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 in soil, vegetation and water of a contaminated region

Arsenic concentrations of surface waters, soils and plants were surveyed in three contaminated villages of Bijar County. Total arsenic in water samples (4.5 to 280 μg/L) was correlated with electrical conductivity, total dissolved solid, total hardness, alkalinity, chloride, sulphate, bicarbonate, calcium and sodium (p<0.001). Total arsenic in the soils ranged from 105.4 to 1500 mg/kg. Some of the soil factors play an important role in soil arsenic content and its bioavailability for organisms. In general, the arsenic concentrations in plants were low, especially in the most common wild species. Among 13 plant species, the highest mean arsenic concentration was found in leaves of Mentha Longifolia (79.4 mg/kg). Arsenic levels in soils and plants were positively correlated, while the ability of the plants to accumulate the element, expressed by their biological accumulation coefficients and arsenic transfer factors, was independent of the soil arsenic concentration. Relationships between the arsenic concentrations in plants, soils and surface water and the environmental aspects of these relationships have been discussed in comparison with literature data. The accumulation of arsenic in environmental samples (soil, sediment, water, plant, etc.) poses a potential risk to human health due to the transfer of this element in aquatic media, their uptake by plants and subsequent introduction into the food chain.     

The source of fluoride toxicity in Muteh area,Isfahan, Iran

Endemic dental fluorosis has been observed in most inhabitants of three villages of Muteh area, located in northwest of Isfahan province, with mottled enamel related to high levels of fluoride in drinking water (1.8–2.2 ppm). Forty-seven groundwater samples from six villages were collected and fluoride concentrations along with physico-chemical parameters were analyzed. Fluoride concentration in this area varies from 0.2 to 9.2 mg/l with highest fluoride level at Muteh gold mine (Chahkhatun mine). Fluoride concentration positively correlates with pH and HCO₃ ⁻ indicating that alkaline pH provides a suitable condition for leaching of fluoride from surrounding rocks. The district is mainly covered by three lithological units, namely, metamorphic and granite rocks, alluvial sediments, and carbonate rocks. Factor analysis shows that parameters can be classified into four components: electrical conductivity (EC), total dissolved solids (TDS), Cl⁻, Na⁺ and K⁺, pH and F⁻, SO₄ ²⁻and Mg²⁺, HCO₃ ⁻ and Ca₂ ⁺. The groundwaters from the three geological units were compared using Mann–Whitney U test. The order of median fluoride concentration is: metamorphic and granite rocks > alluvial sediments > carbonate rocks. Hence, the fluoride content is most probably related to fluoride-bearing minerals such as amphibole and mica group minerals in metamorphic and granitic rocks. The concentration of fluoride in drinking water wells located near the metamorphic complex in Muteh area is above 2 ppm.     

Arsenic distribution, speciation and solubility in shallow groundwater of Owens Dry Lake, California

Generation of dust particles from the Owens Lake playa creates a severe air pollution hazard in the western United States. Much of the dust produced from the dry lakebed is derived from salts formed by evaporation of saline groundwater that often contains high concentrations of dissolved arsenic (As). The objectives of this research were to study the spatial distribution of dissolved arsenic in the shallow groundwater, and to examine factors affecting arsenic solubility and speciation. Evapoconcentration, redox potential, pH, and mineral solubility were examined as factors regulating arsenic biogeochemistry. Dissolved arsenic concentrations ranged from 0.1 to 96 mg L⁻¹ and showed a general increase from the shoreline to the center of the lakebed. Arsenic concentrations were strongly correlated to electrical conductivity (EC) and δD suggesting that evapoconcentration is an important process regulating total As concentrations. Arsenite [As(III)] was the dominant form of inorganic arsenic at Eh values less than about −170 mV while arsenate [As(V)] was predominant at higher Eh values. Organic arsenic was negligible (<0.21%) in all shallow groundwater samples. Dissolved arsenic concentrations do not appear to be strongly regulated by solid-phase reactions. Solid-phase arsenic concentrations generally ranged between 4.0 and 42.6 mg kg⁻¹ and a maximum concentration range (20 to 40 mg kg⁻¹) was reached as solution concentration increased up to 80 mg L⁻¹, indicating minimal sorption and/or precipitation of arsenic. Chemical equilibrium modeling indicated that orpiment (As₂S₃) was the only solid phase with a positive saturation index (indicating over-saturation), but only at high arsenic and sulfide concentrations. The findings of this research are important for assessing the potential environmental impacts of elevated arsenic concentrations on dust mitigation efforts taking place at Owens Dry Lake.     

Geochemical distribution of arsenic in waters,sediments and weathered gold mineralized rocks from Iron Quadrangle,Brazil

The Iron Quadrangle has been the scenery of the most important gold production in Brazil. It is estimated that during the three centuries of gold mining in the Iron Quadrangle, at least 390,000 t of arsenic was discharged into the drainage system. This study presents geochemical data for the three river basins in the region, with focus on surface water and stream sediment monitoring. Samples of primary and oxidized sulfide ores as well as of tailings and groundwater from the major gold mines were also studied. The highest As concentrations in water and stream sediments occur in the vicinity of mining areas. In surface water, up to 300 g As/l were found whereas the As contents in stream sediments were in the range of 20 to 4,000 mg/kg. The As³⁺/As⁵⁺ concentration ratios obtained for some water samples range from 1.10^у to 4.10^ф. The As mobility associated with ore-deposit weathering could be traced in some closed gold mines by observation of in-situ pyrite and arsenopyrite oxidation, precipitation of scorodite and gippsite, As adsorption onto goethite, and final liberation of As into underground and surface waters. This process is likely to produce large volumes of mine effluents containing total As and trivalent As up to 1,960 and 60 g/l, respectively. River sediments and tailings pile samples were submitted to a leaching procedure showing maximal arsenic release from 1 to 4% of the original total As in the samples. There are potential risks for As hazards in some areas induced by, for instance, the dispersion of old tailings by flooding, occupation of poisoned soils for settlements, and occasional consumption of contaminated surface and groundwater.     

A geochemistry study of arsenic speciation in overburden from Mae Moh Lignite Mine, Lampang, Thailand

The aim of this study was to investigate the geochemical characteristics of arsenic in the solid material samples of the Mae Moh Mine and also the Mae Moh power plants fly ash samples were systematically studied. Arsenic concentration in overburden, coal lignite and fly ash are variable (depending on source of solid samples). The results show that the strata of overburden, J seam of coal and fly ash are rich in arsenic and also relatively soluble from fly ash; it occurs as a surface precipitate on the ash particle. The experimental study on speciation in the strata also indicates that the arsenic speciation of Mae Moh solid samples are mainly arsenate, As (V), which are approaching exceed 80%. Arsenic content in the main of overburden is in the range of 14.3–888.8 mg/kg, which is larger than the arsenic background soil values. Solid materials polluted wastewater; the arsenic speciation was present predominantly as arsenate in the surface water of a series of Mae Moh solid materials basins.     

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.     

Arsenic content, fractionation, and ecological risk in the surface sediments of lake

The Nansi Lake has been seriously affected by long-term intensive industrial and urban activities. The objectives of this study were to determine the content, distribution, and ecological risk of arsenic and investigate the geochemical relationships between arsenic forms and sediment mineral phases of the Nansi Lake. Twenty samples of surface sediments were collected and analyzed for arsenic contents and chemical forms. Results indicated that total content of arsenic in the sediment samples averaged 13.45?mg/kg and ranged from 8.27 to 21.75?mg/kg. The arsenic was mostly associated with iron oxides (67.3%), followed by the association with the residual fraction (19.2%). In addition, total content of arsenic was positively correlated with the organic matter and iron contents in the sediment. The molar ratios of iron oxide bound arsenic content to iron content are lower than the maximal molar ratios of arsenic to iron for natural hematite, magnetite, and goethite. The total content of arsenic in the sediment samples was usually higher than threshold effect concentration of 9.79?mg/kg, but lower than probable effect concentration of 33.0?mg/kg for arsenic in freshwater sediments. Adverse effects or toxicity to the aquatic organisms, caused by arsenic in the sediments of the Nansi Lake, will likely occur at these levels of arsenic contamination.     

Naturally occurring arsenic in groundwater and identification of the geochemical sources in the Duero Cenozoic Basin, Spain

Arsenic concentrations surpassing potability limit of 10 μg/L in the groundwater supplies of an extensive area in the Duero Cenozoic Basin (central Spain) have been detected and the main sources of arsenic identified. Arsenic in 514 samples of groundwater, having mean values of 40.8 μg/L, is natural in origin. Geochemical analysis of 553 rock samples, assaying arsenic mean values of 23 mg/kg, was performed. Spatial coincidence between the arsenic anomaly in groundwater and the arsenic lithogeochemical distribution recorded in the Middle Miocene clayey organic-rich Zaratan facies illustrates that the rocks of this unit are the main source of arsenic in groundwater. The ferricretes associated to the Late Cretaceous–Middle Miocene siliciclastics also constitute a potential arsenic source. Mineralogical study has identified the presence of arsenic in iron oxides, authigenic pyrite, manganese oxides, inherited titanium–iron oxides, phyllosilicates and organomineral compounds. Arsenic mobilization to groundwater corresponds to arsenic desorption from iron and manganese oxides and from organic matter.     

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

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

Arsenic Geochemistry of the Great Dismal Swamp,Virginia, USA: Possible Organic Matter Controls

Surface water samples for arsenic (As) concentration and speciation analysis were collected from organic matter-rich blackwaters of the Lake Drummond portion of the Great Dismal Swamp in southeastern Virginia, USA. Arsenic concentrations and speciation were determined by selective hydride generation, gas chromatography with photoionization detection. Surface waters from the Great Dismal Swamp are high in dissolved organic carbon (DOC) concentrations (445–9,600 μmol/kg) and of low pH (4.2–6.4). Total dissolved As concentrations [i.e., As(III) + As(V)], hereafter As_T, range from 2.2 nmol/kg to 21.4 nmol/kg. Arsenite, As(III), concentrations range from ∼1 nmol/kg to 17.7 nmol/kg, and As(V) ranges from ∼1 nmol/kg to 14.1 nmol/kg. Arsenate, As(V), is the predominant form of dissolved As in the inflow waters to the Great Dismal Swamp, whereas within the swamp proper arsenite, As(III), dominates. Arsenite accounts for 8–37% of As_T in inflow waters west of the Suffolk Scarp, and between 54% and 81% of As_T in Lake Drummond and Great Dismal Swamp waters east of the scarp. Arsenite is strongly correlated to DOC (r = 0.94) and inversely related to pH (r = −0.9), both at greater than the 99% confidence level. Arsenate is weakly related to pH and DOC (r = 0.4 and −0.37, respectively), and neither relationship is statistically significant. No statistical relationships exist between As(V) or As(III) and PO₄ concentrations. The predominance of As(III) and its strong correlation with DOC in Great Dismal Swamp waters suggest that DOC may inhibit As(III) adsorption or form stable aqueous complexes with As(III) in these waters. Alternatively, phytoplankton and/or bacterially mediated reduction of As(V) may be important processes in the organic-rich blackwaters and/or sediment porewaters of the swamp, leading to the prevalence of As(III) in the water column.     

Investigating water quality and arsenic contamination in drinking water resources in the Tavşanlı District (Kütahya,Western Turkey)

Arsenic is a natural component of the earth’s crust, and it is transported into surface water and groundwater through the dissolution of rocks, minerals and ores. In addition, arsenic leaching processes contaminate water sources and this geogenic arsenic contamination causes significant water quality problems in many parts of the world. In this study, water quality, arsenic contamination and human health risks of drinking water resources in the Tav?anl? District were determined and the origins were discussed. For this purpose, geological and hydrogeological properties were investigated. In situ measurements and chemical analyses were carried out on water samples taken from drinking water sources such as wells, springs and surface waters for hydrogeochemical studies. According to the obtained results, water resources are Ca–Mg–HCO₃, Mg–HCO₃ and Na–HCO₃ type. Total As (As_T) concentration of the water samples sometimes exceeds the permissible limit given by the TSI-266 (Standards for drinking waters, Turkish Standards Institution, Ankara, 2005) and WHO (Guidelines for drinking-water quality, World Health Organization, Geneva, 2008) for drinking water. H₃AsO ₃ ⁰ and HAsO₄ ^2? are dominant arsenic species in groundwater and surface water, respectively. Typically high total arsenic concentrations can be found in regions characterized by magmatic rocks. In addition, As concentrations in surface waters were found to be higher than in groundwater in the region, due to the anthropogenic influence of mining activities in the region.     

Metal contamination of the environment by placer and primary gold mining in the Adola region of southern Ethiopia

Primary and placer gold mining sites in southern Ethiopia were studied to see the contribution of mining to the accumulation of metals in different environmental media. Sediment, water and plant samples were analyzed for Al, Mn, Fe, As, Ni, Cr, Cu, Co, Pb, W, Sb, Mo, Zn and V. Water parameters (pH, Eh, TDS, anions and cations) were also measured. The sediment analyses results show that the most abundant metals are Ni (average 224.7 mg/kg), Cr (199 mg/kg), Cu (174.2 mg/kg), V (167.3 mg/kg), Zn (105.5 mg/kg), Pb (61.5 mg/kg) and As (59.7 mg/kg) in the primary gold mining sites while the placer sites show high concentration of V (average 301.2 mg/kg), Cr (260.4 mg/kg), Zn (179 mg/kg), Ni (113.4 mg/kg), Cu (46.7 mg/kg), As (32.2 mg/kg) and Co (31 mg/kg). The metals Cu, Ni, W, Cr, As and Pb in primary and Sb, W, Cr, Ni, Zn, As and Mo in placer gold mining sites have geoaccumulation indexes (I _geo) from one to four indicating considerable accumulation of these metals. Waters from both primary and placer mining sites are near neutral to alkaline. Arsenic (average 92.8 μg/l), Ni (276.6 μg/l), Pb (18.7 μg/l), Sb (10.7 μg/l), Mn (1 mg/l), Fe (8.3 mg/l) and Al (23.8 mg/l) exceeded the guideline value for drinking water. Plants show high concentration of Cr (average 174.5 mg/kg), Ni (163.5 mg/kg), Zn (96 mg/kg) and W (48 mg/kg). Zinc, W, Mo, Ni and Cr show the maximum biological absorption coefficient (BAC) ranging 0.4–1.7, 0.1–104.6, 1.1–2.6, 0.2–1.6 and 0.2–3.6, respectively, and the results suggest bioaccumulation of these elements in plants. The minerals especially sulfides in the ore aggregate are the ultimate source of the metals. The release of the metals into the environmental media is facilitated (in addition to normal geologic processes) by human activities related to gold mining.     

Exposure and bioavailability of arsenic in contaminated soils from the La Parrilla mine, Spain

Arsenic derived from mining activity may contaminate water, soil and plant ecosystems resulting in human health and ecotoxicological risks. In this study, exposure assessment of arsenic (As) in soil, spoil, pondwater and plants collected from the areas contaminated by mine tailings and spoils in and around the La Parrilla mine, Caceres province, Spain, was carried out using AAS method. Water solubility, bioavailability and soil–plant transfer coefficients of As and phytoremediation potential of plants were determined. Arsenic concentrations varied from 148 to 2,540 mg/kg in soils of site 1 and from 610 to 1,285 mg/kg in site 2 exceeding the guideline limit for agricultural soil (50 mg/kg). Arsenic concentrations in pond waters varied from 8.8 to 101.4 μg/l. High concentrations of water-soluble As in the soils that ranged from 0.10 to 4.71 mg/kg in site 1 and from 0.46 to 4.75 mg/kg in site 2 exceeded the maximum permitted level of water-soluble As (0.04 mg/kg) in agricultural soils. Arsenic concentrations varied from 0.8 to 149.5 mg/kg dry wt in the plants of site 1 and from 2.0 to 10.0 mg/kg in the plants of site 2. Arsenic concentrations in plants increased in the approximate order: Retama sphaerocarpa < Pteridium aquilinum < Erica australis < Juncus effusus < Phalaris caerulescens < Spergula arvensis in site 1. The soil–plant transfer coefficients for As ranged from 0.001 to 0.21 in site 1 and from 0.004 to 0.016 in site 2. The bioconcentration factor based on water-soluble As of soil varied from 3.2 to 593.9 in the plants of site 1 whereas it varied from 2.1 to 20.7 in the plants of site 2. To our knowledge, this is the first study in Europe to report that the fern species P. aquilinum accumulates extremely low contents of As in its fronds despite high As levels in the soils. Therefore, the S. arvensis, P. caerulescens and J. effusus plant species grown in this area might be used to partly remove the bioavailable toxic As for the purpose of minimization of mining impacts until hypothetical hyperaccumulating and/or transgenic plants could be transplanted for the phytoremediation of As contaminated soils.     

Arsenic in soil and vegetation of a contaminated area

Plant and soil samples were collected from one uncontaminated and four contaminated sites (in the Dashkasan mining area western Iran). Total and water-soluble arsenic in the soil ranged from 7 to 795 and from 0.007 to 2.32 mg/kg, respectively. The highest arsenic concentration in soil was found at the ore dressing area (up to 1,180 mg/kg) and lowest at an uncontaminated area (up to 11 mg/kg). A total of 49 plant species belonging to 15 families were collected from four sampling sites. A significant positive correlation was detected between the concentrations of arsenic in plant dry matter and those in soils. The highest arsenic concentrations were found in Hyoscyamus kurdicus Bornm. (up to 205 mg/kg) and Helichrysum oligocephalum DC. (up to 162 mg/kg). These two accumulator species could have potential for soil clean-up by phytoextraction. The data have been compared with those for the Zarshuran mining area (north-western Iran) obtained in a former study.     

Environmental and health risk assessment in abandoned mining area, Zlata Idka, Slovakia

The Zlata Idka village is a typical mountainous settlement. As a consequence of more than 500 years of mining activity, its environment has been extensively affected by pollution from potentially toxic elements. This paper presents the results of an environmental-geochemical and health research in the Zlata Idka village, Slovakia. Geochemical analysis indicates that arsenic (As) and antimony (Sb) are enriched in soils, groundwater, surface water and stream sediments. The average As and Sb contents are 892 mg/kg and 818 mg/kg in soils, 195 mg/kg and 249 mg/kg in stream sediments, 0.028 mg/l and 0.021 mg/l in groundwater and 0.024 mg/l and 0.034 mg/l in surface water. Arsenic and Sb concentrations exceed upper permissible limits in locally grown vegetables. Within the epidemiological research the As and Sb contents in human tissues and fluids have been observed (blood, urine, nails and hair) in approximately one third of the village’s population (120 respondents). The average As and Sb concentrations were 16.3 μg/l and 3.8 μg/l in blood, 15.8 μg/l and 18.8 μg/l in urine, 3,179 μg/kg and 1,140 μg/kg in nails and 379 μg/kg and 357 μg/kg in hair. These concentrations are comparatively much higher than the average population. Health risk calculations for the ingestion of soil, water, and vegetables indicates a very high carcinogenic risk (>1/1,000) for as content in soil and water. The hazard quotient [HQ=average daily dose (ADD)/reference dose (RfD)] calculation method indicates a HQ>1 for groundwater As and Sb concentrations.     

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

The stoichiometry and stability of arsenic gaseous complexes were determined in the system As-H₂O ± NaCl ± HCl ± H₂S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As^(III) and As^(V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As^(III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As^(III) was measured from 250 to 450°C at the saturated vapor pressure of the system (P_sat) with a special titanium reactor that allows in situ sampling of the vapor phase. The values of partition coefficients for arsenious acid (H₃AsO₃) between an aqueous solution (pure H₂O) and its saturated vapor (K = mAs_vapor /mAs_liquid) were found to be independent of As^(III) solution concentrations (up to ∼1 to 2 mol As/kg) and equal to 0.012 ± 0.003, 0.063 ± 0.023, and 0.145 ± 0.020 at 250, 300, and 350°C, respectively. These results are interpreted by the formation, in the vapor phase, of As(OH)₃(gas), similar to the aqueous As hydroxide complex dominant in the liquid phase. Arsenic chloride or sulfide gaseous complexes were found to be negligible in the presence of HCl or H₂S (up to ∼0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As^(III)-H₂O (±NaCl) solutions up to 500°C demonstrate that the As(OH)₃ complex dominates As speciation both in dense H₂O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As^(III) measured in the H₂O-NaCl system up to 450°C are consistent with the As speciation derived from these spectroscopic measurements and can be described by a simple relationship as a function of the vapor-to-liquid density ratio and temperature. Arsenic^(III) partitioning between vapor and As-concentrated solutions (>2 mol As/kg) or As₂O₃ solid is consistent with the formation, in the vapor phase, of both As₄O₆ and As(OH)₃. Arsenic^(V) (arsenic acid, H₃AsO₄) vapor-liquid partitioning at 350°C for dilute aqueous solution was interpreted by the formation of AsO(OH)₃ in the vapor phase.The results obtained were combined with the corresponding properties for the aqueous As(III) hydroxide species to generate As(OH)₃(gas) thermodynamic parameters. Equilibrium calculations carried out by using these data indicate that As(OH)₃(gas) is by far the most dominant As complex in both volcanic gases and boiling hydrothermal systems. This species is likely to be responsible for the preferential partition of arsenic into the vapor phase as observed in fluid inclusions from high-temperature (400 to 700°C) Au-Cu (-Sn, -W) magmatic-hydrothermal ore deposits. The results of this study imply that hydrolysis and hydration could be also important for other metals and metalloids in the H₂O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.     

Geostatistical analysis of arsenic concentration in the groundwater of Malda district of West Bengal, India

The problem of arsenic (As) poisoning in the upper deltaic plain of the Ganga-Bhagirathi river system in the Bengal Basin of West Bengal, India is an alarming issue. Four blocks (Kaliachak-1, 2, 3 and English Bazar) of Malda district, West Bengal were critically studied. Geomorphologically, the area exhibits three terraces: the present Youngest terrace (T₀-terrace), the Older Shaugaon Surface (T₁-terrace) and the Oldest Baikunthapur Surface (T₂-terrace). On the basis of numerous measurements, including As-content, pH, DO, specific conductivity and salinity, it was observed that maximum As-content beyond the permissible limit (0.05 mg/L, Indian standard) occurs within a depth range of 10–30 m with a non-linear distribution pattern. Variance test also found that a block effect was highly significant in an As-distribution pattern. Mean arsenic level of Kaliachak block-1 is 0.2253 mg/L, followed by Kaliachak-2 with arsenic level 0.1923, Kaliachak-3 with arsenic level 0.1755 and English Bazar with arsenic level 0.1324. The arsenious belt lies mainly within the Older terrace (T₁). The very recent flood plain deposits of silvery white, fine sands lying very close to the Ganga River margin do not contain significant amounts of As. Elevated As-concentration in the ground water was observed in alluvial sands, grayish white to brownish in color and occurring away from the Ganga margin. The Oldest terrace (T2) further away from the Ganga margin (e.g. English Bazar) and Barind surface contains less arsenic. Barind surface acts as a hard capping with ferruginous sands and lateritic concretions-chocolate, mottled and purple brown in color-occurring northeast of the studied area. Arsenic content of ground water in the same locality within a radius of ∼ 20 m varies within wide limits. Thus, it poses problem to delineate its distribution pattern. Such a patchy occurrence possibly could not be explained satisfactorily solely by geomorphology. Chemical analysis of aquifer clay samples of the cores shows a maximum Ascontent of up to 3 mg/kg, whereas the bulk samples (sandclay mixture) of the cores contain a maximum of 17 mg/kg As-value. Therefore, it is not always true that clay contains elevated As-value.     

Distribution of arsenic and its mobility in shallow aquifer sediments from Ambikanagar, West Bengal, India

Sediments from a core retrieved during installation of a shallow drinking water well in Ambikanagar (West Bengal, India) were analyzed for various physical and chemical parameters. The geochemical analyses included: (1) a 4-step sequential extraction scheme to determine the distribution of As between different fractions, (2) As speciation (As³⁺ vs. As⁵⁺), and (3) C, N and S isotopes. The sediments have a low percentage of organic C and N (0.10-0.56% and 0.01-0.05%, respectively). Arsenic concentration is between 2 and 7 mg kg⁻¹, and it is mainly associated with the residual fraction, less susceptible to chemical weathering. The proportion of As³⁺ in these sediments is high and ranges from 24% to 74%. Arsenic in the second fraction (reducible) correlates well with Mn, and in the residual fraction As correlates well with several transition elements. The stable isotope results indicate microbial oxidation of organic matter involving SO₄ reduction. Oxidation of primary sulfide minerals and release of As from reduction of Fe-(oxy)hydroxides do not seem important mechanisms in As mobilization. Instead, the dominance of As³⁺ and presence of As⁵⁺ reducing microorganisms in this shallow aquifer imply As remobilization involving microbial processes that needs further investigations.     

西藏搭格架高温热泉中砷的地球化学异常及其存在形态

西藏搭格架高温热泉是我国大陆少有的大型间歇性喷泉,砷元素作为对人类威胁极大的环境问题普遍存在于热泉之中,搭格架高温热泉中砷元素质量浓度最高已达到了9.75 mg/L,其对地表水和浅层地下水的污染不容忽视。硫代砷是富含硫化物热泉中砷的存在形态之一,鉴于国内相关研究较少,本文对西藏搭格架地热区的热泉样品进行了水化学分析,并利用水文地球化学模拟软件PHREEQC开展了对热泉中砷元素存在形态的地球化学模拟。结果表明：西藏搭格架热泉中砷元素的存在形态有亚砷酸盐、砷酸盐和硫代砷,其中亚砷酸盐与砷酸盐是砷的主要存在形态,且在pH影响下两者之间存在相互转化关系;各种硫代砷按质量浓度由高至低依次为一硫代砷酸盐、三硫代砷酸盐、二硫代砷酸盐、一硫代亚砷酸盐、四硫代砷酸盐;硫代砷形态占总砷浓度比例主要受热泉中硫化物质量浓度、Eh（氧化还原电位）和pH等因素的控制,在硫化物质量浓度总体偏低的情况下,硫化物质量浓度的上升可促进其他形态的砷向硫代砷形态转化,强还原性环境有利于硫代砷形态的存在;此外,在中性环境下,硫代砷占总砷浓度比例随pH上升亦有上升趋势。