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.     

Principal component analysis and hierarchical cluster analyses of arsenic groundwater geochemistry in the Hetao basin,Inner Mongolia

Although high As groundwater has been observed in shallow groundwater of the Hetao basin, little is known about As distribution in deep groundwater. Quantitative investigations into relationships among chemical properties and among samples in different areas were carried out. Ninety groundwater samples were collected from deep aquifers of the northwest of the basin. Twenty-two physicochemical parameters were obtained for each sample. Statistical methods, including principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to analyze those data. Results show that As species were highly correlated with Fe species, NH₄-N and pH. Furthermore, result of PCA indicates that high As groundwater was controlled by geological, reducing and oxic factors. The samples are classified into three clusters in HCA, which corresponded to the alluvial fans, the distal zone and the flat plain. Moreover, the combination of PCA with HCA shows the different dominant factors in different areas. In the alluvial fans, groundwater is influenced by oxic factors, and low As concentrations are observed. In the distal zone, groundwater is under suboxic conditions, which is dominated by reducing and geological factors. In the flat plain, groundwater is characterized by reducing conditions and high As concentrations, which is dominated by the reducing factor. This investigations indicate that deep groundwater in the alluvial fans mostly contains low As concentrations but high NO₃ and U concentrations, and needs to be carefully checked prior to being used for drinking water sources.     

Occurrence,distribution and source of arsenic in deep groundwater wells in Maydavood area,southwestern Iran

Groundwater in some deep wells of Maydavood aquifer, southwestern Iran, contains relatively high concentrations of arsenic. Detailed hydrochemical analysis of these groundwaters (with ICP-OES instrument) showed that concentrations of iron, manganese, nickel, and vanadium are also high in them and concentrations of total arsenic in 81% of deep wells are greater than World Health Organization’s permissible value (10 ppb). XRF analysis of surrounding geological formations and aquifer sediments proposed that original source of arsenic in aquifer material can be attributed to minerals from Asmari Formation. It appears that a key mechanism for arsenic mobilizing to deep wells is microbial biodegradation of petroleum related organic matters (PROMs), which exist in aquifer sediments and originates from the bedrock of the aquifer (Gachsaran Formation). This process is followed by microbially mediated reductive dissolution of arsenic-bearing iron/manganese oxyhydroxides/oxides and further by nickel and vanadium mobilizing to groundwater. According to hydrogeochemical conditions and cluster analysis, water wells in Maydavood aquifer are divided to four subgroups: the wells with mildly reducing condition (subgroup I), moderately reducing condition (subgroup II), reducing condition (subgroup III), and high reducing condition (subgroup IV). Affected wells to arsenic are belonged to subgroups III and IV.     

区域地下水演化的地球化学研究进展

由于区域地质特征、水文地质条件、气候影响和人类活动的差异性,导致区域地下水演化的地球化学过程复杂、影响因素众多.在总结近年来国内外区域地下水化学演化研究大量成果的基础上,综述了地下水演化的地球化学系统分析方法,地下水演化研究的水文地球化学方法、同位素地球化学和元素地球化学方法和技术以及地下水演化的地球化学模拟方法和技术及常用软件.指出在今后的一段时期内,区域地下水自然演化与人类活动的复合作用、地下水与地表水的相互作用、微生物-水-岩相互作用将是区域地下水地球化学研究的热点领域,其中物理、化学、生物的耦合作用将是区域地下水演化的地球化学研究的重点领域.     

Uranium geochemistry in groundwater from tertiary sediments

Dissolved U concentrations and activity ratios (ARs) of the U isotopes in the ²³⁸U decay series were measured in ground and surface waters as part of an investigation to delineate the water quality in a proposed uranium mining area of northwest Nebraska. In oxidizing groundwaters from 67 wells completed in the Tertiary sediments, increasing U concentrations in the direction of groundwater flow generally were associated with a maturation of the formation water as evidenced by evolutionary trends in major ion character. The increased U levels probably are associated with leaching as shown by the positive correlation between U concentrations and total dissolved solids (TDS) (r = +0.83). The inverse relationships between TDS and U ARs (r = ?0.73) and U levels and ARs (r = 0.72) indicate that the decay of excess U-234 is related to maturation of the formation water and to sediment leaching along the flowpath. The data are described by a model which incorporates etching, decay and recoil and suggests that aquifer residence time can be estimated from the TDS level.The levels of soluble U in a reducing uraniferous hydrogeologic unit near Crawford, Nebraska are affected by the proximity of the sample collection to ore. In groundwater samples having similar chemistries (Na-SO₄ + Cl type), similar Ehs, and collected from a close-knit pattern, U concentrations ranged from 0.01 to 2,037 μg l^?1 and ARs ranged from 0.75 to 12.6. This high variability in U levels and ARs is indicative of uranium ore in small areal studies where low ARs almost always are associated with high U concentrations.     

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.     

Slow arsenic poisoning of the contaminated groundwater users

This paper gives impact of Arsenic contaminated water on human health as well as overview of the extent and severity of groundwater arsenic contamination in Bangladesh. Scalp hair is the most important part of the human body to monitor the accumulation of this type of poison. Therefore, an experiment has been carried out by Neutron Activation Analysis (NAA) at Atomic Energy Research Establishment (AERE), Savar, Dhaka, Bangladesh on human hair of corresponding tube well water users of these areas to determine the total accumulation of arsenic to their body. Hair samples collected from the region where the groundwater was found highly contaminated with arsenic. The obtained results of arsenic concentration in the lower age (Hb) categories of users (below 12 years of age users) is in the range of 0.33 to 3.29 /gmg/g (ppm) and that in the Hu categories (upper 12 years of age users) is 0.47 to 6.64 μg/g (ppm). Where as maximum permissible range is 1 ppm certified from WHO. Results show that the peoples are highly affected where the groundwater is highly contaminated with arsenic and acts as the primary source of arsenic poisoning among the peoples of those areas. The results indicate that human population is affected with arsenic locally using the contaminated water for a long time.     

Sources of salinity and arsenic in groundwater in southwest Bangladesh

Background

High salinity and arsenic (As) concentrations in groundwater are widespread problems in the tidal deltaplain of southwest Bangladesh. To identify the sources of dissolved salts and As, groundwater samples from the regional shallow Holocene aquifer were collected from tubewells during the dry (May) and wet (October) seasons in 2012–2013. Thirteen drill cores were logged and 27 radiocarbon ages measured on wood fragments to characterize subsurface stratigraphy.

Results

Drill cuttings, exposures in pits and regional studies reveal a >5 m thick surface mud cap overlying a ~30 m thick upper unit of interbedded mud and fine sand layers, and a coarser lower unit up to 60 m thick dominated by clean sands, all with significant horizontal variation in bed continuity and thickness. This thick lower unit accreted at rates of ~2 cm/year through the early Holocene, with local subsidence or compaction rates of 1–3 mm/year. Most tubewells are screened at depths of 15–52 m in sediments deposited 8000–9000 YBP. Compositions of groundwater samples from tubewells show high spatial variability, suggesting limited mixing and low and spatially variable recharge rates and flow velocities. Groundwaters are Na–Cl type and predominantly sulfate-reducing, with specific conductivity (SpC) from 3 to 29 mS/cm, high dissolved organic carbon (DOC) 11–57 mg/L and As 2–258 ug/L, and low sulfur (S) 2–33 mg/L.

Conclusions

Groundwater compositions can be explained by burial of tidal channel water and subsequent reaction with dissolved organic matter, resulting in anoxia, hydrous ferric oxide (HFO) reduction, As mobilization, and sulfate (SO₄) reduction and removal in the shallow aquifer. Introduction of labile organic carbon in the wet season as rice paddy fertilizer may also cause HFO reduction and As mobilization. Variable modern recharge occurred in areas where the clay cap pinches out or is breached by tidal channels, which would explain previously measured ¹⁴C groundwater ages being less than depositional ages. Of samples collected from the shallow aquifer, Bangladesh Government guidelines are exceeded in 46 % for As and 100 % for salinity.

     

High arsenic contents in groundwater of central Spain

The chemical and microbiological characteristics of groundwater from two provinces of central Spain were studied. In some zones of this area, the concentrations of As in groundwater exceed the guideline concentrations, set internationally between 10 g/l and 50 g/l, reaching levels over 100 g/l. A narrow correlation between the contents of arsenic and HCO₃^– was observed. These data suggest a possible mechanism of the As mobilization from aquifer sediments to groundwater: the bicarbonate ions could displace HAsO₄^2– adsorbed on aquifer oxyhydroxides. Sediments containing relatively high contents of adsorbed arsenic are deposited in surface water environments with low carbonate concentrations. Subsequently, the sediments become exposed to groundwater with highly dissolved carbonate content, and arsenic can be mobilized by displacement from mineral surfaces. In addition, the presence of Pseudomonas genera bacteria, which secrete siderophores (Fe chelating agents) could mobilize As adsorbed on Fe oxides through their dissolution. These combined microbiological and chemical processes might have increased the natural mobility of As.     

Redox control of arsenic mobilization in Bangladesh groundwater

Detailed hydrochemical measurements, δ³⁴S_SO4 and ³H analyses were performed on 37 groundwater samples collected during February 1999, January and March 2000 from 6 locations in eastern and southeastern Bangladesh to examine redox processes that lead to As mobilization in groundwater. The study sites were chosen based on available nation-wide As surveys to span the entire spectrum of As concentrations in Bangladesh groundwater, and to represent 3 of 5 major geological units of the Ganges-Brahmaputra Delta: uplifted Pleistocene terrace, fluvial flood plain and delta plain. Arsenic was found to be mobilized under Fe-reducing conditions in shallow aquifers (<35 m depth), presumably of Holocene age. It remained mobile under SO₄-reducing conditions, suggesting that authigenic sulfide precipitation does not constitute a significant sink for As in these groundwaters. The redox state of the water was characterized by a variety of parameters including dissolved O₂, NO₃⁻, Mn²⁺, Fe²⁺ concentrations, and SO₄²⁻/Cl⁻ ratios. High dissolved [As] (> 50 μg/l; or > 0.7 μM ) were always accompanied by high dissolved [HCO₃⁻] (> 4 mM), and were close to saturation with respect to calcite. Groundwater enriched in As (200–800 μg/l; or 2.7–10.7 μM) and phosphate (30–100 μM) but relatively low in dissolved Fe (5–40 μM) probably resulted from re-oxidation of reducing, As and Fe enriched water. This history was deduced from isotopic signatures of δ³⁴S_SO4 and ³H₂O (³H) to delineate the nature of redox changes for some of the reducing groundwaters. In contrast, As is not mobilized in presumed Pleistocene aquifers, both shallow (30–60 m) and deep (150–270 m), because conditions were not reducing enough due to lack of sufficient O₂ demand.     

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.     

Arsenic distribution, concentration and speciation in groundwater of the Osijek area, eastern Croatia

Groundwater is the main source of drinking water for the population of nearly 200,000 people in eastern Croatia. The largest town in the region is Osijek whose citizens are supplied with drinking water obtained from groundwater from the “Vinogradi” well field. This study investigated and determined As occurrence in groundwater of the Osijek area. Groundwater samples were taken from 18 water wells and 12 piezometers with a depth ranging between 21 and 200 m. Over the 10-a period to 2007, a mean As concentration of 240 μg L⁻¹ was found. There was no statistically significant secular change in concentration over that period, however small but significant seasonal variations were noted, with the highest seasonal As concentrations over the period May 2006-February 2007 being observed in summer. The predominant As species observed was As(III), constituting 85% and 93% of total As in piezometers and water wells, respectively. Higher concentrations of As tended to be found in deeper wells with the mean As concentration in shallow groundwater (<50 m) and deep groundwater (>50 m) being 27 μg L⁻¹, and 205 μg L⁻¹, respectively. Geochemically, the groundwaters show similarities to those in other parts of the Pannonian Basin. Arsenic(tot) is weakly correlated with pH and Fe, negatively correlated with Mn and has no significant correlation with any of EC, COD-Mn or alkalinity.     

Suboxic trace metal geochemistry in the Eastern Tropical North Pacific

We analyzed Al, Ti, Fe, Mn, Cu, Ba, Cd, U, Mo, V, and Re in water column, settling particulate, and sediment (0 to 22 cm) samples from the intense oxygen minimum zone (OMZ) of the eastern tropical North Pacific near Mazatlán, Mexico. The goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique “suboxic” geochemical signature.The water column was characterized by a Mn maximum, reaching ∼8 nmol kg⁻¹ at 400 m. Concentrations of Cu, Ba, Cd, Mo, Re, U, and V were unaffected by the low O₂ conditions and were comparable to those of the open ocean. Sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin. Al, Ti, and Fe were mostly (at least 79%) lithogenic. About 75% of the Mn was nonlithogenic. Significant amounts (at least 58%) of Cu, Ba, Cd, and Mo were nonlithogenic.Sediment geochemistry varied across the continental shelf and slope. Cadmium, U, and Re have prominent maxima centered at 310 m, with 12.3 ppm, 10.9 ppm, and 68.3 ppb, respectively, at the core top. High values of Mo (averaging 6.8 ppm) and V (averaging 90 ppm) are seen in OMZ surface sediment. Additional down-core enrichment occurs for all redox-sensitive elements in the top 10 cm. For U, Mo, V, and Re, surface sediments are a poor indicator of metal enrichment. Comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition, especially for Cd, U, and Mo.We evaluated Re/Mo and Cd/U ratios as tracers for redox environments. Rhenium and Mo concentrations and Re/Mo ratios do not lead to consistent conclusions. Concurrent enrichments of Re and Mo are an indicator of an anoxic depositional environment. In contrast, high Re/Mo ratios are an indicator of suboxic conditions. Cadmium is enriched in surface sediments, while U has considerable down-core enrichment. The concentrations of Cd and U and the Cd/U ratio do not follow patterns predicted from thermodynamics. Though the water column is suboxic, these four redox-sensitive elements indicate that the sediments are anoxic. The implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column.     

Micromorphology and geochemistry of groundwater silcretes in the eastern South Downs, UK

Groundwater silcretes have been recognized recently as major terrestrial silicon sinks and yet their origins are poorly understood. This paper aims to further the understanding of the micro‐fabric, geochemistry and formation of groundwater silcretes, through detailed analyses of silcrete boulders from the South Downs, Sussex, UK. In‐depth petrological investigations of silcrete blocks identified three varieties of silcrete across the study area (saccharoid, hard and pebbly conglomeratic or silcrete breccia), similar to those elsewhere in England. Silcrete fabrics were universally simple and preserved host material structures. Optically continuous quartz overgrowths were the dominant cement and developed on framework grains in the absence of silt‐ and clay‐sized particles. Finer‐grained silica cements occurred in isolated patches and as vein‐ or cap‐like geopetal features. These caps and veins formed through the silicification of illuviated clay‐rich material that entered the host sediment prior to, or in the early stages of, overgrowth formation. Titanium contents were related to the amount of fine‐grained silica and appear to reflect variations in host material chemistry. Subsequent to silicification, the silcretes were altered by at least two phases of ferruginization, characterized by the ingress of iron minerals and partial fabric dissolution or replacement. The study reveals strong similarities in the micromorphology and geochemistry of groundwater silcretes in the study area and those developed in sandy host sediments in neighbouring parts of northwest Europe. Variations that do occur could be explained by differences in the host sediment, geological setting or tectonic history of the respective basins (or sub‐basins), suggesting that there may be a common mechanism for silcrete formation across north‐west Europe. Silcrete development appears to be related to the release of silica accompanying acid leaching of the host material or adjacent strata. In the South Downs, this probably resulted from oxidation of pyrite in the argillaceous and lignitic sediments overlying the host sands. It is envisaged that palaeoenvironmental conditions were of limited importance for silcrete development and that there was no specific ‘era’ of formation, with phased development accompanying landscape evolution through the Neogene into the Pleistocene.     

The occurrence and geochemistry of arsenic in groundwaters of the Newark basin of Pennsylvania

Elevated As concentrations in groundwater in the eastern United States have been recognized predominantly in the accretionary geologic terranes of northern New England. A retrospective examination of more than 18,000 existing groundwater samples from the Pennsylvania Department of Environmental Protection (PA DEP) Drinking Water and Sampling Information System database indicates that elevated groundwater As concentrations occur throughout the northern half of the Piedmont Province of Pennsylvania. Chemical analyses of 53 samples collected in 2005 from drinking water wells in this area all had detectable As, and 23% of these samples contained elevated (>133 nmol/L or >10 μg/L) concentrations of As. Elevated concentrations of As in the groundwater samples were most common in the Mesozoic sedimentary strata composed of sandstone and red mudstone with interbedded gray shale, and gray to black siltstone and shale. Arsenic was typically not elevated in groundwater of diabase intrusions of the Newark Basin or in crystalline and calcareous aquifers to the north of the Newark Basin. Geochemical parameters such as pH and oxidation–reduction potential can indicate mobility mechanisms of As in some regions. In this area, measured groundwater conditions were predominantly oxidizing (Eh > +50 mV), and more than 85% of samples contained arsenate as the dominant As species. Variations in pH were strongly correlated to the As concentration, with highest As concentrations observed at pH values greater than 6.4. The original source of As is most likely the black and gray shales that contain some arsenian pyrite with groundwater concentrations likely to be controlled by adsorption/desorption reactions with Fe oxides in the red mudstone aquifer materials.     

重庆温泉及地下热水的分布及成因

重庆地区地下热水资源较为丰富,且地下热水的分布也比较特殊。着重对重庆温泉及地下热水的分布特征、水化学特征、热储构造、形成条件和成因模式等问题进行了总结。重庆附近地下热储为三叠系中、下统碳酸盐岩,地下热水的分布受到背斜构造控制,温泉大多在高隆起背斜轴部、两翼及倾末端出露,与常见的受断裂控制的断裂-深循环型地下热水的分布不同,属于盆地-出露型的地下热水分布类型,水温为32~64 ℃,属于中低温温泉。受背斜构造的影响,地下热水主要溶滤三叠系中、下统雷口坡组和嘉陵江组碳酸盐岩,TDS为2~3 g/L,水化学类型多为SO4—Ca型,长期溶滤作用使地下热水趋于淡化,但尚未达到淡水阶段。地下热水热源主要为正常的地热增温,大气降水为其补给来源,补给区高程约为670~1 500 m。大气降水在重庆各背斜核部岩溶露头区入渗,地下水沿着背斜两翼向热储层深部径流并获得加热后,顺构造线方向自南、自北向背斜中部或向背斜倾末端径流,在河流深切的峡谷地段碳酸盐岩裸露区或埋藏区出露成泉,或在背斜两翼人工揭露形成钻井温泉和坑道温泉。     

Scinario of arsenic pollution in groundwater: West Bengal

目前,西孟加拉地区地下水砷污染问题日益严重并且已经波及到食物链中.由于吸收了砷污染地下水,谷物和蔬菜中砷含量日渐累积,超出了健康规定范围.尽管提出了若干补救方案,但是考虑到农业人口的社会经济状况,建议使用地表水灌溉方案.然而,实际中该方案仍然较难施行,且并无其他更经济有效的措施.若干年后,含水层可以减缓严酷的健康环境现状并为人们提供安全的饮用水.     

Origin of arsenic in the groundwater of the Rioverde basin, Mexico

Groundwater in the semiarid Rioverde basin in the northern part of Mexico was investigated with respect to major and minor elements including arsenic, as well as As(III) and As(V). The total arsenic concentrations varied from less than 5 to 50 g/L. The in situ arsenic determination method produced reliable results with deviations from -5.6 to 2.2 g/L compared to laboratory HGAAS. Since arsenic and barium were found to be inversely correlated, it was suspected that precipitation of barium arsenate controlled arsenic solubility. Thermodynamically modeling by means of PHREEQC indicated that BaHAsO₄·H₂O (not BaAsO₄) might be a limiting phase, however only at higher concentrations than those determined in this study. Increased arsenic groundwater concentrations were found with lacustrine sediments and decreased concentrations with fluvial Quaternary sediments. Increased total arsenic concentrations correlate with increased As(III) concentrations in the groundwater of the lacustrine sediments.