Contrasting sorption behaviours affecting groundwater arsenic concentration in Kandal Province,Cambodia

Natural arsenic(As)contamination of groundwater which provides drinking water and/or irrigation supplies remains a major public health issue,particularly in South and Southeast Asia.A number of studies have evaluated various aspects of the biogeochemical controls on As mobilization in aquifers typical to this region,however many are predicated on the assumption that key biogeochemical processes may be deduced by sampled water chemistry.The validity of this assumption has not been clearly established even though the role of sorption/desorption of As and other heavy metals onto Fe/Mn(hydr)oxides is an important control in As mobilization.Here,selective chemical extractions of sand-rich and clay-rich sediments from an As-affected aquifer in Kandal Province,Cambodia,were undertaken to explore the potential role of partial re-equilibrium through sorption/desorption reactions of As and related solutes(Fe,Mn and P)between groundwater and the associated solid aquifer matrix.In general,groundwater As is strongly affected by both pH and Eh throughout the study area.However,contrasting sorption behaviour is observed in two distinct sand-dominated(T-Sand)and clay dominated(T-Clay)transects,and plausibly attributed to differing dominant lithologies,biogeochemical and/or hydrogeological conditions.Sorption/desorption processes appear to be re-setting groundwater As concentrations in both transects,but to varying extents and in different ways.In T-Sand,which is typically highly reducing,correlations suggest that dissolved As may be sequestered by sorption/re-adsorption to Fe-bearing mineral phases and/or sedimentary organic matter;in T-Clay Eh is a major control on As mobilization although binding/occlusion of Fe-bearing minerals to sedimentary organic matter may also occur.Multiple linear regression analysis was conducted with groups categorised by transect and by Eh,and the output correlations support the contrasting sorption behaviours encountered in this study area.Irrespective of transect,however,the key biogeochemical processes which initially control As mobilization in such aquifers,may be "masked" by the re-setting of As concentrations through in-aquifer sorption/desorption processes.     

Arsenic and manganese in tube well waters of Prey Veng and Kandal Provinces,Cambodia

Twenty-eight tube well water samples were collected in February, 2006, from households in the Cambodian provinces of Prey Veng and Kandal. Concentrations of total As in both provinces ranged from not detectable (ND) up to about 900 μg/L, with about 54% of all the samples collected exceeding the WHO drinking water guide value of 10 μg/L. In addition, about 32% of all samples contained concentrations of Mn exceeding the WHO drinking water guide value of 400 μg/L. It is interesting to note that more than half (about 56%) of tube wells with Mn over 400 μg/L had the non-detectable As. Barium, Sr and Fe were also detected in most of tube well samples, which were typically circum-neutral and reducing. Arsenic speciation was dominated (80%) by dissolved inorganic As(III). The occurrence and composition of the well waters is consistent with the As being mobilized from aquifer sediments by natural processes in a highly reducing environment. The highest estimated cumulative As intake for individuals using the sampled well waters as drinking water is estimated to be around 400 mg As/a – this is comparable to intakes that have resulted elsewhere in the world in serious As-related illnesses and highlights the possibility that such adverse health impacts may arise in Cambodia unless appropriate remedial measures are taken.     

Linking organic matter deposition and iron mineral transformations to groundwater arsenic levels in the Mekong delta,Cambodia

Enriched As in drinking water wells in south and Southeast Asia has increased the risk of cancer for nearly 100 million people. This enrichment is generally attributed to the reductive dissolution of Fe oxides; however, the complex expression of As enrichment in these areas is not yet well understood. Here, the coupled sedimentological and geochemical factors that contribute to the extent and spatial distribution of groundwater As concentrations in the Mekong River delta, Cambodia in an avulsed scroll bar sequence are examined. X-Ray absorption spectroscopy (XAS) was used to determine Fe and As speciation in redox preserved sediment collected from drilled cores. Dissolved As, Fe and S solution concentrations in existing and newly drilled wells (cores) differed considerably depending on their source sedimentology. The rapid burial of organic matter in the scroll bar sequence facilitated the development of extensive Fe-reducing conditions, and As release into the aquifer. In older features organic C levels are high enough to sustain extensive Fe reduction and provide ample SO₄ which is reduced to sulfide. This S reduction impacts As levels; As is sequestered in sulfide minerals outside of the scrollbar sequence, decreasing pore water concentrations. In contrast, As is depleted in sediments from the scroll sequence, and associated with elevated pore water aqueous concentrations. The concentration and form of organic C in the scrollbar sequence is related to depositional environment, and can facilitate Fe and S mineral transformations, distinct sedimentary environments explain a portion of the inherent heterogeneity of aquifer As concentrations.     

高砷地下水的反向地球化学模拟:以中国吉林砷中毒病区为例

饮水型砷中毒分布在中国台湾、新疆、内蒙、山西、吉林等地。笔者采用GIS的空间数据叠加技术、化验测试与环境模拟技术,进行了地下水砷的反向地球化学模拟研究。研究表明,受构造运动控制,低洼地带堆积了巨厚的粉砂淤泥质沉积物和富含有机质的湖积物,为砷的赋存提供了空间。地下水砷的富集受水中Fe、Mn、pH、Cl-、PO34-、HCO3-、SO24-、Se的影响,其中,重碳酸钙型水中砷含量最低,氯化物重碳酸钠型水砷含量最高。臭葱石(FeAsO4:2H2O)等含铁、含锰矿物在进入地下水的溶解过程中,形成铁(锰)氧化物和砷化合物(砷酸盐或亚砷酸盐)。随着Eh降低,氧化物被还原形成更为活泼的离子组分,吸附在氧化物表面的砷化合物随之解吸,还原环境有利于砷从沉积物中向水中溶解、迁移。研究结果为实施安全供水提供了重要依据。     

Distribution of inorganic arsenic species in groundwater from Central-West Part of Santa Fe Province,Argentina

The distribution of inorganic arsenic species in groundwater used as drinking water supply by the peri-urban and rural population from central-western area of Santa Fe Province, Argentina, was studied. An analytical methodology based on an online system of atomic absorption spectrometry with hydride generation and flow injection (FI-HGAAS) was used for total inorganic arsenic determination. For speciation purposes, the distinction between As(V) and As(III) was performed through the on line coupling of FI-HGAAS to a solid phase system based on an anionic exchanger able to retain As(V) as oxyanion, allowing As(III) to be selectively determined. The concentration of As(V) was calculated as the difference between total arsenic and As(III) concentrations. Effects of matrix interference due to the nonselective behavior of the exchange resins were carefully laid. Results for 59 samples collected from 27 localities showed an almost exclusive predominance of pentavalent forms.     

Influences of groundwater extraction on flow dynamics and arsenic levels in the western Hetao Basin,Inner Mongolia,China

Data on spatiotemporal variations in groundwater levels are crucial for understanding arsenic (As) behavior and dynamics in groundwater systems. Little is known about the influences of groundwater extraction on the transport and mobilization of As in the Hetao Basin, Inner Mongolia (China), so groundwater levels were recorded in five monitoring wells from 2011 to 2016 and in 57 irrigation wells and two multilevel wells in 2016. Results showed that groundwater level in the groundwater irrigation area had two troughs each year, induced by extensive groundwater extraction, while groundwater levels in the river-diverted (Yellow River) water irrigation area had two peaks each year, resulting from surface-water irrigation. From 2011 to 2016, groundwater levels in the groundwater irrigation area presented a decreasing trend due to the overextraction. Groundwater samples were taken for geochemical analysis each year in July from 2011 to 2016. Increasing trends were observed in groundwater total dissolved solids (TDS) and As. Owing to the reverse groundwater flow direction, the Shahai Lake acts as a new groundwater recharge source. Lake water had flushed the near-surface sediments, which contain abundant soluble components, and increased groundwater salinity. In addition, groundwater extraction induced strong downward hydraulic gradients, which led to leakage recharge from shallow high-TDS groundwater to the deep semiconfined aquifer. The most plausible explanation for similar variations among As, Fe(II) and total organic carbon (TOC) concentrations is the expected dissimilatory reduction of Fe(III) oxyhydroxides.     

大同盆地地下水砷异常及其成因研究

大同盆地是中国典型的原生高砷地下水分布区。笔者对大同盆地高砷地下水的分布特征、水化学演化过程、砷的来源以及控制高砷地下水形成的地球化学过程等近期研究成果进行了总结。盆地周边石炭—二叠纪煤系地层是盆地高砷环境的主要原生物源,含水层系统中铁磁性矿物为砷的主要载体,盆地内富含有机质的湖相沉积物是次生富砷介质。在盆地中心,地下水径流受阻,蒸发成为主要的排泄方式,浓缩作用使得地下水中TDS含量增大。在富含有机质的地层中,有机质在细菌或微生物作用下不断发生分解,使得地下水环境呈还原性。在高pH、低Eh条件下,由于铁锰氧化物或氢氧化物等水合物或粘土矿物对砷的吸附性降低,一部分被吸附的砷从这些矿物表面解吸;同时部分铁锰氧化物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。在还原条件下,水中的SO24-和有机碳可被还原成H2S和CH4等低价态化合物,尽管生成的硫化物达到一定浓度时可与水中的亚铁离子和砷反应生成FeAsS沉淀,降低了地下水中砷含量,但由于地下水中Fe和硫酸盐含量有限,Fe普遍含量较低,硫酸盐耗尽后,CH4生成细菌就会成为主导力量,砷就会继续在地下水中积聚。此外,由于pH的升高,还可引起其他不同的酸根离子的解吸,如磷酸根、钒酸根、铀酰和钼酸根等也趋向于在溶液中积累,这些被吸附的阴离子以竞争吸附方式,进一步促进砷的解吸。     

Arsenic in groundwater of the Bengal Basin, Bangladesh: Distribution, field relations, and hydrogeological setting

Arsenic contaminates groundwater across much of southern, central and eastern Bangladesh. Groundwater from the Holocene alluvium of the Ganges, Brahmaputra and Meghna Rivers locally exceeds 200 times the World Health Organisation (WHO) guideline value for drinking water of 10 µg/l of arsenic. Approximately 25% of wells in Bangladesh exceed the national standard of 50 µg/l, affecting at least 25 million people. Arsenic has entered the groundwater by reductive dissolution of ferric oxyhydroxides, to which arsenic was adsorbed during fluvial transport. Depth profiles of arsenic in pumped groundwater, porewater, and aquifer sediments show consistent trends. Elevated concentrations are associated with fine-sands and organic-rich sediments. Concentrations are low near the water table, rise to a maximum typically 20–40 m below ground, and fall to very low levels between about 100 and 200 m. Arsenic occurs mainly in groundwater of the valley-fill sequence deposited during the Holocene marine transgression. Groundwater from Pleistocene and older aquifers is largely free of arsenic. Arsenic concentrations in many shallow hand-tube wells are likely to increase over a period of years, and regular monitoring will be essential. Aquifers at more than 200 m below the floodplains offer good prospects for long-term arsenic-free water supplies, but may be limited by the threats of saline intrusion and downward leakage of arsenic.

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Resumen El arsénico ha contaminado gran parte de las aguas subterráneas en el Sur, centro y Este de Bangla Desh. Su concentración en las aguas subterráneas del aluvial Holoceno de los ríos Ganges, Brahmaputra y Meghna supera localmente en un factor 200 el valor guía del arsénico en el agua potable, establecido por la Organización Mundial de la Salud (OMS) en 10 µg/L. Aproximadamente, el 25% de los pozos de Bangla Desh superan el estándar nacional de 50 µg/L, afectando al menos a 25 millones de personas. El arsénico ha llegado a las aguas subterráneas por la disolución reductora de hidróxidos férricos a los que se adsorbe durante el transporte fluvial. Los perfiles del arsénico en las aguas subterráneas bombeadas, agua de poro y sedimentos del acuífero muestran tendencias coherentes. Las concentraciones elevadas están asociadas a arenas finas y sedimentos ricos en materia orgánica. Las concentraciones de arsénico son bajas cerca del nivel freático, se incrementan hasta un máximo que se localiza generalmente a entre 20 y 40 m bajo la cota del terreno, y disminuyen a valores muy pequeños entre alrededor de 100 y 200 m. El arsénico se encuentra sobretodo en las aguas subterráneas existentes en la secuencia de sedimentación que tuvo lugar en el valle durante la transgresión marina del Holoceno. Las aguas subterráneas del Pleistoceno y acuíferos más antiguos están mayoritariamente libres de arsénico. Es probable que las concentraciones de arsénico aumenten en los próximos años en muchos pozos de tipo tubo perforados manualmente, por lo que será esencial efectuar un muestreo regular. Los acuíferos ubicados a más de 200 m bajo las llanuras de inundación ofrecen buenas perspectivas de abastecimiento a largo plazo sin problemas de arsénico, pero pueden estar limitados por las amenazas de la intrusión salina y de la precolación de arsénico desde niveles superiores.

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Résumé Larsenic contamine les eaux souterraines dans la plus grande partie du sud, du centre et de lest du Bangladesh. Les eaux des nappes alluviales holocènes du Gange, du Brahmapoutre et de la Meghna dépassent localement 200 fois la valeur guide donnée par lOMS pour leau de boisson, fixée à 10 µg/l darsenic. Environ 25% des puits du Bangladesh dépassent la valeur standard nationale de 50 µg/l, affectant au moins 25 millions de personnes. Larsenic a été introduit dans les nappes par la dissolution par réduction doxy-hydroxydes ferriques sur lesquels larsenic était adsorbé au cours du transport fluvial. Des profils verticaux darsenic dans leau souterraine pompée, dans leau porale et dans les sédiments des aquifères montrent des tendances convergentes. Les concentrations élevées sont associées à des sédiments à sable fin et riches en matières organiques. Les concentrations sont faibles au voisinage de la surface de la nappe, atteignent un maximum typiquement entre 20 et 40 m sous le sol, puis tombent à des niveaux très bas entre 100 et 200 m. Larsenic est surtout présent dans les eaux souterraines de la séquence de remplissage de vallée déposée au cours de la transgression marine holocène. Les eaux souterraines des aquifères pléistocènes et plus anciens sont très largement dépourvus darsenic. Les concentrations en arsenic dans de nombreux puits creusés à la main doivent probablement augmenter au cours des prochaines années ; aussi un suivi régulier est essentiel. Les aquifères à plus de 200 m sous les plaines alluviales offrent de bonnes perspectives pour des alimentations en eau sans arsenic à long terme, mais ils peuvent être limités par les risques dintrusion saline et la drainance descendante de larsenic.

     

Arsenic contamination in surface drainage and groundwater in part of the southeast Asian tin belt,Nakhon Si Thammarat Province,southern Thailand

The occurrence of human health problems resulting from arsenic contamination of domestic water supplies in Ron Phibun District, Nakhon Si Thammarat Province, southern Thailand was first recognized in 1987. The area has an extensive history of bedrock and alluvial mining, the waste from which is typically rich in arsenopyrite and related alteration products. In 1994 a collaborative study was instigated involving Thai and British government authorities to establish the distribution and geochemical form of As in surface drainage and aquifer systems in the affected area, the probable sources of As contamination, and the potential for problem alleviation. Hydrochemical analyses of surface- and groundwaters have confirmed the presence of dissolved As at concentrations exceeding WHO potable water guidelines by up to a factor of 500. Contamination of the shallow alluvial aquifer system is systematically more severe than the underlying carbonate-hosted aquifer. Deep boreholes may therefore provide the best available potable water source for the local population. The presence of up to 39% of total As as arsenite (H₃AsO₃) within the carbonate aquifer may, however, constitute a hidden toxicological risk, not evident in the shallow groundwater (in which arsenate species account for > 95% of total As). Mineralogical investigations of As-rich tailings and flotation wastes were undertaken to evaluate their likely impact on water quality. The results indicate that although some flotation wastes contain up to 30% As, the rate of leaching is extremely low. Consequently the As loading of drainage emanating from such waste is below the subregional average. Analyses of the silty alluvium that covers much of the central sector of the study area have highlighted As concentrations of up to 5000 mg kg^–1, probably carried by disseminated arsenopyrite. Following sulfide dissolution, the mobility of As in this material may be high (with resultant contamination of shallow groundwater) due to the low Fe content of the soil. On the basis of the data acquired, a range of pollution mitigation schemes are currently under investigation including Fe supplementation of alluvium and microbial degradation of disseminated arsenopyrite.     

黑河流域地下水同位素年龄及可更新能力研究

通过对黑河流域地下水的放射性同位素如氚(T)和¹⁴C的测定, 对该流域浅层和深层地下水的年龄以及其更新速率进行了估算. 结果表明: 整体上看, 从黑河流域的上游、中游至下游, 浅层和深层地下水年龄逐渐增加, 地下水更新速率也逐渐增大. 其中, 黑河上游浅层和深层地下水平均更新速率分别为1.96%·a^-1和1.76%·a^-1, 可更新能力最强; 中游浅层和深层地下水平均更新速率为1.25%·a^-1和0.68%·a^-1, 可更新能力次之; 下游浅层和深层地下水平均更新速率分别为0.74%·a^-1和0.18%·a^-1, 可更新能力最差. 黑河流域不同地带地下水由于循环条件的不同, 浅层和深层地下水年龄存在较大的差异. 其中, 中游山前平原补给条件较好, 浅层和深层地下水年龄较小; 中、下游远离河道地区浅层和深层地下水补给条件差, 显示了更老的年龄. 黑河流域埋深40 m以上的浅层地下水平均更新速率(1.13%·a^-1)高于埋深40~100 m之间的中层地下水(0.65%·a^-1)以及埋深100 m以下深层地下水(0.55%·a^-1). 因此, 在黑河流域地下水开发过程中要合理开发浅层地下水, 适当缩减开发深层地下水.     

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.     

Arsenic contamination in groundwater from parts of Ambagarh-Chowki block, Chhattisgarh, India: source and release mechanism

Arsenic contamination in tube-well water in Ambagarh-Chowki block, central India, is restricted to local areas confined within the N-S trending Dongargarh rift zone. Affected areas are preferentially located in acid volcanics, close to shear zones and also in granites. Dug-wells even in severely contaminated areas generally have As concentration ≤10 μg/l. But in Kaurikasa area, several tube-wells and dug-wells are severely polluted. Weathered rocks and soils are also enriched in As from severely contaminated areas. As preferentially occurs in iron-enriched soil and similarly altered biotite, chlorite in granite. As sorbed in hydrated iron oxide (HFO) that preferably occurs in acid-leachable fraction and possibly as coatings on kaolinite, illite and goethite in soil or as coatings and along cleavage traces on weathered biotite and chlorite. Reductive dissolution of HFO released sorbed As to groundwater and enriched it in Fe. Pyrite in volcanic and shear zone rocks, although locally As-bearing is a minor source of As in groundwater.     

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.     

浙江北部地区地下水高氟和高砷分布特点和建议

在分析了浙江北部地区地下水类型、特征、地下水开采现状和水位变化基础上,通过对不同类型地下水深井样品测试数据的研究,查明了区域地下水高氟和高砷的分布特点.高氟区主要出现于妙西花岗岩裂隙水和白雀岩溶水分布区,高砷区主要位于南浔第Ⅱ承压含水层局部区域.研究认为高氟和高砷地下水分布区与区域土壤和浅层地下水中总氟和总砷含量没有直接联系,深井地下水中的高氟和高砷主要与深部断裂构造有关.研究地区的这种高氟和高砷地下水目前仍然为很多居民所饮用,作者认为长期饮用这种高氟和高砷地下水容易导致地方病的产生,建议在高氟和高砷地下水分布区停止生活用水开采,有条件的企事业单位应实行改水方案.