, mottle clay, pebble and boulder beds, which at higher location or with thin cover of Newer Alluvium sediments are safe in arsenic contamination in groundwater. 91% of tubewell water samples show significantly higher concentrations of iron beyond its permissible limit of 1 mg/l. The iron content in these two districts varies from 0.5 to as much as 48 mg/l. Most of the arsenic contaminated villages of Cachar and Karimganj districts are located in entrenched channels and flood plains of Newer Alluvium sediments in Barak-Surma-Langai Rivers system. However, deeper tubewells (>60 m) in Plio-Pleistocene Older Alluvium aquifers would be a better option for arsenic-safe groundwater. The arsenic in groundwater is getting released from associated Holocene sediments which were likely deposited from the surrounding Tertiary Barail hill range.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.     

Arsenic Distribution Pattern in Different Sources of Drinking Water and their Geological Background in Guanzhong Basin,Shaanxi, China

To study arsenic(As) content and distribution patterns as well as the genesis of different kinds of water, especially the different sources of drinking water in Guanzhong Basin, Shaanxi province, China, 139 water samples were collected at 62 sampling points from wells of different depths, from hot springs, and rivers. The As content of these samples was measured by the intermittent flowhydride generation atomic fluorescence spectrometry method(HG-AFS). The As concentrations in the drinking water in Guanzhong Basin vary greatly(0.00–68.08 μg/L), and the As concentration of groundwater in southern Guanzhong Basin is different from that in the northern Guanzhong Basin. Even within the same location in southern Guanzhong Basin, the As concentrations at different depths vary greatly. As concentration of groundwater from the shallow wells(50 m deep, 0.56–3.87 μg/L) is much lower than from deep wells(110–360 m deep, 19.34–62.91 μg/L), whereas As concentration in water of any depth in northern Guanzhong Basin is 10 μg/L. Southern Guanzhong Basin is a newly discovered high-As groundwater area in China. The high-As groundwater is mainly distributed in areas between the Qinling Mountains and Weihe River; it has only been found at depths ranging from 110 to 360 m in confined aquifers, which store water in the Lishi and Wucheng Loess(Lower and Middle Pleistocene) in the southern Guanzhong Basin. As concentration of hot spring water is 6.47–11.94 μg/L; that of geothermal water between 1000 and 1500 m deep is 43.68–68.08 μg/L. The high-As well water at depths from 110 to 360 m in southern Guanzhong Basin has a very low fluorine(F) value, which is generally 0.10 mg/L. Otherwise, the hot springs of Lintong and Tangyu and the geothermal water in southern Guanzhong Basin have very high F values(8.07–14.96 mg/L). The results indicate that highAs groundwater in depths from 110 to 360 m is unlikely to have a direct relationship with the geothermal water in the same area. As concentration of all reservoirs and rivers(both contaminated and uncontaminated) in the Guanzhong Basin is 10 μg/L. This shows that pollution in the surface water is not the source of the high-As in the southern Guanzhong Basin. The partition boundaries of the high- and low-As groundwater area corresponds to the partition boundaries of the tectonic units in the Guanzhong Basin. This probably indicates that the high-As groundwater areas can be correlated to their geological underpinning and structural framework. In southern Guanzhong Basin, the main sources of drinking water for villages and small towns today are wells between 110–360 m deep. All of their As contents exceed the limit of the Chinese National Standard and the International Standard(10 μg/L) and so local residents should use other sources of clean water that are 50 m deep, instead of deep groundwater(110 to 360 m) for their drinking water supply.     

Arsenic mobilization in alluvial soils of Punjab, North–West India under flood irrigation practices

A laboratory investigation was carried out to examine the mechanism of arsenic (As) mobilization under flooded conditions (24 and 240 h) in 18 alluvial soils of Punjab, North–West India. Total dissolved As increased from a range of 3–16 μg L^?1 (mean 9 μg L^?1) to a range of 33–1,761 μg L^?1 (mean 392 μg L^?1) with the increase in flooding period from 24 to 240 h. The amount of As mobilization varied depending upon redox potential (pe) created by flooding conditions. After 24 h of flooded conditions, pe of soil water suspension ranged from ?1.75 to 0.77 (mean ?0.24). Increasing the flooding period to 240 h, pe of soil water suspension decreased in the range of ?4.49 to ?2.74 (mean ?3.29). Pourbaix diagram identified arsenate (HAsO₄ ^2?) as predominant species in most of the alluvial soil–water suspensions under oxidized conditions, after 24 h of equilibration period, which ultimately transformed to arsenite (H₃AsO₃ ⁰) after 240 h of anaerobic condition due to more reduced status. The solid phase identified was orpiment (As₂S₃). Identification of iron and manganese species in alluvial soil water suspension by Pourbaix diagram indicated decline in both soluble Fe²⁺ and SO₄ ^2? concentration due to the formation of iron sulfide mineral phase after 240 h under anaerobic conditions. In these soils, decline in soluble Fe was also due to the precipitation of vivianite [Fe₃(PO₄)₂·8H₂O]. Elevated arsenic content and low pe value were measured in aquifers located in paddy growing fields comparative to aquifers of other sites. Large degree of variability in As concentrations was recorded in aquifers located at same sites. Thus, it is better to analyze each aquifer for their As content rather than to depends on the prediction on As content of neighbouring wells. The present investigation elucidates that flood irrigation practices in Punjab for growing paddy crop could induce the geochemical conditions favorable to mobilize arsenic from surface soils which could eventually elevate its content in the underlying shallow aquifers. Water abstracted from these aquifers by hand pumps or tube wells for drinking purposes could create hazards for local population due to loading with arsenic concentration above the safe limits. Thus, to avoid further contamination of shallow aquifers with arsenic, it is advisable to shift the flooded rice cultivation to other upland crops having lesser water requirement.     

The behavior of arsenic and antimony at Pezinok mining site,southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.     

Arsenic mobilization in shallow aquifers of Datong Basin: Hydrochemical and mineralogical evidences

To better understand the sources and mobilization processes responsible for arsenic enrichment in groundwater in the central part of Datong Basin where serious arsenic poisoning cases have been reported, hydrochemical characteristics of the groundwater and the geochemical and mineralogical features of the aquifer sediments were studied. The aqueous arsenic levels are strongly depth-dependent in the study area and the high arsenic concentrations are found at depths between 15 m and 60 m, with a maximum up to 1820 μg/L. The hydrochemical characteristics of high arsenic groundwater from the Datong Basin indicate that the mobilization of arsenic is related to reductive dissolution of Fe oxides/oxyhydroxides and/or desorption from the Fe oxides/oxyhydroxides at high pH (above 8.0). The bulk chemical results of sediments show the arsenic and iron are moderately correlated, suggesting that arsenic is associated with iron-bearing minerals. Results of sequential-extraction experiment show that solid-phase arsenic is similarly distributed among the different pools of reservoir in the aquifer sediments. Strongly adsorbed arsenic and co-precipitated arsenic are its dominant species in the solid-phase. Geochemical studies using chemical analysis, X-ray diffraction and scanning electron microscopy on magnetically separated fractions demonstrate that iron oxides/oxyhydroxides with residual magnetite and chlorite, illite, iron oxides/oxyhydroxides-coated quartz and feldspar, and ankerite are the dominant carriers of arsenic in the sediments. The major processes of arsenic mobilization are probably linked to desorption of As from Fe oxides/oxyhydroxides and reductive dissolution of Fe-rich phases in the aquifer sediments under reducing and alkaline conditions.     

Investigation of fluoride contamination and its mobility in groundwater of Simlapal block of Bankura district,West Bengal,India

The occurrence of dental/skeletal fluorosis among the people in the study area provided the motivation to assess the distribution, severity and impact of fluoride contamination in groundwater of Bankura district at Simlapal block, West Bengal, India. To meet the desired objective, groundwater samples were collected from different locations of Laxmisagar, Machatora and Kusumkanali regions of Simlapal block at different depths of tube wells in both pre- and post-monsoon seasons. Geochemical results reveal that the groundwaters are mostly moderate- to hard-water type. Of total groundwater samples, 37% are situated mainly in relatively higher elevated region containing fluoride above 1.5 mg/L, indicating that host aquifers are severely affected by fluoride contamination. Machatora region is highly affected by fluoride contamination with maximum elevated concentration of 12.2 mg/L. Several symptoms of fluorosis among the different age-groups of people in Laxmisagar and Machatora areas are indicating consumption of fluoridated water for prolonged period. The groundwater samples were mainly Na–Ca–HCO₃ type and rock dominance indicating the dissolution of minerals taking place. Ion exchange between OH^? ion and F^? ion present in fluoride-bearing mineral is the most dominant mechanism of fluoride leaching. High concentration of Na⁺ and HCO₃ ^? increases the alkalinity of the water, providing a favorable condition for fluoride to leach into groundwater from its host rocks and minerals.     

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.     

Spatial variation in arsenic and fluoride concentrations of shallow groundwater from the town of Shahai in the Hetao basin,Inner Mongolia

Twenty-nine wells were selected for groundwater sampling in the town of Shahai, in the Hetao basin, Inner Mongolia. Four multilevel samplers were installed for monitoring groundwater chemistry at depths of 2.5–20 m. Results show that groundwater As exhibits a large spatial variation, ranging between 0.96 and 720 μg/L, with 71% of samples exceeding the WHO drinking water guideline value (10 μg/L). Fluoride concentrations range between 0.30 and 2.57 mg/L. There is no significant correlation between As and F⁻ concentrations. Greater As concentrations were found with increasing well depth. However, F⁻ concentrations do not show a consistent trend with depth. Groundwater with relatively low Eh has high As concentrations, indicating that the reducing environment is the major factor controlling As mobilization. Low As concentrations (<10 μg/L) are found in groundwater at depths less than 10 m. High groundwater As concentration is associated with aquifers that have thick overlying clay layers. The clay layers, mainly occurring at depths <10 m, have low permeability and high organic C content. These strata restrict diffusion of atmospheric O₂ into the aquifers, and lead to reducing conditions that favor As release. Sediment composition is an additional factor in determining dissolved As concentrations. In aquifers composed of yellowish-brown fine sands at depths around 10 m, groundwater generally has low As concentrations which is attributed to the high As adsorption capacity of the yellow–brown Fe oxyhydroxide coatings. Fluoride concentration is positively correlated with pH and negatively correlated with Ca²⁺ concentration. All groundwater samples are over-saturated with respect to calcite and under-saturated with respect to fluorite. Dissolution and precipitation of Ca minerals (such as fluorite and calcite), and F⁻ adsorption–desorption are likely controlling the concentration of F⁻ in groundwater.     

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.     

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.     

Arsenic variability and groundwater age in three water supply wells in southeast New Hampshire

Three wells in New Hampshire were sampled bimonthly over three years to evaluate the temporal variability of arsenic concentrations and groundwater age.All samples had measurable concentrations of arsenic throughout the entire sampling period and concentrations in individual wells had a mean variation of more than 7 μg/L.The time series data from this sampling effort showed that arsenic concentrations ranged from a median of 4 μg/L in a glacial aquifer well(SGW-65)to medians of 19μg/L and37 μg/L in wells(SGW-93 and KFW-87)screened in the bedrock aquifer,respectively.These high arsenic concentrations were associated with the consistently high pH(median≥8)and low dissolved oxygen(median0.1 mg/L)in the bedrock aquifer wells,which is typical of fractured crystalline bedrock aquifers in New Hampshire.Groundwater from the glacial aquifer often has high dissolved oxygen,but in this case was consistently low.The pH also is generally acidic in the glacial aquifer but in this case was slightly alkaline(median = 7.5).Also,sorption sites may be more abundant in glacial aquifer deposits than in fractured bedrock which may contribute to lower arsenic concentrations.Mean groundwater ages were less than 50 years old in all three wells and correlated with conservative tracer concentrations,such as chloride;however,mean age was not directly correlated with arsenic concentrations.Arsenic concentrations at KFW-87 did correlate with water levels,in addition,there was a seasonal pattern,which suggests that either the timing of or multiple sampling efforts may be important to define the full range of arsenic concentrations in domestic bedrock wells.Since geochemically reduced conditions and alkaline pHs are common to both bedrock and glacial aquifer wells in this study,groundwater age correlates less strongly with arsenic concentrations than geochemical conditions.There also is evidence of direct hydraulic connection between the glacial and bedrock aquifers,which can influence arsenic concentrations.Correlations between arsenic concentrations and the age of the old fraction of water in SGW-65 and the age of the young fraction of water in SGW-93 suggest that water in the two aquifers may be mixing or at least some of the deeper,older water captured by the glacial aquifer well may be from a similar source as the shallow young groundwater from the bedrock aquifer.The contrast in arsenic concentrations in the two aquifers may be because of increased adsorption capacity of glacio-fluvial sediments,which can limit contaminants more than fractured rock.In addition,this study illustrates that long residence times are not necessary to achieve more geochemically evolved conditions such as high pH and reduced conditions as is typically found with older water in other regions.     

Hydrogeochemical and multi-tracer investigations of arsenic-affected aquifers in semi-arid West Africa

The semi-arid Sahel regions of West Africa rely heavily on groundwater from shallow to moderately deep(100 m b.g.l.)crystalline bedrock aquifers for drinking water production.Groundwater quality may be affected by high geogenic arsenic(As)concentrations(10μg/L)stemming from the oxidation of sulphide minerals(pyrite,arsenopyrite)in mineralised zones.These aquifers are still little investigated,especially concerning groundwater residence times and the influence of the annual monsoon season on groundwater chemistry.To gain insights on the temporal aspects of As contamination,we have used isotope tracers(noble gases,~3H,stable water isotopes(~2 H,~(18)O))and performed hydrochemical analyses on groundwater abstracted from tube wells and dug wells in a small study area in southwestern Burkina Faso.Results revealed a great variability in groundwater properties(e.g.redox conditions,As concentrations,water level,residence time)over spatial scales of only a few hundred metres,characteristic of the highly heterogeneous fractured underground.Elevated As levels are found in oxic groundwater of circum-neutral pH and show little relation with any of the measured parameters.Arsenic concentrations are relatively stable over the course of the year,with little effect seen by the monsoon.Groundwater residence time does not seem to have an influence on As concentrations,as elevated As can be found both in groundwater with short(50 a)and long(10~3 a)residence times as indicated by ~3He/~4He ratios spanning three orders of magnitude.These results support the hypothesis that the proximity to mineralised zones is the most crucial factor controlling As concentrations in the observed redox/pH conditions.The existence of very old water portions with residence times10~3 years already at depths of50 m b.g.l.is a new finding for the shallow fractured bedrock aquifers of Burkina Faso,suggesting that overexploitation of these relatively low-yielding aquifers may be an issue in the future.     

内蒙古河套平原典型高砷区地下水中砷的演化规律

通过对高砷地下水典型区完整地质单元不同深度含水层地下水进行监测,分析了与砷释放、迁移和富集有关的敏感因素（水位、Eh、总铁、亚铁等）的时间和空间变化规律,探讨了高砷地下水的形成机理。结果发现,地下水灌溉区和黄河水灌溉区,地下水水位均受人为灌溉活动的影响。地下水砷含量在空间和时间尺度上发生有规律的变化。在空间尺度上,地下水中砷含量随着深度的增加而升高,井深小于10 m的地下水砷含量在1.88～2.58 μg/L;井深在10~15 m之间的地下水中砷含量在18.2～217 μg/L;井深在15~25 m之间的地下水中砷含量在38.3～226 μg/L。受人为灌溉影响,地下水中砷的含量会随着地下水位的抬升而升高。地下水砷含量随时间变化的原因是水位抬升使水位变化造成氧化还原环境改变。地下水系统中含砷铁氧化物矿物的还原性溶解、脱硫酸作用等是控制地下水砷含量的主要水文地球化学过程。     

Mobility of arsenic in a Bangladesh aquifer: Inferences from geochemical profiles, leaching data, and mineralogical characterization

Aquifer geochemistry was characterized at a field site in the Munshiganj district of Bangladesh where the groundwater is severely contaminated by As. Vertical profiles of aqueous and solid phase parameters were measured in a sandy deep aquifer (depth >150 m) below a thick confining clay (119 to 150 m), a sandy upper aquifer (3.5 to 119 m) above this confining layer, and a surficial clay layer (<3.5 m). In the deep aquifer and near the top of the upper aquifer, aqueous As levels are low (<10 μg/L), but aqueous As approaches a maximum of 640 μg/L at a depth of 30 to 40 m and falls to 58 μg/L near the base (107 m) of the upper aquifer. In contrast, solid phase As concentrations are uniformly low, rarely exceeding 2 μg/g in the two sandy aquifers and never exceeding 10 μg/g in the clay layers. Solid phase As is also similarly distributed among a variety of reservoirs in the deep and upper aquifer, including adsorbed As, As coprecipitated in solids leachable by mild acids and reductants, and As incorporated in silicates and other more recalcitrant phases. One notable difference among depths is that sorbed As loads, considered with respect to solid phase Fe extractable with 1 N HCl, 0.2 M oxalic acid, and a 0.5 M Ti(III)-citrate-EDTA solution, appear to be at capacity at depths where aqueous As is highest; this suggests that sorption limitations may, in part, explain the aqueous As depth profile at this site. Competition for sorption sites by silicate, phosphate, and carbonate oxyanions appear to sustain elevated aqueous As levels in the upper aquifer. Furthermore, geochemical profiles are consistent with the hypothesis that past or ongoing reductive dissolution of Fe(III) oxyhydroxides acts synergistically with competitive sorption to maintain elevated dissolved As levels in the upper aquifer. Microprobe data indicate substantial spatial comapping between As and Fe in both the upper and deep aquifer sediments, and microscopic observations reveal ubiquitous Fe coatings on most solid phases, including quartz, feldspars, and aluminosilicates. Extraction results and XRD analysis of density/magnetic separates suggest that these coatings may comprise predominantly Fe(II) and mixed valence Fe solids, although the presence of Fe(III) oxyhydroxides can not be ruled out. These data suggest As release may continue to be linked to dissolution processes targeting Fe, or Fe-rich, phases in these aquifers.