Arsenic, antimony and other toxic elements in the drinking water of Eastern Thessaly in Greece and its possible effects on human health

Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l⁻¹, As 1–125 μg l⁻¹, Br 6–60 μg l⁻¹, Cl 500–25,000 μg l⁻¹, Cr 1–6 μg l⁻¹, Cu 1–15 μg l⁻¹, Fe 10–352 μg l⁻¹, Mg 2,940–40,100 μg l⁻¹, Mn 0–8 μg l⁻¹, Na 3,650–13,740 μg l⁻¹, P 20–48 μg l⁻¹, Pb 0–7 μg l⁻¹, Sb 0–21 μg l⁻¹, Si 3,310–13,240 μg l⁻¹ and Zn 7–994 μg l⁻¹. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.     

Interrelationship of TOC,As, Fe,Mn, Al and Si in shallow alluvial aquifers in Chapai-Nawabganj,Northwestern Bangladesh: implication for potential source of organic carbon

Two boreholes and ten piezometers in the Ganges flood plain were drilled and installed for collecting As-rich sediments and groundwater. Groundwater samples from the Ganges flood plain were collected for the analysis of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃ ⁻, SO₄ ²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction was performed to characterize the major mineral contents of aquifer sediments and X-ray fluorescence (XRF) to analyze the major chemical composition of alluvial sediments. Results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescence index (15–38 QSU) of humic substance in groundwater was measured using spectrofluorometer, the results revealed that groundwater in the Ganges flood plain contains less organic matter (OM). Arsenic concentration in water ranges from 2.8 to 170 μg/L (mean 50 μg/L) in the Ganges flood plain. Arsenic content in sediments ranges from 2.1 to 14 mg/kg (mean 4.58 mg/kg) in the flood plains. TOC ranges from 0.49 to 3.53 g/kg (mean 1.64 g/kg) in the Ganges flood plain. Arsenic is positively correlated with TOC (R ² = 0.55) in sediments of this plain. Humic substances were extracted from the sediments from the Ganges flood plain. Fourier transform infrared analysis of the sediments revealed that the plain contains less humic substances. The source of organic carbon was assigned from δ¹³C values obtained using elemental analysis-isotope ratio mass spectrometry (EA-IRMS); the values (−10 to −29.44‰) strongly support the hypothesis that the OM of the Ganges flood plain is of terrestrial origin.     

Groundwater contamination with arsenic in Sherajdikhan,Bangladesh: geochemical and hydrological implications

An integrated study has been carried out to elucidate the distribution and occurrence of arsenic in selected groundwater samples in the area of Sherajdikhan, Bangladesh. Arsenic and other parameters (T, pH, EC, Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃ ⁻, SO₄ ²⁻, HCO₃ ⁻, PO₄ ³⁻, Fe, Mn and DOC) have been measured in groundwater samples collected from shallow/deep tube wells at different depths. Hydrogeochemical data suggest that the groundwaters are generally Ca–Mg–HCO₃ and Mg–Ca–HCO₃ types with bicarbonate (HCO₃ ⁻) as the dominant anion, though the other type of water has also been observed. Dissolved arsenic in groundwater ranged from 0.006 to 0.461 mg/l, with 69% groundwater samples exceeded the Bangladesh limit for safe drinking water (0.05 mg/l). Correlation and principal component analysis have been performed to find out possible relationships among the examined parameters in groundwater. Low concentrations of NO₃ ⁻ and SO₄ ²⁻, and high concentrations of DOC, HCO₃ ⁻ and PO₄ ³⁻ indicate the reducing condition of subsurface aquifer where sediments are deposited with abundant organic matter. Distinct relationship of As with Fe and Mn, and strong correlation with DOC suggests that the biodegradation of organic matter along with reductive dissolution of Fe–Mn oxyhydroxides has being considered the dominant process to release As in the aquifers studied herein.     

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.     

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer,southeastern Bangladesh

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25–33 m) and deep (191–318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl⁻ and higher proportions of Na⁺ relative to Ca²⁺, Mg²⁺, and K⁺ in groundwater suggest the influence by a source of Na⁺ and Cl⁻. Use of chemical fertilizers may cause higher concentrations of NH₄⁺ and PO₄³⁻ in shallow well samples. In general, most ions are positively correlated with Cl⁻, with Na⁺ showing an especially strong correlation with Cl⁻, indicating that these ions are derived from the same source of saline waters. The relationship between Cl⁻/HCO₃⁻ ratios and Cl⁻ also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO₃⁻ reflect the degree of water–rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO₄²⁻ and NO₃⁻ and high concentrations of dissolved Fe and PO₄³⁻ and NH₄⁺ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO₄²⁻ and NO₃⁻ but correlate weakly with Mo, Fe concentrations and positively with those of P, PO₄³⁻ and NH₄⁺ ions.     

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.     

Bioavailability of arsenic in the soil horizon: a laboratory column study

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long-term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the leaching behavior of As in surface soils is of high importance, because such behavior may increase the bioavailability of As in the soil horizon. In this study, we have investigated the role of phosphate ions in leaching and bioavailability of As in the soil horizon, where drinking groundwater contains elevated levels of As (≥50 μg/L). Soil and groundwater samples were characterized in the laboratory and measured for physical and chemical constituents. The soils are generally neutral to slightly alkaline in character (pH range 7.5–8.1) with low to moderate levels of free Fe₂O₃, Al₂O₃, CaCO₃, organic carbon, and clay content. The measured electrical conductivity (mean 599 μS/cm) of the soils demonstrates their non-saline nature. The Eh values (range −37 to −151 mV) of the groundwater indicate anoxic condition with low to moderate levels of bicarbonate (range 100–630 mg/L) and phosphate (range 0.002–4.0 mg/L). The arsenic content (range 50–690 μg/L; mean 321 μg/L) in groundwater has exceeded both WHO recommended guideline values (10 μg/L) and the National safe drinking water limit (50 μg/L). Regression analyses demonstrate that the bioavailability of As in the soil horizon is mainly controlled by the composition of free Fe₂O₃ and CaCO₃ content of the soils. However, application of P could increase bioavailability of As in the soil horizon and become available to plants for uptake.     

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

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

Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra River Plain,Bangladesh

The geochemical study of groundwaters and core sediments from the Old Brahmaputra plain of Bangladesh was conducted to investigate the distribution of arsenic and related trace elements. Groundwaters from tube wells are characterized by pH of 6.4–7.4, dissolved oxygen (DO) of 0.8–1.8 mg/l, Ca contents of 5–50 mg/l, and Fe contents of 0.2–12.9 mg/l. Arsenic concentrations ranged from 8 to 251 μg/l, with an average value of 63 μg/l. A strong positive correlation exists between As and Fe (r ² = 0.802; p = 0.001) concentrations in groundwater. The stratigraphic sequences in the cores consist of yellowish silty clays at top, passing downward into grayish to yellowish clays and sands. The uppermost 3 m and lower parts (from 13 to 31 m) of the core sediments are oxidized (average oxidation reduction potential (ORP) +170 and +220 mV, respectively), and the ORP values gradually become negative from 3 to 13 m depths (−35 to −180 mV), indicating that anoxic conditions prevail in the shallow aquifers of the Brahmaputra plain. Age determinations suggest that clay horizons at ~10 m depth were deposited at around 2,000 and 5,000 years BP (¹⁴C ages) during the transgressive phase of sea-level change. Elevated concentrations of As, Pb, Zn, Cu, Ni, Cr, and V are present in the silts and clays, probably due to adsorption onto clay particles. Significant concentrations of As occur in black peat and peaty sediments at depths between 9 and 13 m. A strong positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed onto Fe oxides in aquifer sediments.     

Arsenic associations in sediments from shallow aquifers of northwestern Hetao Basin,Inner Mongolia

Understanding the mechanism of arsenic mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Hetao Basin in Inner Mongolia, northern China. Aquifer geochemistry was characterized at three field sites (SH, HF, TYS) in Hangjinhouqi County of northwestern Hetao Basin. The results of bulk geochemistry analysis of sediment samples indicated that total As concentrations have a range of 6.8–58.5 mg/kg, with a median of 14.4 mg/kg. The highest As concentrations were found at 15–25 m depth. In the meanwhile, the range of As concentration in the sediments from background borehole is 3–21.8 mg/kg, with a median value of 9 mg/kg. The As sediments concentrations with depth from the SH borehole were correlated with the contents of Fe, Sb, B, V, total C and total S. Generally, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments. Distinct lithology profile and different geochemical characteristics of aquifer sediments indicate the sediments are associated with different sources and diverse sedimentary environments. Up to one third of arsenic in the sediments could be extracted by ammonium oxalate, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. Sequential extraction results indicate that arsenic occurs as strongly adsorbed on and/or co-precipitated with amorphous Fe oxyhydroxides in sediments accounting for 35 and 20%, respectively, of the total contents of arsenic. The release of As into groundwater may occur by desorption from the mineral surface driven by reductive dissolution of the Fe oxide minerals. Furthermore, small proportions of As associated with iron sulfides occur in the reductive sediments.     

Geochemical characteristics of the mud volcano fluids in southwestern Taiwan and their possible linkage to elevated arsenic concentration in Chianan plain groundwater

Fluid and mud samples were collected from Wushanting (WST), Hsiaokunshui (HKS), Yenshuikeng (YSK), Kuantzeling (KZL), and Kunshuiping (KSP) mud volcanoes of southwestern Taiwan. Concentrations of major ions and trace elements in mud volcanic fluids were analyzed to find the possible linkage to elevated arsenic (As) concentrations in the Chianan plain groundwater. The elevated Na⁺, K⁺, and Cl⁻ concentrations indicated possible marine origin of the fluids. The trace element concentrations in the mud volcanic fluids were generally low, but the As concentrations were up to 0.12 mg/L. High contents of As, Fe, and Mn were observed in the mud samples. Saturation index calculations indicated that both carbonate and oxide minerals acted as potential sinks for As in the mud volcanic fluids. Arsenic in the dewatering fluids and muds may be transported by the subsurface flow and surface streams as suspended solids and eventually deposited in the Chianan plain aquifers. Under reducing conditions, As may be released from the host minerals (such as Fe- and Mn-oxides/hydroxides), thereby causing widespread groundwater As pollution.     

Distribution of arsenic in sediment of Hangjinhou Banner- Linhe transect in Hetao Basin,North China

In this research, we laid a Hangjinhou Banner-Linhe District drilling transect along western piedmont of Hetao Basin to the modern Yellow River, which passes through the Langshan Mountain piedmont alluvial-proluvial fan, the Yellow River paleochannel, alluvial-fluvial plain of the Yellow River and the modern Yellow River flood plain successively and based on which we collected sedimentary samples of different geomorphic units. Based on hydrogeology and sedimentology and by means of stratum tracing and transects comparison, the analysis result comes out that the arsenic (As) sediments in Hetao Basin is distributed in obvious zoning form and is closely related to the sedimentary environment. The paleochannel zone in northern Basin has the highest content of As sediments, average content reaching 12.24 μg/g. In the horizontal direction of the profile, the distribution regularity of As is consistent to that of elements like Mn, Fe, Al and TOC, since they have experienced the same geochemical process in sediments. In the vertical direction, the high-arsenic sediments are mainly formed of grey black silty-fine sand layers or interbedding layers of silty-fine sand and muddy clay, rich in organic matter. The sedimentary environments are mainly shallow lakes and depressions, where the content of As is related to that of elements like Sb, Mn, B, V, etc., and particularly has significant relation with Fe.     

Desalination of a sedimentary rock aquifer system invaded by Pleistocene Champlain Sea water and processes controlling groundwater geochemistry

The objective of this study was to identify geochemical processes and Quaternary geological events responsible for the variations in groundwater geochemistry observed in a sedimentary rock aquifer system, including brackish to saline groundwater. Inorganic constituents and environmental isotopes were analyzed for 146 groundwater samples. Dissolution of carbonates dominates in recharge areas, resulting in Ca-, Mg-HCO₃ groundwater. Further along flow paths, under confined conditions, Ca²⁺–Na⁺ ion exchange causes groundwater evolution to Na-HCO₃ type. Na-Cl groundwater is also found and it falls on a seawater mixing line. Using conservative tracers, Cl⁻ and Br⁻, the original Champlain Sea water is shown to have been, in the region, a mixture of about 34% seawater and 66% freshwater, a composition still retained by some groundwater. Na-Cl groundwater thus results from mixing with former Champlain Sea water and also from solute diffusion from overlying marine clay. The system is thus found to be at different stages of desalinization, from the original Champlain Sea water still present in hydraulically stagnant areas of the aquifer to fully flushed conditions in parts, where more flow occurs, especially in recharge zones. The geochemical processes are integrated within the hydrogeological context to produce a conceptual geochemical evolution model for groundwater of the aquifer system.     

Arsenic and fluoride in a loess aquifer in the central area of Argentina

The objective of this study is to analyze the geochemical conditions associated with the presence of arsenic (As) and fluoride (F) in the phreatic aquifer of Coronel Moldes, in the central sector of the Argentine Chacopampean plain. The studied aquifer is composed of silty sand sediments of aeolian origin, typically loess-like sediments. The geochemical composition of water varies from sodium bicarbonate to sodium sulfate-chloride water. As contents range from low concentrations, below detection level, to 250 μg/l. High values of F (up to 12 mg/l) were recorded. A high As–F correlation was found (R ² = 0.84). The pH varied from 7.31 to 8.85 and the nitrates reached concentrations up to 200 mg/l, indicating an oxidant environment. The highest values of As and F agreed with sodium bicarbonate waters as well as with the highest values of pH recorded. There was a high correlation between As and F⁻ as well as between As and the Na/Ca ratio. The composition and texture of loess, low permeability and hydraulic gradients together with the geochemical features of sodium bicarbonate waters are proper conditions for the mobilization of As and F in groundwater in the central area of Argentina.     

Hydrogeochemical genesis of groundwaters with abnormal fluoride concentrations from Zhongxiang City,Hubei Province,central China

The groundwaters from Zhongxiang City, Hubei Province of central China, have high fluoride concentration up to 3.67 mg/L, and cases of dental fluorosis have been found in this region. To delineate the nature and extent of high fluoride groundwaters and to assess the major geochemical factors controlling the fluoride enrichment in groundwater, 14 groundwater samples and 5 Quaternary sediment samples were collected and their chemistry were determined in this study. Some water samples from fissured hard rock aquifers and Quaternary aquifers have high fluoride concentrations, whereas all karst water samples contain fluoride less than 1.5 mg/L due to their high Ca/Na ratios. For the high fluoride groundwaters in the fissured hard rocks, high HCO₃ ⁻ concentration and alkaline condition favor dissolution of fluorite and anion exchange between OH⁻ in groundwater and exchangeable F⁻ in some fluoride-bearing minerals. For fluoride enrichment in groundwaters of Quaternary aquifers, high contents of fluoride in the aquifer sediments and evapotranspiration are important controls.     

The hydrogeochemistry of a heavily used aquifer in the Mexican wine-producing Guadalupe Valley, Baja California

The Guadalupe Valley aquifer is the only water source for one of the most important wine industries in Mexico, and also the main public water supply for the nearby city of Ensenada. This groundwater is monitored for major ion, N-NO₃, P-PO₄, Fe, As, Se, Mo, Cd, Cu, Pb, Zn and Sb concentrations, as well as TDS, pH, dissolved oxygen and temperature. High concentrations of N-NO₃ (26 mg l⁻¹), Se (70 μg l⁻¹), Mo (18 μg l⁻¹) and Cu (4.3 μg l⁻¹) suggest that groundwater is being polluted by the use of fertilizers only in the western section of the aquifer, known as El Porvenir graben. Unlike the sites located near the main recharge area to the East of the aquifer, the water in El Porvenir graben has low tritium concentrations (<1.9 TU), indicating a pre-modern age, and thus longer water residence time. No significant variations in water quality (generally <10%) were detected throughout 2001–2002 in the aquifer, suggesting that reduced rainfall and recharge during this dry period did not significantly affect water quality. However, the wells nearest to the main recharge area in the Eastern aquifer show a slight but constant increase in TDS with time, probably as a result of the high (∼200 L S⁻¹) uninterrupted extraction of water at this specific recharge site. Relatively high As concentrations for the aquifer (10.5 μg l⁻¹) are only found near the northern limit of the basin associated with a geological fault.     

Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study

Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (Sb_T) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg⁻¹; in the Upper Floridan aquifer, Sb_T concentrations range from 8.1 to 1,462 pmol kg⁻¹; and for the Aquia aquifer, Sb_T concentrations range between 23 and 512 pmol kg⁻¹. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO₄ reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)₃⁰ species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)₆⁻ species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb₂S₄ ⁻ and Sb₂S₄ ²⁻, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO₄, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO₄ couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.     

A study of arsenic,iron and other dissolved ion variations in the groundwater of Bishnupur District,Manipur, India

The presence of arsenic (As) in groundwater and its effect on human health has become an issue of serious concern in recent years. The present study assessed the groundwater quality of the Bishnupur District, Manipur, with respect to drinking water standards. Higher concentrations of pH, iron and phosphate were observed at several locations. Phosphate and iron levels were highest in the pre-monsoon, followed by monsoon and post-monsoon seasons. The arsenic concentrations were highest during post-monsoon (1–200 μg L⁻¹) as compared to pre-monsoon (1–108 μg L⁻¹) and monsoon (2–99 μg L⁻¹). Kwakta and Ngakhalawai show higher levels of arsenic concentration as compared to the prescribed World Health Organization (WHO) and Bureau of Indian Standards (BIS) norms. Arsenic showed a strong positive correlation with phosphate and negative correlation with sulphate, suggesting a partial influence of anthropogenic sources. The study suggests that the Bishnupur area has an arsenic contamination problem, which is expected to increase in the near future.     

Adsorption kinetic control of As(III &; V) mobilization and sequestration by Mangrove sediment

Elevated concentrations of arsenic in the sediment and pore water in the Sundarban wetlands pose an environmental risk. Adsorption and desorption are hypothesized to be the major processes controlling arsenic retention in surface sediment under oxic/suboxic condition. This study aims to investigate sorption kinetics of As(III & V) and its feedback to arsenic mobilization in the mangrove sediment. It ranges from sand to silty clay loam and shows the adsorption of As(III & V) following the Langmuir relation. Estimates of the maximum adsorption capacity are 59.11 ± 13.26 μg g⁻¹ for As(III) and 58.45 ± 8.75 μg g⁻¹ at 30°C for As(V) in the pH range 4 to 8 and salinity 15–30 psu. Extent of adsorption decreases with increasing pH from 4 to 8 and desorption is the rate-limiting step in the reaction of arsenic with sediment. Arsenic in the sediment could be from a Himalayan supply and co-deposited organic matter drives its release from the sediment. Arsenic concentration in the sediment is well below its maximum absorption capacity, suggesting the release of sorbed arsenic in pore water by the microbial oxidation of organic matter in the sediment with less feedback of adsorption.     

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.