Mobility of arsenic in West Bengal aquifers conducting low and high groundwater arsenic. Part I: Comparative hydrochemical and hydrogeological characteristics

The present study demonstrates the importance of hydrogeochemical characteristics (groundwater flow and recharge) of an aquifer in the release of As to groundwater. The study area (∼20 km²) is located in Chakdaha block, Nadia district, West Bengal, which hosts groundwaters of variable As content. The spatial distribution pattern of As is patchy with areas containing groundwater that is high in As (>200 μg L⁻¹) found in close vicinity to low As (<50 μg L⁻¹) groundwaters (within 100 m). The concentration of groundwater As is found to decrease with depth. In addition, the data shows that there is no conspicuous relationship between high groundwater As concentration and high groundwater abstraction, although the central cone of depression has enlarged over 2 a and is extending towards the SE of the study area. The river Hooghly, which forms the NW boundary of the study site, shows dual behaviour (effluent and influent during pre- and post-monsoon periods, respectively), complicating the site hydrogeology. The observed groundwater flow lines tend to be deflected away from the high As portion of the aquifer, indicating that groundwater movement is very sluggish in the As-rich area. This leads to a high residence time for this groundwater package, prolonging sediment–water interaction, and hence facilitating groundwater As release.     

Behavior of arsenic and geochemical modeling of arsenic enrichment in aqueous environments

Arsenic is present in aqueous environments in +III and +V oxidation states. In oxidizing environments, the principle attenuation mechanism of As migration is its adsorption on Fe(III) oxide and hydroxides. The adsorption affinity is higher for As(V) under lower pH conditions and for As(III) under higher pH conditions. Ferric oxide and hydroxides can dissolve under low Eh and pH conditions releasing adsorbed As. Oxidation-reduction processes often involve high organic matter content in sediments and also contamination by organics such as BTEX. Arsenic may desorb under high pH conditions. Changes of pH can be related to some redox reactions, cation exchange reactions driving dissolution of carbonates, and dissolution of silicates. In very reducing environments, where SO₄ reduction takes place, secondary sulfide minerals like As-bearing pyrite and orpiment, As₂S₃, can incorporate As. Geochemical modeling can be divided into two principal categories: (a) forward modeling and (b) inverse modeling. Forward modeling is used to predict water chemistry after completion of predetermined reactions. Inverse modeling is used to suggest which processes take place along a flowpath. Complex coupled transport and geochemistry programs, which allow for simulation of As adsorption, are becoming available. A common modeling approach is based on forward modeling with surface complexation modeling (SCM) of As adsorption, which can incorporate the effect of different adsorbent/As ratios, adsorption sites density, area available for adsorption, pH changes and competition of As for adsorption sites with other dissolved species such as phosphate. The adsorption modeling can be performed in both batch and transport modes in codes such as PHREEQC. Inverse modeling is generally used to verify hypotheses on the origin of As. Basic prerequisites of inverse modeling are the knowledge of flow pattern (sampling points used in model have to be hydraulically connected) and information about mineralogy including As mineral phases. Case studies of geochemical modeling including modeling of As adsorption are presented.     

Mobility of arsenic in West Bengal aquifers conducting low and high groundwater arsenic. Part II: Comparative geochemical profile and leaching study

Aquifer sediments from areas of low- and high-As groundwater were characterized mineralogically and geochemically at a field site in the Nadia district of West Bengal, India. Leaching experiments and selective extraction of the sediments were also carried out to understand the release mechanism of As in the sub-surface. The correlation between measured elements (major, minor and trace) from low- and high-As groundwater areas are only significant for As, Fe and Mn. The borehole lithology and percentage of silt and clay fraction demonstrates the dominance of finer sediments in the high-As aquifer. Multivariate analysis of the geochemical parameters showed the presence of four different mineral phases (heavy-mineral fraction, phyllosilicates/biotite/Fe-oxyhydroxides, carbonates and sulphides) in the sediments. Selective extraction of sediment reveals that amorphous Fe-oxyhydroxide acts as a potential sink for As in the sub-surface. The result is consistent with microbially mediated redox reactions, which are controlled in part by the presence of natural organic matter within the aquifer sediments. The occurrences of As-bearing redox traps, primarily formed of Fe- and Mn-oxides/hydroxides, are also important factors that control the release of As into groundwater at the study site.     

Mobilization of natural arsenic in groundwater: targeting low arsenic aquifers in high arsenic occurrence areas

研究表明饮用水中微小数量的砷会对人类健康产生不利影响.世界上居住在贫穷地区的人数超过了100万,目前他们正直接饮用来自含水层中砷离子含量(>10μg/L)非安全标准的地下水.砷有时称为毒中之王,在水环境中常常以五价氧化物形式出现.自2000年以来,许多国家开始执行更为严格的10μg/L(WHO认可的居民安全饮水标准)饮用水标准,可以确定地说,在世界范围内的饮用水中检测到砷的情况越来越多.亚洲地区砷中毒的人数比世界其他地区总和还多.最受影响的地区位于南亚和东南亚富砷带,环绕恒河一雅鲁藏布江-梅克纳河三角洲及恒河平原上游的冲洪积扇含水层、红河三角洲、湄公河和伊洛瓦底江;在中国境内包括内蒙黄河冲积盆地,山西大同盆地、新疆准噶尔盆地,其中的地下水富含砷和氟化物而引发砷中毒和氟中毒.尽管还未完全掌握其中的水文地质及生物地球化学作用的详细过程,但对大多数沉积介质含水层,在还原条件下砷离子容易从沉积介质转移到地下水中.孟加拉研究实例表明地质时期尺度的冲刷降低了沉积介质中的As和有机物含量从而形成低砷地下水.这一认识为孟加拉国的降砷策略提供了科学指导,是未来水文学,矿物学,地质学和生物地球化学方面很有意义的研究方向,并有利于地砷病区低砷地下水的可持续利用.     

Rejection of arsenic minerals in sulfide flotation — A literature review

Arsenic is one of the most dangerous inorganic pollutants and thus a penalty element in many base metal concentrates. Arsenic removal in sulphide flotation has been studied extensively with various approaches, including pre-oxidation of flotation pulp, E_h control during flotation and the use of selective depressants/collectors. Pre-oxidation of flotation pulp using oxidizing agents or aeration conditioning represents a simple approach in arsenic removal and was found effective in many cases. Selective flotation of arsenic minerals through E_h control has made significant advances in recent years with promising results achieved. In addition, various depressants and collectors have also been studied in arsenic removal. In this communication, the various approaches used in selective flotation of arsenic minerals are reviewed with emphasis on the development in recent years.     

Uranium and arsenic in hydrothermal process

The paragenetic association of uranium and native arsenic in an undisclosed sulfide-uranium deposit indicates the possibility of high arsenic concentration in hydrothermal solutions depositing pitchblende at low temperatures. --E. A. Alexandrov.     

Identifying groundwater arsenic contamination mechanisms in relation to arsenic concentrations in water and host rocks

Leaching and oxidation of high arsenic (As) host rocks tend to be induced by circulation of deep geothermal waters, which increase As concentration in shallow groundwater. The purpose of this study is to identify the mechanism of groundwater As contamination in relation to leaching and oxidation along the border between the South Minahasa and Bolaang Mongondow districts, North Sulawesi, Indonesia. This region contains Miocene sedimentary rock-hosted disseminated gold deposits associated with hydrothermal alteration in a fault zone. Abnormally high As concentrations were observed in hot and cold springs and in surrounding shallow groundwater for a total mineralization area of 8 × 10 km². Two methods were adopted in this study: (1) microscopic and spectroscopic analyses of rock samples for mineral identification and (2) geostatistics for spatial modeling of As concentrations in groundwater. Jarosite was identified as the chief fill mineral in rock defects (cracks and pores). The presence of this mineral may indicate release of As into the environment, as can occur as an alteration product derived from oxidation and leaching of pyrite, As-rich pyrite or sulfide minerals by geothermal waters. Moreover, As concentrations in groundwater were estimated using geostatistics for spatial modeling. The co-kriging map identified local anomalies in groundwater As concentrations over the permissible limit (10 ppb). Such anomalies did not appear through ordinary kriging. Integration of the results indicates that As contamination in shallow groundwater probably is controlled by heterogeneous distributions of jarosite and variations in intensity and extent of hydrothermal activities.     

Characteristics of arsenic adsorption from aqueous solution: Effect of arsenic species and natural adsorbents

Batch and column experiments were conducted on As adsorption from aqueous solution by natural solids to test the feasibility of these materials to act as adsorbents for As removal from groundwater and drinking water. The solids considered are natural hematite and natural siderite. The As species studied are As(V), As(III) and dimethylarsinic acid (DMA). Arsenic(III), As(V) and DMA were removed to different extents by the solids studied from water solutions containing these three As species, with the highest efficiency for As(V). In aqueous solutions with a mixture of As species, adsorption kinetics depend on the species. On both materials, As(V) was preferentially adsorbed in the batches and first reached equilibrium, followed by DMA and As(III). The As adsorption took place more slowly on natural hematite and natural siderite compared with ferrihydrite. The results demonstrate that the amount of As removed from As(III) batches was greater than that from As(V) batches due to a surface alteration of the solids caused by As(III) oxidation. Although the highest efficiency for As retention was observed on hematite HIO1 in the batch experiments, siderite used as column filling was more efficient in removing As from water containing the As species studied in comparison with hematite. The coating of fresh Fe(III)-oxides was much more intensive in the siderite-packed column than in the hematite-packed column. The combination of siderite and hematite would promote the column filling performance in removing As from aqueous solution.     

Effect of arsenic concentration on microbial iron reduction and arsenic speciation in an iron-rich freshwater sediment

Depth profiles in the sediment porewaters of the Chattahoochee River (Georgia, USA) show that iron oxides scavenge arsenate in the water column and settle to the sediment-water interface (SWI) where they are reduced by iron-reducing bacteria. During their reduction, these particles seem to release arsenic to the porewaters in the form of arsenate only. Sediment slurry incubations were conducted to determine the effect of low concentrations of arsenic (?10 μM) on biogeochemical processes in these sediments. Experiments confirm that any arsenate (As(V)) added to these sediments is immediately adsorbed in oxic conditions and released in anoxic conditions during the microbial reduction of authigenic iron oxides. Incubations in the presence of ?1 μM As(V) reveal that arsenate is released but not concomitantly reduced during this process. Simultaneously, microbial iron reduction is enhanced significantly, spurring the simultaneous release of arsenate into porewaters and secondary formation of crystalline iron oxides. Above 1 μM As(V), however, the microbial reductive dissolution of iron oxides appears inhibited by arsenate, and arsenite is produced in excess in the porewaters. These incubations show that even low inputs of arsenic to riverine sediments may affect microbial processes, the stability of iron oxides and, indirectly, the cycling of arsenic. Possible mechanisms for such effects on iron reduction are proposed.     

Rujevac Sb-Pb-Zn-As polymetallic deposit,Boranja orefield,Western Serbia: native arsenic and arsenic mineralization

Rujevac is a low-temperature hydrothermal polymetallic Sb-Pb-Zn-As vein-type ore deposit, hosted within a volcanogenic-sedimentary zone situated in the Rujevac-Crvene Stene-Brezovica Diabase-Chert Formation (DCF) of the Podrinje Metallogenic District (PMD), Serbia. It is located several kilometers SE from the Boranja contact aureole, which is an integral part of the PMD in Western Serbia. Genetically related to the Tertiary granodioritic magma, the mineral assemblages are characterized by specific features. The mineral association of this deposit consists of sulfides, Pb-Sb(As) sulfosalts, native metals, oxides, hydroxides and gangue minerals. Chemical composition of the ore is very complex, where contents of valuable metals range as follows: Sb (0.17–24.31 wt.%), Zn (0.21–6.29 wt.%), Pb (0.15–6.33 wt.%), As (0.06–1.28 wt.%), Cd (25–747 ppm), Ag (7–408 ppm), Hg (13–473 ppm), and Tl (<1–29 ppm). Electron Probe Microanalyses (EPMA) of native arsenic from both the Rujevac and Stragari deposits showed contents of As up to 98.8 and 97.1 wt.%, with impurity contents of Sb up to 1.3 and 6.6 wt.%, and Tl up to 2 and 1.3 wt.%, respectively. Rhombohedral unit-cell parameters for native arsenic from Rujevac and Stragari deposits amount to: a?=?3.760(2), c?=?10.555(3) Å, V?=?129.23(7) ų and a?=?3.763(1), c?=?10.560(5) Å, V?=?129.48(8) ų, respectively. Mineral assemblages, deposition order and genesis of the Rujevac polymetallic deposit were also discussed in detail. Native arsenic mineralization here has been additionally compared with similar well-known global deposits.     

蒲阳河流域地下水水化学及同位素特征

保定西部山前地区位于太行山及华北平原交界带,为缓解极端气候灾害对生产生活的影响,维持地下水资源的可持续开发利用,开展相关的地下水水化学及同位素特征研究。研究区地下水化学类型以HCO3—Ca·Mg、HCO3·SO4—Ca·Mg及SO4·HCO3—Ca·Mg为主,区内地下水主要来源于大气降水,流域内地表水补给地下水;地下水中化学成分为Ca2＋、Mg2＋、HCO-3、SO2-4,主要来源于岩石风化作用,同时受到人类活动的影响,地下水中硝酸盐含量明显升高;由于受到褶皱构造的控制,流域的上游及平原区均出现年龄大于60年的地下水,多数岩溶水年龄较复杂,从现代水到大于60年的水均有分布。研究成果为流域内水资源的合理开发利用提供建议,区内岩溶地下水的开发将在一定程度上缓解极端天气的影响。     

高砷含水层沉积物含铁矿物特性及其对砷的水文地球化学作用

含水层沉积物中含铁矿物的特征与活性会影响砷的迁移转化行为。通过内蒙古含水层沉积物含铁矿物的溶解、还原动力学实验,研究了沉积物含铁矿物特征和活性及其与砷运移的关系。结果表明,沉积物中具还原活性的铁氧化物总量(m0)与岩性有关,细砂为52 μmol/g,黏土为45 μmol/g。初始还原速率k′均在10-5 s-1的数量级。表征活性均匀度的参数γ值介于合成铁氧化物矿物和表层沉积物之间。沉积物中Fe(Ⅲ)氧化物的还原活性主要介于人造纤铁矿与针铁矿的活性水平范围内。沉积物中可能存在两类活性水平不同的Fe(Ⅲ)氧化物。As更倾向于吸附在活性较强的Fe(Ⅲ)氧化物上。还原环境中,活性较强的Fe(Ⅲ)氧化物的还原性溶解,促进了沉积物中砷的释放。     

A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump

At the abandoned As mine in Nishinomaki, Japan, discharged water from the mining and waste dump area is acidic and rich in As. However, the As concentration in the drainage has been decreased to below the maximum contaminant level (0.01 mg/l for drinking water, Japan) without any artificial treatments before mixing with a tributary to populated areas. This implies that the As concentration in water from the waste dump area has been naturally attenuated. To elucidate the reaction mechanisms of the natural attenuation, analysis of water quality and characterization of the precipitates from the stream floor were performed by measuring pH, ORP and electric conductivity on-site, as well as X-ray diffraction, ICP-mass spectrometry and ion-chromatography. Selective extractions and mineral alteration experiments were also conducted to estimate the distribution of As in constituent phases of the precipitates and to understand the stability of As-bearing phases, respectively. The water contamination resulted from oxidation of sulfide minerals in the waste rocks, i.e., the oxidation of pyrite and realgar and subsequent release of Fe, SO₄, As(V) and proton. The released Fe(II) transformed to Fe(III) by bacterial oxidation; schwertmannite then formed immediately. While the As concentrations in the stream were lowered nearly to background level downstream, those in the ochreous precipitates were up to several tens of mg/g. The As(V) was effectively removed by the formed schwertmannite and had been naturally attenuated. Although schwertmannite is metastable with respect to goethite, the experiments show that the transformation of schwertmannite to goethite may be retarded by the presence of absorbed As(V) in the structure. Therefore, the attenuation of As in the drainage and the retention of As by schwertmannite are expected to be maintained for the long term.     

Modeling transport of arsenic through modified granular natural siderite filters for arsenic removal

Groundwater arsenic(As)contamination is a hot issue,which is severe health concern worldwide.Recently,many Fe-based adsorbents have been used for As removal from solutions.Modified granular natural siderite(MGNS),a special hybrid Fe(II)/Fe(III)system,had higher adsorption capacity for As(III)than As(V),but the feasibility of its application in treating high-As groundwater is still unclear.In combination with transport modeling,laboratory column studies and field pilot tests were performed to reveal both mechanisms and factors controlling As removal by MGNS-filled filters.Results show that weakly acid pH and discontinuous treatment enhanced As(Ⅲ)removal,with a throughput of 8700 bed volumes(BV)of 1.0 mg/L As(Ⅲ)water at breakthrough of 10 μg/L As at pH 6.Influent HCO_3~-inhibited As removal by the filters.Iron mineral species,SEM and XRD patterns of As-loading MGNS show that the important process contributing to high As(Ⅲ)removal was the mineral transformation from siderite to goethite in the filter.The homogeneous surface diffusion modeling(HSDM)shows that competition between As(III)and HCO_3~-with adsorption sites on MGNS was negligible.The inhibition of HCO_3~-on As(Ⅲ)removal was connected to inhibition of siderite dissolution and mineral transformation.Arsenic loadings were lower in field pilot tests than those in the laboratory experiments,showing that high concentrations of coexisting anions(especially HCO_3~-and SiO_4~(4-)),high pH,low EBCT,and low groundwater temperature decreased As removal.It was suggested that acidification and aeration of highAs groundwater and discontinuous treatment would improve the MGNS filter performance of As removal from real high-As groundwater.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

原生高砷地下水的类型、化学特征及成因

由于分布广、危害大,原生高砷地下水严重威胁全球内数亿居民的身体健康。研究原生高砷地下水的分布、化学特征及成因有助于进一步理解地下水中砷的迁移转化规律,并确保高砷区地下水的可持续利用。在查阅大量文献资料的基础上,结合近10年的高砷地下水研究经验,把原生高砷地下水分为还原性中性高砷地下水（Ⅰ 1型）和还原性弱碱性高砷地下水（Ⅰ 2型）、氧化性弱碱性高砷地下水（Ⅱ型）和氧化性弱酸性高砷地下水（Ⅲ型）。Ⅰ 1型高砷地下水主要分布于河流三角洲地区,Ⅰ 2型分布于干旱半干旱封闭内陆盆地,Ⅱ型主要分布于干旱半干旱平原盆地,Ⅲ型主要分布于富含黄铁矿或硫化物矿物的基岩地区。Ⅰ 1型高砷地下水处于还原环境,pH呈中性,Fe/Mn氧化物矿物的还原性溶解是造成As富集的主要原因。Ⅰ 2型高砷地下水处于还原环境,pH呈弱碱性,除了Fe/Mn氧化物矿物的还原性溶解外,As的解吸附是含水层中砷释放的重要原因。Ⅱ型高砷地下水处于氧化弱氧化环境,pH呈弱碱性,As的解吸附是含水层中砷释放的主要原因。Ⅲ型高砷地下水处于氧化环境,pH呈弱酸性,黄铁矿及其他硫化物矿物的氧化溶解导致了含水层中砷的释放。对于Ⅰ 2型高砷地下水,需要深入研究Fe/Mn氧化物矿物的还原性溶解以及As的解吸附对地下水砷富集的相对贡献量。     

Groundwater transport of arsenic and chromium at a historical tannery,Woburn, Massachusetts,U.S.A.

The geochemical environment in hide piles at a historical tanning and rendering site (Woburn, Massachusetts, U.S.A.) is strongly reducing, as reflected by the presence of H₂S and CH₃HS in the pile offgas. The presence of a reducing environment in the Subjacent groundwater, along with DOC (≥ 100mg/l) from hide breakdown, results in reduction of As(V) to As(III), and subsequent methylation to monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA). The reducing conditions also result in precipitation of FeS_(am), while hydrophilic organic acids have increased Cr(III) solubility. Three spatially sequential geochemical redox facies were recognized in groundwater downgradient from the hide piles. Typically, a reduced core zone was present adjacent to the hide piles, characterized by S²⁻ ≥ 1mg/l, Fe²⁺ <5mg/l,NH₃ ≥ 200mg/l and the presence of MMAA in conjunction with DOC (−30mg/l). This facies transitions through an intermediate zone, represented by Fe²⁺ > 20mg/l, NH₃ (5–200 mg/l) and the sporadic presence of measurable S²⁻ (1–2 mg/l), to an oxidizing peripheral zone characterized by conditions representative of background (i.e. DO> 1mg/l, Eh> 0mV, Fe²⁺ < 20mg/l, S²⁻ < 1mg/l,NH₃ < 5mg/l and NO₃⁻ >NH₃), accompanied by precipitation of amorphous ferric hydroxide, sorption of As and co-precipitation-sorption of Cu, Pb and Zn. Electron microprobe analysis of hide-pile materials demonstrated authigenic precipitation of amorphous ferric hydroxide and gypsum, in agreement with the results of geochemical modeling.     

Model for the formation of arsenic contamination in groundwater. 1. Datong Basin,China

Mineral equilibria were analyzed in the system As-bearing rock-meteoric water. It was shown that carbonate rocks are the most probable source of As and Sr in the waters of the Datong Basin (People's Republic of China). The reason for groundwater enrichment in As is the shift of the equilibrium FeCO₃ (siderite) + H₂O = FeOOH(goethite) + CO₂(g) + H₂(g) to the left (toward siderite formation) owing to organic matter oxidation by atmospheric oxygen and an increase in the equilibrium partial pressure of CO₂, while the Eh of the system remains below ?0.30 ± 0.06 V.