江汉平原高砷地下水监测场砷的动态变化特征分析

江汉平原高砷地下水的发现引起了广泛关注,通过对该区域高砷地下水监测场不同深度不同季节地下水样品的分析,揭示了地下水的水化学特征及高砷地下水的垂向分布规律。同时,结合地下水和地表水的水位波动,探讨了地下水中砷含量的动态变化特征。结果表明：地下水水化学类型主要为HCO3 Ca·Mg型,为强的还原性地下水环境,Fe、Mn含量高。大部分监测点都是25 m监测井水中砷的含量最高。地下水中砷含量的季节性动态变化特征与地下水水位密切相关。10 m监测井砷含量与水位变化的关系最明显,随着水位的下降（抬升）,地下水砷含量出现明显的降低（升高）响应。25 m和50 m监测井地下水中砷含量的动态变化与测压水位的动态变化不完全同步,存在一定的滞后效应,且含水层深度越大,滞后效应越明显。     

长江中游河湖平原浅层地下水中砷空间异质性的同位素指示

近年来陆续有报道发现长江中游河湖平原广泛分布着高砷地下水,鄱阳湖平原与江北平原（古彭蠡泽）作为长江中游南北两岸典型的河湖平原,其地下水资源丰富,但砷的空间分布规律尚不清楚,区域供水安全存在风险.本研究在两个区域系统采集98个浅层地下水（< 40 m）样品和8个地表水样品,通过水化学、氢氧稳定同位素分析,查明地下水中砷的空间分布异质性及其影响因素.研究发现江北平原浅层地下水砷含量为0.65~956.72 μg/L（平均值210.78 μg/L）,高砷地下水集中分布于长江古河道;鄱阳湖平原浅层地下水砷含量为0.09~267.45 μg/L（平均值11.85 μg/L）,高砷地下水仅分布于赣江三角洲局部地区.江北平原地下水δD与δ18O值相对鄱阳湖平原更偏负,且与地表水的差异更大.地下水化学及主成分分析结果表明物源和含水层结构差异是影响鄱阳湖平原和江北平原砷空间分布异质性的关键因素,来自长江物源的古彭蠡泽区域沉积物为高砷含水层的形成提供了物质来源,湖相含水层中含砷铁氧化物的还原性溶解是地下水砷富集的主要过程.地下水氢氧稳定同位素指示江北平原较鄱阳湖平原地下水赋存环境更封闭,地下水循环交替速度缓慢,有利于砷的富集.      

天鹅洲长江故道湿地地下水砷的时空分布特征及控制机理

高砷地下水不仅直接危害供水安全,还可通过与湿地之间的交互作用,影响湿地水质进而威胁湿地生态安全.长江中游河湖平原已被报道广泛分布有高砷地下水,而位于长江中游故道区域的天鹅洲湿地地下水中砷的空间分布特征尚不明确,湿地与地下水的交互作用对地下水中砷季节性动态的控制机理尚不明确.本研究在天鹅洲湿地采集2个水文地质钻孔的35件沉积物样品、12个分层监测井不同季节的共72组地下水样和18组地表水样,通过水位-水化学监测、沉积物地球化学组成分析和砷、铁形态表征探究天鹅洲湿地地下水中砷的时空分布规律及控制机理.研究发现天鹅洲湿地地下水砷含量为1.08~147 μg/L,牛轭湖外侧浅井（10 m）地下水砷含量普遍高于深井（25 m）和牛轭湖内侧浅井（10 m）、深井（25 m）地下水,枯水期和平水期的砷含量高于丰水期.牛轭湖外侧浅层地下水系统具有更厚的粘土、亚粘土沉积,沉积物中总砷、强吸附态砷和易还原的铁氧化物的含量更多,吸附砷的水铁矿等无定形铁氧化物还原性溶解导致砷释放进入地下水中.枯水期天鹅洲湿地底部向牛轭湖外侧浅层含水层输送不稳定的有机质,使天鹅洲湿地地下水-地表水界面成为砷释放的热点区域.丰水期时牛轭湖外侧含水层受长江补给的影响,还原环境发生改变使地下水中的砷和铁被氧化固定从而不利于砷向地下水释放.      

江汉平原高砷含水层沉积物地球化学特征

选取江汉平原典型地下水砷中毒区仙桃市沙湖原种场为研究区,对3个长50m的钻孔沉积物砷含量与赋存形态及其他化学组成进行了分析。结果表明区内沉积物砷质量分数为1.35~107.5mg/kg(平均值为12.8mg/kg)。黏土或亚黏土层中砷含量较高,这与细粒沉积物中铁锰氧化物、黏土矿物对砷的吸附有关。地下20m左右深度内含水层沉积物中砷含量最高,相应地下水中砷质量浓度高达到1 000μg/L。草酸-草酸铵选择性提取结果指示沉积物中10%~77%(平均38%)的As与无定形铁氢氧化物结合,表明无定形铁氢氧化物还原性溶解可能是控制砷释放与还原的主要地球化学过程,并且有机质生物氧化机制极大地促进了该过程。然而,沉积物中仅1.2%~23%的铁被草酸-草酸铵提取,含水层中砷浓度主要受铁的氢氧化物还原性溶解影响,但其他形式的铁、有机物的吸附作用亦控制着砷的含量。     

银北平原浅层高砷地下水砷富集水化学特征研究

宁夏银川平原是继河套平原之后,在黄河流域发现的又一个高砷地下水分布区.为了总结其高砷地下水的水化学特征,并探索水化学因素对地下水砷释放和富集的影响机制,本文以银川平原北部（银北平原）作为典型研究区,采取野外水文地质调查、水样采集与测试、砷与水化学组分散点图相关分析及水文地球化学方法进行了综合研究.结果表明,银北平原地下水砷含量在0.2~177 μg/L之间;高砷地下水（大于50 μg/L） pH值多在7.5~8.5,水化学类型主要为HCO3-Na·Ca、Cl·HCO₃-Na及Cl·HCO₃-Na·Ca型,E_h多在-200~-100 mV.银北平原砷含量较高的地下水中COD、NH₄⁺、HCO3^-含量相应也较高,而NO3^-和SO₄^2-含量较低.高砷富有机质的冲-湖积含水层经过长期演化,形成偏碱性的中强还原性地下水环境和特殊的水化学特征,也具备极大的砷释放能力.较高的pH导致砷从铁锰氧化物或氢氧化物等水合物或黏土矿物表面解吸.其次部分铁锰氧化物在高pH、低E_h条件下可被还原为低价态可溶性铁锰,从而使与其结合的砷也得以释放进入地下水中.此外重碳酸根与砷酸根、亚砷酸根的竞争吸附行为促使含水层砷的解吸.     

河套平原临河区高砷地下水分布及水化学特征

文章通过地质环境、地下水野外调查以及水质分析测试等方法手段,较系统地研究和分析了河套平原临河区高砷地下水的分布及水化学特征。结果表明,该区高砷地下水主要分布在调查区的西北部,在区域上属于河套平原的沉积中心地带,局部呈小片状分布,短距离内地下水中的砷含量变化较大;该区砷含量≥0.05mg/L的地下水绝大部分为微咸水(TDS为1～3g/L),个别为淡水(TDS<1g/L)和咸水(TDS为3～10g/L),其氧化还原电位(ORP)均显示负值的还原环境。通过与非高砷区的对比研究,高砷区地下水中的铁含量超标率明显高于非高砷区(58%),达到91.3%。研究认为该区域高砷地下水的形成与沉积环境和沉积物的特征有很大的关系。     

江汉平原砷中毒病区地下水砷形态季节性变化特征

查明地下水中砷的时间变异性规律及机理是高砷地下水研究的难点和热点, 也是防控地下水砷污染的根本.选择在雨季前后对浅层潜水和孔隙承压水进行了动态监测.研究表明地下水砷含量和形态与地下水位波动存在明显的响应关系: 雨季开始后随着地下水位抬升, 地下水还原环境增强, As(Ⅴ)和Asp转化成As(Ⅲ), 颗粒态铁大幅降低, 导致水中溶解的砷和铁大幅增加, 地下水砷含量在雨季达到最高且As(Ⅲ)所占比例达到90%;雨季结束后随着水位逐渐降低, 地下水中As(Ⅲ)所占比例和溶解的砷含量下降.农业活动对浅层潜水砷形态季节性变化有明显的影响.孔隙承压水的砷形态分布变化较浅层潜水幅度大, 其变化与水位波动存在滞后效应.自然或人为活动引起的地下水位季节性变化改变了含水层的氧化还原环境, 补给水源与地下水之间的混合过程带来新的物质输入促进地下水系统中砷的迁移转化.      

江汉平原第四系沉积物中砷的垂向分布规律及其对地下水中砷浓度的影响

含水层沉积物是江汉平原地下水中砷的主要来源,沉积物地球化学特征对地下水的水化学具有重要控制作用。为查明江汉平原第四系沉积物中砷的垂向分布及赋存环境,在典型高砷地下水分布区内选取2个深钻(JH002孔及YLW01孔,深度分别为230m和201m)采集沉积物样品进行了地球化学分析。结果表明全新统和上更新统含水层沉积物以黏土、粉土、淤泥质黏土、粉砂、细砂为主,指示着弱水动力的沉积环境;2个钻孔沉积物地球化学特征相似,w(As)=2.0~22.6mg/kg(平均9.0mg/kg),w(Fe)=11.8~55.0mg/g(平均37.8mg/g),w(S)=0.1~2.1mg/g(平均0.4mg/g)。中、下更新统沉积物岩相变化较大,以砂和砾石居多,局部含有黏土夹层,指示着沉积时较强的水动力沉积环境;其中JH002孔沉积物w(As)=2.7~160.5mg/kg(平均40.9mg/kg),w(Fe)=20.1~179.5mg/g(平均50.5mg/g),w(S)=0.1~17.7mg/g(平均4.9mg/g);YLW01孔沉积物砷、铁、硫质量分数均低于JH002孔,w(As)=5.2~56.1mg/kg(平均16.2mg/kg),w(Fe)=10.9~117.5 mg/g(平均36.4 mg/g),w(S)=0.3~7.8mg/g(平均1.8mg/g)。YLW01孔中、下更新统沉积物颗粒较JH002孔更细,所处的水动力条件更弱,砷、铁、硫质量分数均低于JH002孔,说明沉积历史环境影响着砷、铁、硫等元素的分布。沉积物地球化学数据聚类分析结果表明全新统和上更新统砷与铁具有显著的相关性,而中、下更新统沉积物砷与硫化物矿物紧密相关。结合不同深度含水层水化学特征差异指示上更新统含水层中含砷铁氧化物的还原性溶解导致浅层地下水中砷的富集,富硫的中、下更新统深层含水层中强还原环境下砷受到硫化物矿物的固定作用难以释放进入地下水中。     

内蒙古河套平原高砷地下水赋存环境特征

内蒙古河套平原是世界地方性砷中毒较为严重的地区之一。笔者以平原西部的重病区杭锦后旗为研究区,对高砷地下水赋存环境进行了调查研究。研究表明:高砷区沉积物中As的含量为7.7～34.6mg/kg,其中粘性土和亚粘性土中As含量相对较高。高砷地下水的pH值为7.0～8.3,平均Eh值为-155.1mV,平均矿化度为1.58g/L,主要的水化学类型包括:Cl-HCO3-Na型、Cl-Na型、HCO3-Cl-Na型,As的含量为15.5～1093μg/L,且主要以As(Ⅲ)形态存在,水中DOC(0.73～35.76mg/L)、HCO3-(283.75～1290.48mg/L)、NH4+(0.27～10.48mg/L)的浓度较高,硝酸盐和硫酸盐含量较低。研究区的氟中毒现象也较严重,高氟地下水中氟含量为1.11～6.01mg/L。绝大多数高氟水中砷含量也超标,出现了一种高砷水与高氟水并存的现象。综合判断,河套平原的高砷地下水赋存环境处于还原性环境。还原条件下,高砷区沉积物中的铁/锰氧化物的还原溶解易使吸附的砷释放到地下水中。这是研究区高砷地下水形成的主要原因。     

河套平原西部地下水砷富集机制研究

干旱内陆盆地高砷含量的地下水威胁着当地饮用水安全，其形成机制尚不完全清楚。为厘清这类高砷地下水的形成机制，本文以河套平原西部地下水为研究对象，分析其中As等部分氧化还原敏感元素含量和氢、氧同位素组成(δD和δ¹⁸O)。结果表明，地下水样的As的质量浓度为1.5～155μg/L(均值为36.7μg/L),超半数样品超过10μg/L,主要分布于盆地中部的浅层含水层。水样的氢、氧同位素组成和离子间的相关性分析表明，虽然蒸发浓缩作用导致地下水富集Na⁺和Cl^-,但对As的富集影响不显著；在偏碱性环境中因解吸附作用产生的As进入地下水，对As的富集有一定贡献；负载As的铁氧化物还原性溶解和沉积物中的As(V)还原性解吸附是地下水中As富集的主要原因；强还原环境中，硫酸盐还原作用形成的硫代砷可能会促使As在地下水中高度富集。     

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.     

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.     

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.     

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.     

Geochemical and hydrogeological contrasts between shallow and deeper aquifers in two villages of Araihazar, Bangladesh: Implications for deeper aquifers as drinking water sources

Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-³H and bomb-¹⁴C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na⁺-HCO₃^- type, with relatively little dissolved NH₄⁺ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca²⁺-Mg²⁺-HCO₃^- type, with elevated concentrations of dissolved NH₄⁺ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.     

Mineralogical profiling of alluvial sediments from arsenic-affected Ganges-Brahmaputra floodplain in central Bangladesh

Mineral assemblages (heavy and light fractions) and sedimentological characteristics of the Quaternary alluvial aquifers were examined in the central Bengal Basin where As concentrations in groundwater are highly variable in space but generally decrease downward. Chemical compositions of sediment samples from two vertical core profiles (2-150 m below ground level, bgl) were analyzed along with groundwater in moderately As-enriched aquifers in central Bangladesh (Manikganj district), and the As mobilization process in the alluvial aquifer is described. Heavy minerals such as biotite, magnetite, amphibole, apatite and authigenic goethite are abundant at shallow (<100 m below ground level (mbgl)) depths but less abundant at greater depths. It is interpreted that principal As-bearing minerals were derived from multiple sources, primarily from ophiolitic belts in the Indus-Tsangpo suture in the northeastern Himalayan and Indo-Burman Mountain ranges. Authigenic and amorphous Fe-(oxy)hydroxide minerals that are generally formed in river channels in the aerobic environment are the major secondary As-carriers in alluvial sediments. Reductive dissolution (mediated by Fe-reducing bacteria) of Fe-(oxy)hydroxide minerals under anoxic chemical conditions is the primary mechanism responsible for releasing As into groundwater. Authigenic siderite that precipitates under reducing environment at greater depths decreases Fe and possibly As concentrations in groundwater. Presence of Fe(III) minerals in aquifers shows that reduction of these minerals is incomplete and this can release more As if further Fe-reduction takes place with increased supplies of organic matter (reactive C). Absence of authigenic pyrite suggests that SO₄ reduction (mediated by SO₄-reducing bacteria) in Manikganj groundwater is limited in contrast to the southeastern Bengal Basin where precipitation of arsenian pyrite is thought to sequester As from groundwater.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Fe and Mn levels regulated by agricultural activities in alluvial groundwaters underneath a flooded paddy field

Iron and Mn concentrations in fresh groundwaters of alluvial aquifers are generally high in reducing conditions reflecting low SO₄ concentrations. The mass balance and isotopic approaches of this study demonstrate that reduction of SO₄, supplied from agricultural activities such as fertilization and irrigation, is important in lowering Fe and Mn levels in alluvial groundwaters underneath a paddy field. This study was performed to investigate the processes regulating Fe and Mn levels in groundwaters of a point bar area, which has been intensively used for flood cultivation. Four multilevel-groundwater samplers were installed to examine the relationship between geology and the vertical changes in water chemistry. The results show that Fe and Mn levels are regulated by the presence of NO₃ at shallow depths and by SO₄ reduction at the greater depths. Isotopic and mass balance analyses revealed that NO₃ and SO₄ in groundwater are mostly supplied from the paddy field, suggesting that the Fe-and Mn-rich zone of the study area is confined by the agricultural activities. For this reason, the geologic conditions controlling the infiltration of agrochemicals are also important for the occurrence of Fe/Mn-rich groundwaters in the paddy field area.     

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility.In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ∼0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R² of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10⁻⁹ m³/kg SI) and was linearly related (R² of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ∼200 × 10⁻⁹ m³/kg SI).This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10⁻⁶, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.