Effects of human-induced alteration of groundwater flow on concentrations of naturally-occurring trace elements at water-supply wells

The effects of human-induced alteration of groundwater flow patterns on concentrations of naturally-occurring trace elements were examined in five hydrologically distinct aquifer systems in the USA. Although naturally occurring, these trace elements can exceed concentrations that are considered harmful to human health. The results show that pumping-induced hydraulic gradient changes and artificial connection of aquifers by well screens can mix chemically distinct groundwater. Chemical reactions between these mixed groundwaters and solid aquifer materials can result in the mobilization of trace elements such as U, As and Ra, with subsequent transport to water-supply wells. For example, in the High Plains aquifer near York, Nebraska, mixing of shallow, oxygenated, lower-pH water from an unconfined aquifer with deeper, confined, anoxic, higher-pH water is facilitated by wells screened across both aquifers. The resulting higher-O₂, lower-pH mixed groundwater facilitated the mobilization of U from solid aquifer materials, and dissolved U concentrations were observed to increase significantly in nearby supply wells. Similar instances of trace element mobilization due to human-induced mixing of groundwaters were documented in: (1) the Floridan aquifer system near Tampa, Florida (As and U), (2) Paleozoic sedimentary aquifers in eastern Wisconsin (As), (3) the basin-fill aquifer underlying the California Central Valley near Modesto (U), and (4) Coastal Plain aquifers of New Jersey (Ra). Adverse water-quality impacts attributed to human activities are commonly assumed to be related solely to the release of the various anthropogenic contaminants to the environment. The results show that human activities including various land uses, well drilling, and pumping rates and volumes can adversely impact the quality of water in supply wells, when associated with naturally-occurring trace elements in aquifer materials. This occurs by causing subtle but significant changes in geochemistry and associated trace element mobilization as well as enhancing advective transport processes.     

Groundwater chemistry and redox processes: Depth dependent arsenic release mechanism

Patchy occurrences of elevated As are often encountered in groundwater from the shallow aquifers (<50 m) of the Bengal Delta Plain (BDP). A clear understanding of various biogeochemical processes, responsible for As mobilization, is very important to explain this patchy occurrence and thus to mitigate the problem. The present study deals with the periodical monitoring of groundwater quality of five nested piezometeric wells between December 2008 and July 2009 to investigate the temporal changes in groundwater chemistry vis-a-vis the prevalent redox processes in the aquifer. Geochemical modeling has been carried out to identify key phases present in groundwater. A correlation study among different aqueous redox parameters has also been performed to evaluate prevailing redox processes in the aquifer. The long term monitoring of hydrochemical parameters in the multilevel wells together with hydrogeochemical equilibrium modeling has shown more subtle differences in the geochemical environment of the aquifer, which control the occurrence of high dissolved As in BDP groundwater. The groundwater is generally of Ca-HCO₃ type. The dissolved As concentration in groundwater exceeded both WHO and National drinking water standard (Bureau of Indian Standards; BIS, 10 μg L⁻¹) throughout the sampling period. The speciation of As and Fe indicate persistent reducing conditions within the aquifer [As(III): 87-97% of As_T and Fe(II): 76-96% of Fe_T]. The concentration of major aqueous solutes is relatively high in the shallow aquifer (wells A and B) and gradually decreases with increasing depth in most cases. The calculation of SI indicates that groundwater in the shallow aquifer is also relatively more saturated with carbonate minerals. This suggests that carbonate mineral dissolution is possibly influencing the groundwater chemistry and thereby controlling the mobilization of As in the monitored shallow aquifer. Hydrogeochemical investigation further suggests that Fe and/or Mn oxyhydroxide reduction is the principal process of As release in groundwater from deeper screened piezometric wells. The positive correlations of U and V with As, Fe and Mn indicate redox processes responsible for mobilization of As in the deeper screened piezometric wells are possibly microbially mediated. Thus, the study advocates that mobilization of As is depth dependent and concentrations of As in groundwater depends on single/combined release mechanisms.     

Hydrogeochemical characteristics and its role in controlling arsenic mobilization in a shallow aquifer

The relevance of groundwater hydrogeochemistry to explain the occurrence and distribution of arsenic in groundwater is of great interest. The insightful discussions on the control of shallow groundwater (< 50 m) hydrogeochemistry in arsenic mobilization are known to be a viable tool to explain the arsenic menace in shallow groundwater. The present investigation emphasizes the hydrogeochemical driver and/or control over the reductive dissolution of Fe-bearing host minerals and thereby releasing arsenic into the shallow groundwater of the study area. The study suggests that hydrogeochemical evolution is mainly governed by carbonate minerals dissolution, silicate weathering, and competitive ion-exchange processes in the shallow aquifers (< 50 m). The present study also indicates the prevalence of carbonate minerals dissolution over silicate weathering. The emergence of Cl⁻ concentration in the shallow groundwater founds the possibilities of anthropogenic inputs into the shallow aquifers (< 50 m). The reducing environment in shallow aquifers (< 50 m) of the study area is evident in the reductive dissolution of Fe- bearing shallow aquifer minerals which absorb arsenic in the solid phase and mobilize arsenic onto shallow groundwater. The study opted for many statistical approaches to delineate the correlation among major and minor ionic constituents of the groundwater which are very helpful to understand the comprehensive mechanism of arsenic mobilization into shallow groundwater.

     

Occurrence and geochemistry of arsenic in the groundwater of Eastern Croatia

In order to examine the extent of the As enrichment and the factors influencing this enrichment in the groundwater of Eastern Croatia, groundwater samples were collected from 56 production wells in two counties, Osijek-Baranja and Vukovar-Srijem, suspected to be more affected. Hydrochemical analyses were performed at all locations including in situ As speciation at 32 locations. Arsenic was detected in 46 out of 56 groundwater samples with total As concentrations up to 491 μg/L. Thirty-six of the studied wells yielded groundwater with total As concentrations that exceeded the WHO Maximum Contaminant Level for arsenic in drinking water of 10 μg/L. Only inorganic As species were detected with arsenite As(III) as the predominant form. The spatial distribution of As in the groundwater was significantly linked with geological, geomorphological and hydrogeological development of the alluvial basin of the Drava and Sava rivers. The most probable groundwater As sources are deeper sediments from the Middle and Upper Pleistocene. The results obtained suggest that biogeochemical processes controlling As concentration in the groundwater are complex and location-specific. Reductive dissolution of Fe oxides, desorption of As from Fe oxides and/or clay minerals as well as competition for the sorption sites with organic matter and phosphate could be the principal mechanisms that control As mobilization. The extent of those processes vary in the different parts of the Drava and Sava depressions and could be linked to different site related parameters, such as lithology, mineralogy, local hydrology and hydrogeology; thus different processes of As mobilization have been proposed for the different types of water in relation to groundwater evolution.     

Preliminary evidence of a link between surface soil properties and the arsenic content of shallow groundwater in Bangladesh

The extremely heterogeneous distribution of As in Bangladesh groundwater has hampered efforts to identify with certainty the mechanisms that lead to extensive mobilization of this metalloid in reducing aquifers. We show here on the basis of a high-resolution transect of soil and aquifer properties collected in Araihazar, Bangladesh, that revealing tractable associations between As concentrations in shallow (< 20 m) groundwater with other geological, hydrological, and geochemical features requires a lateral sampling resolution of 10–100 m. Variations in the electromagnetic conductivity of surface soils (5–40 mS/m) within a 500 m × 200 m area are documented with 560 EM31 measurements. The results are compared with a detailed section of groundwater As concentrations (5–150 μg/L) and other aquifer properties obtained with a simple sampling device, “the needle-sampler”, that builds on the local drilling technology. By invoking complementary observations obtained in the same area and in other regions of Bangladesh, we postulate that local groundwater recharge throughout permeable sandy soils plays a major role in regulating the As content of shallow aquifers by diluting the flux of As released from reducing sediments.     

Dissolved organic matter tracers reveal contrasting characteristics across high arsenic aquifers in Cambodia:A fluorescence spectroscopy study

Organic matter in the environment is involved in many biogeochemical processes,including the mobilization of geogenic trace elements,such as arsenic,into groundwater.In this paper we present the use of fluorescence spectroscopy to characterize the dissolved organic matter(DOM)pool in heavily arsenicaffected groundwaters in Kandal Province,Cambodia.The fluorescence DOM(fDOM)characteristics between contrasting field areas of differing dominant lithologies were compared and linked to other hydrogeochemical parameters,including arsenic and dissolved methane as well as selected sedimentary characteristics.Absorbance-corrected fluorescence indices were used to characterize depth profiles and compare field areas.Groundwater fDOM was generally dominated by terrestrial humic and fulvic-like components,with relatively small contributions from microbially-derived,tryptophan-like components.Groundwater fDOM from sand-dominated sequences typically contained lower tryptophan-like,lower fulvic-like and lower humic-like components,was less bioavailable,and had higher humification index than clay-dominated sequences.Methane concentrations were strongly correlated with fDOM bioavailability as well as with tryptophan-like components,suggesting that groundwater methane in these arsenic-prone aquifers is likely of biogenic origin.A comparison of fDOM tracers with sedimentary OM tracers is consistent with the hypothesis that external,surface-derived contributions to the aqueous DOM pool are an important control on groundwater hydrogeochemistry.     

Hydrochemistry and isotope geochemistry as tools for groundwater hydrodynamic investigation in multilayer aquifers: a case study from Lomellina, Po plain, South-Western Lombardy, Italy

A multicriteria approach in studying hydrodynamics of a multilayer aquifer system has been used in the Lomellina region (Northern Italy). It involves the reconstruction of the hydrogeological framework coupled to the definition of the hydrochemical and isotopic features of the aquifers. A shallow phreatic aquifer, reaching depths of about 60–80 m from the surface, and deeper aquifers containing confined groundwater, were distinguished. Groundwater generally shows mineralisation decreasing with depth; dissolved ions depict calcium-bicarbonate hydrochemical facies and stable isotopes define the recharge mechanisms, the origin of groundwater, and the hydraulic confinement of deep aquifers. The phreatic aquifer is fed by local infiltration and by streams and irrigation channels. Tritium and Carbon-14 groundwater dating indicate long residence times (on the order of thousands of years) for confined aquifers. The confined aquifers show essentially passive hydrodynamic conditions and maintain a higher piezometric level than the phreatic aquifer. This inhibits the possibility of recent water penetrating far below the surface. The hydrogeological setting of the Lomellina region displays features which are common to other sectors of the Po plain. As a consequence, the results of this study, although conducted on a restricted area, are highly illustrative of groundwater hydrodynamics in large sedimentary aquifers.     

Deeper groundwater chemistry and geochemical modeling of the arsenic affected western Bengal basin,West Bengal,India

A regional scale hydrogeochemical study of a ∼21,000-km² area in the western Bengal basin shows the presence of hydrochemically distinct water bodies in the main semiconfined aquifer and deeper isolated aquifers. Spatial trends of solutes and geochemical modeling indicate that carbonate dissolution, silicate weathering, and cation exchange control the major-ion chemistry of groundwater and river water. The main aquifer water has also evolved by mixing with seawater from the Bay of Bengal and connate water. The isolated aquifers contain diagenetically altered water of probable marine origin. The postoxic main aquifer water exhibits overlapping redox zones (metal-reducing, sulfidic and methanogenic), indicative of partial redox equilibrium, with the possibility of oxidation in micro-scale environments. The redox processes are depth-dependent and hydrostratigraphically variable. Elevated dissolved As in the groundwater is possibly related to Fe(III) reduction, but is strongly influenced by coupled Fe–S–C redox cycles. Arsenic does not show good correlations with most solutes, suggesting involvement of multiple processes in As mobilization. The main river in the area, the Bhagirathi–Hoogly, is chemically distinctive from other streams in the vicinity and probably has little or no influence on deep groundwater chemistry. Arsenic in water of smaller streams (Jalangi and Ichamati) is probably introduced by groundwater discharge during the dry season.     

Arsenic mobilization in shallow aquifers of Datong Basin: Hydrochemical and mineralogical evidences

To better understand the sources and mobilization processes responsible for arsenic enrichment in groundwater in the central part of Datong Basin where serious arsenic poisoning cases have been reported, hydrochemical characteristics of the groundwater and the geochemical and mineralogical features of the aquifer sediments were studied. The aqueous arsenic levels are strongly depth-dependent in the study area and the high arsenic concentrations are found at depths between 15 m and 60 m, with a maximum up to 1820 μg/L. The hydrochemical characteristics of high arsenic groundwater from the Datong Basin indicate that the mobilization of arsenic is related to reductive dissolution of Fe oxides/oxyhydroxides and/or desorption from the Fe oxides/oxyhydroxides at high pH (above 8.0). The bulk chemical results of sediments show the arsenic and iron are moderately correlated, suggesting that arsenic is associated with iron-bearing minerals. Results of sequential-extraction experiment show that solid-phase arsenic is similarly distributed among the different pools of reservoir in the aquifer sediments. Strongly adsorbed arsenic and co-precipitated arsenic are its dominant species in the solid-phase. Geochemical studies using chemical analysis, X-ray diffraction and scanning electron microscopy on magnetically separated fractions demonstrate that iron oxides/oxyhydroxides with residual magnetite and chlorite, illite, iron oxides/oxyhydroxides-coated quartz and feldspar, and ankerite are the dominant carriers of arsenic in the sediments. The major processes of arsenic mobilization are probably linked to desorption of As from Fe oxides/oxyhydroxides and reductive dissolution of Fe-rich phases in the aquifer sediments under reducing and alkaline conditions.     

Arsenic enrichment in unconfined sections of the southern Gulf Coast aquifer system, Texas

Groundwater arsenic concentrations exceeding the federal drinking water standard are common in the southern Gulf Coast aquifer system in Texas, including in aerobic, unconfined groundwater which provides much of the municipal and domestic water supplies for the region. The objective of this study was to determine geochemical factors affecting the occurrence and distribution of groundwater As in unconfined portions of the southern Gulf Coast aquifer system through a comparative transect study of groundwater across three major hydrostratigraphic units (the Catahoula Formation, Jasper aquifer and Evangeline aquifer) and analysis of regional water quality data. Results show that As concentrations decrease with increasing distance from the Catahoula Formation, which is consistent with Miocene volcanic ash as the main source of As to groundwater in the region. Arsenic concentrations correlate with V, SiO₂ and K, all of which were released during weathering of volcanic sediments and their degradation products. In all three units, carbonate weathering and active recharge in the unconfined zones result in circum-neutral pH and oxidizing groundwater, which are typically amenable to As immobilization by adsorption of arsenate onto mineral oxides and clays. However, As concentrations exceed 10 μg/L in approximately 30% of wells. Silica that was co-released with As may compete for sorption sites and reduce the capacity for arsenate adsorption.     

贵德盆地三河流域高砷地下水中溶解性有机物三维荧光特性及其指示意义

溶解性有机物(dissolved organic matter, DOM)可以通过多种方式控制含水层中砷的迁移转化。贵德盆地承压含水层地下水砷含量显著高于潜水含水层。为查明承压水中溶解性有机物对砷浓度的影响,对研究区地表水、潜水以及承压水进行吸光度和三维荧光光谱的分析,利用平行因子分析法确定了水样中有机物成分及荧光特征。结果表明,贵德盆地水体中DOM包含陆源类腐殖质(C1)、受人为影响的腐殖质(C2)、类醌化合物(C3)和微生物来源的腐殖质(C4)4种组分。陆源类腐殖质C1可在地下水中富集,占总有机质的40%~55%。相比于地下水,C2和C3则在地表水中占据较高的比例。高砷承压水中C2、C3所占比例高于低砷潜水。其中,C1可以通过络合作用促进溶解性砷浓度的提高,C3作为电子穿梭体可以促进含砷铁氧化物或氢氧化物的还原性溶解从而释放砷。微生物降解有机质生成的HCO-3可以与砷竞争吸附,促进砷的解吸附。此外,还原性溶解产生的Fe(II)与HCO-3形成FeCO3固定一部分的砷。该研究表明,地下水中的天然有机物通过络合作用和作为电子穿梭体促进铁氧化物还原导致地下水砷的富集,为分析黄河上游地区高砷地下水的成因提供理论依据。     

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.     

Characterisation of organic matter and microbial communities in contrasting arsenic-rich Holocene and arsenic-poor Pleistocene aquifers,Red River Delta,Vietnam

High concentrations of geogenic As in the groundwaters of south and SE Asia, which are used as drinking waters, are causing severe health impacts to the exposed human populations. It is widely accepted that As mobilisation from sediments into these shallow reducing groundwaters requires active metal-reducing microbes and electron donors such as organic matter (OM). Although OM in such Holocene aquifers has been characterised, there is a dearth of data on Pleistocene aquifers from the same areas. Reported here are preliminary studies of OM and microbial communities present in two aquifers, one of Pleistocene and one of Holocene age, with contrasting concentrations of As (viz. Pleistocene: low As <10 μg/L; Holocene: high As up to 600 μg/L) from Van Phuc village in the Red River Delta, Vietnam. Results revealed OM inputs from multiple sources, including potential contributions from naturally occurring petroleum seeping into the shallow aquifer sediments from deeper thermally mature source rocks. Although concentrations vary, no noticeable systematic differences in biomarker distribution patterns within the OM were observed between the two sites. Microbial analyses did not show a presence of microbial communities previously associated with As mobilisation. All clone libraries were dominated by α-, β-, and γ-Proteobacteria not known to be able to reduce Fe(III) or sorbed As(V). Furthermore, representatives of the Fe(III)-reducing genus Geobacter could only be detected at very low abundance by PCR, using highly selective 16S rRNA gene primers, supporting the hypothesis that metal reduction is not a dominant in situ process in these sediments. No correlation between As concentration in groundwater and OM composition nor microbial community in the host sediments was found. This suggests that either (i) As is not being significantly mobilised in situ in these sediments, instead As appears to be mobilised elsewhere and transported by groundwater flow to the sites or (ii) sorption/desorption processes, as implicated by geochemical data from the cores, play a critical role in controlling As concentrations at these sites.     

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.     

内蒙古河套平原典型高砷区地下水中砷的演化规律

通过对高砷地下水典型区完整地质单元不同深度含水层地下水进行监测,分析了与砷释放、迁移和富集有关的敏感因素（水位、Eh、总铁、亚铁等）的时间和空间变化规律,探讨了高砷地下水的形成机理。结果发现,地下水灌溉区和黄河水灌溉区,地下水水位均受人为灌溉活动的影响。地下水砷含量在空间和时间尺度上发生有规律的变化。在空间尺度上,地下水中砷含量随着深度的增加而升高,井深小于10 m的地下水砷含量在1.88～2.58 μg/L;井深在10~15 m之间的地下水中砷含量在18.2～217 μg/L;井深在15~25 m之间的地下水中砷含量在38.3～226 μg/L。受人为灌溉影响,地下水中砷的含量会随着地下水位的抬升而升高。地下水砷含量随时间变化的原因是水位抬升使水位变化造成氧化还原环境改变。地下水系统中含砷铁氧化物矿物的还原性溶解、脱硫酸作用等是控制地下水砷含量的主要水文地球化学过程。     

Arsenic release from chlorine-promoted alteration of a sulfide cement horizon: Evidence from batch studies on the St. Peter Sandstone,Wisconsin, USA

Elevated As concentrations have been measured in wells in the St. Peter Sandstone aquifer of eastern Wisconsin, USA. The primary source is As-bearing sulfide minerals (pyrite and marcasite) within the aquifer. There is concern that well disinfection by chlorination may facilitate As release to groundwater by increasing the rate and extent of sulfide oxidation. The objective of this study was to examine the abiotic processes that mobilize As from the aquifer solids during controlled exposure to chlorinated solutions. Thin sections made from sulfidic aquifer material were characterized by quantitative electron probe micro-analysis before and after 24 h exposure to solutions of different Cl₂ concentrations. Batch experiments using crushed aquifer solids were also conducted to examine changes in solution chemistry over 24 h. Results of the combined experiments indicate that Cl₂ addition affects As release and uptake in two ways. First, Cl₂ increases oxidation of sulfide minerals, releasing more As from the mineral structure. Chlorine addition also increases the rate of Fe(II) oxidation and subsequent hydrous ferric oxide (HFO) precipitation, allowing for increased uptake of As onto the mineral surface. Although HFOs can act as sinks for As, they can release As if biogeochemical conditions (e.g. redox, pH) change. These results have implications not only for disinfection of drinking water wells in the study area, but also suggest that introduction of oxidants may adversely affect water quality during aquifer storage and recovery programs in aquifers containing As-bearing minerals.     

Comparison of dissolved and particulate arsenic distributions in shallow aquifers of Chakdaha, India, and Araihazar, Bangladesh

Background  

The origin of the spatial variability of dissolved As concentrations in shallow aquifers of the Bengal Basin remains poorly understood. To address this, we compare here transects of simultaneously-collected groundwater and aquifer solids perpendicular to the banks of the Hooghly River in Chakdaha, India, and the Old Brahmaputra River in Araihazar, Bangladesh.     

Elevated naturally occurring arsenic in a semiarid oxidizing system, Southern High Plains aquifer, Texas, USA

High groundwater As concentrations in oxidizing systems are generally associated with As adsorption onto hydrous metal (Al, Fe or Mn) oxides and mobilization with increased pH. The objective of this study was to evaluate the distribution, sources and mobilization mechanisms of As in the Southern High Plains (SHP) aquifer, Texas, relative to those in other semiarid, oxidizing systems. Elevated groundwater As levels are widespread in the southern part of the SHP (SHP-S) aquifer, with 47% of wells exceeding the current EPA maximum contaminant level (MCL) of 10 μg/L (range 0.3–164 μg/L), whereas As levels are much lower in the north (SHP-N: 9%  As MCL of 10 μg/L; range 0.2–43 μg/L). The sharp contrast in As levels between the north and south coincides with a change in total dissolved solids (TDS) from 395 mg/L (median north) to 885 mg/L (median south). Arsenic is present as arsenate (As V) in this oxidizing system and is correlated with groundwater TDS (Spearman’s ρ = 0.57). The most likely current source of As is sorbed As onto hydrous metal oxides based on correlations between As and other oxyanion-forming elements (V, ρ = 0.88; Se, ρ = 0.54; B, ρ = 0.51 and Mo, ρ = 0.46). This source is similar to that in other oxidizing systems and constitutes a secondary source; the most likely primary source being volcanic ashes in the SHP aquifer or original source rocks in the Rockies, based on co-occurrence of As and F (ρ = 0.56), oxyanion-forming elements and SiO₂ (ρ = 0.41), which are found in volcanic ashes. High groundwater As concentrations in some semiarid oxidizing systems are related to high evaporation. Although correlation of As with TDS in the SHP aquifer may suggest evaporative concentration, unenriched stable isotopes (δ²H: −65 to −27; δ¹⁸O: −9.1 to −4.2) in the SHP aquifer do not support evaporation. High TDS in the SHP aquifer is most likely related to upward movement of saline water from the underlying Triassic Dockum aquifer. Mobilization of As in other semiarid oxidizing systems is caused by increased pH; however, pH in the SHP aquifer is near neutral (10–90 percentiles, 7.0–7.6). Although many processes, such as competitive desorption with SiO₂, VO₄, or PO₄, could be responsible for local mobilization of As in the SHP aquifer, the most plausible explanation for the regional As distribution and correlation with TDS is the counterion effect caused by a change from Ca- to Na-rich, water as shown by the high correlation between As and Na/(Ca)^0.5 ratios (ρ = 0.57). This change in chemistry is related to mixing with saline water that moves upward from the underlying Dockum aquifer. This counterion effect may mobilize other anions and oxyanion-forming elements that are correlated with As (F, V, Se, B, Mo and SiO₂). Competition among the oxyanions for sorption sites may enhance As mobilization. The SHP case study has similar As sources to those of other semiarid, oxidizing systems (original volcanic ash source followed by sorption onto hydrous metal oxides) but contrasts with these systems by showing lack of evaporative concentration and pH mobilization of As but counterion mobilization of As instead in the SHP-S aquifer.     

Organic carbon mobilization in a Bangladesh aquifer explained by seasonal monsoon-driven storativity changes

Currently, the most widely accepted hypothesis to explain high As concentrations in Bangladesh groundwaters is that dissolved organic C (DOC) reduces solid Fe (hydr)oxides and mobilizes sorbed arsenate. The nature of the DOC and its release mechanism are still controversial. Based on weekly to biweekly sampling over the course of one monsoon cycle at six monitoring wells of different depths, it is proposed that storativity changes drive natural DOC release from clay–peat layers to the adjacent aquifers. With a decrease in hydraulic heads during the dry season, total mineralization and DOC concentrations increased. With the onset of the rainy season and an increase in hydraulic heads, release of clay–peat derived components stopped and vertical water displacement due to groundwater recharge from rainwater occurred, causing aquifer flushing and a decrease in total mineralization and DOC concentrations. Total As and DOC concentrations correlated over depth. However, at the depth of maximum concentrations, the As peak was observed during the rainy season. At present, the reason for this inverse seasonal trend between As and DOC is unclear. Higher mineralization or DOC concentrations could lead to increased As sorption or the increased arsenite release is a time-lag abiotic or microbial response to the DOC peak. The vulnerability of the Pleistocene aquifer towards increased As concentrations was found to be much higher than previously assumed. Though sorption capacities were determined to be higher than in the Holocene aquifer, probably due to intact Fe (hydr)oxides, long-term continuous As input from overlying clay and peat layers by the proposed seasonal storativity changes has led to increased aqueous As concentrations of 85 μg/L, considerably higher than drinking water standards. Until now, aquifer and especially aquitard and aquiclude hydraulics have not been considered sufficiently when attempting to explain As mobilization in Bangladesh.     

Natural salinity sources in the groundwaters of Jordan—Importance of sustainable aquifer management

In recent years, voices in Jordan became lauder to exploit the fresh to brackish deep groundwater overlain by fresh groundwater bodies. In this article the implications of such a policy on the existing fresh water bodies are worked out through studying the sources of salinity in the different aquifer systems and the potentials of salinity mobilization by artificial changes in the hydrodynamic regimes. It is concluded that extracting the groundwater of deep aquifers overlain by fresh water bodies, whether the deep groundwater is fresh to brackish, brackish or salty, is equivalent to extracting groundwater from the overlying fresh groundwater bodies because of the hydraulic connections of the deep and the shallow aquifers’ groundwaters. The consequences are even more complicated and severe because exploiting the deep groundwater containing brackish or salty water will lead to refilling by fresh groundwater leaking from the overlying aquifers. The leaking water becomes salinized as soon as it enters the pore spaces of the emptied deep aquifer matrix and by mixing with the deep aquifer brackish or saline groundwater. Therefore, the move to exploit the deep groundwater is misleading and damaging the aquifers and is unjust to future generation's rights in the natural wealth of Jordan or any other country with similar aquifers’ set-up. In addition, desalination produces brines with high salinity which cannot easily be discharged in the highlands of Jordan (with only very limited access to the open sea) because they will on the long term percolate down into fresh water aquifers.