大同盆地地下水中砷活化机理同位素地球化学研究

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英文题名：Isotope Geochemical Studies on Arsenic Mobilization in Groundwater in Datong Basin 作者：李梦娣 论文级别：博士 学科专业名称：地下水科学与工程 中文关键词：砷 ; 同位素 ; 生物地球化学过程 ; 氧化还原 ; 大同盆地 英文关键词：Arsenic ; isotope ; biogeochemical processes ; redox ; Datong Basin 学位年度：2013 导师：王焰新 学科代码：081501 学位授予单位：中国地质大学 论文提交日期：2013-09-01

摘要

地下水饮用水源中高含量的砷(As)的毒性已经引起全球范围关注。在本次研究的大同盆地,全新世含水层中天然成因的砷破坏了居民安全饮用水的长期供应。世界范围的学者针对天然环境中砷的迁移转化提出了多种不同的机制,以及详细的砷地球化学行为的反应模型。含水层的地质属性控制的氧化还原条件,金属氧化物/氢氧化物和相关的生物地球化学过程,决定性地影响着地下水中砷的浓度。最近,人为活动因素,如农业灌溉,对地下水系统中砷的富集的影响引起了越来越多的重视。
     本论文研究主体旨在揭示大同盆地地地下水系统中砷的含量,以及水文,地球化学和生物地球化学过程对砷迁移的影响。综合同位素学以及地下水水文地球化学揭示了氧化还原反应,吸附/解吸,和生物地球化学过程的主要控制因素。解译变量包括氧同位素(δ18O-H2O)和氢同位素(δD和3H),硝酸盐氮同位素(δ15N-NO3),硫酸盐和硫化物的硫同位素(δ34S-SO4和δ34S-sulfide),硫酸氧同位素(δ18O-SO4)和钼同位素(δ98/95Mo)。结果表明,多同位素综合研究可有效地揭示氧化还原条件变化和伴随的氧化还原反应引起的砷的释放和固定。
     依据地下水的水化特征,大同盆地地下水可分为四个主要类型：Na-HCO3水,Ca+Mg-HCO3水,Na-Cl和Na-Cl+SO4水。调查揭示了局部和区域尺度的地下水成分的变化特点,来自边山补给区的地下水(主要为Ca+Mg-HCO3型水)中砷的浓度水平普遍较低,而Na-HCO,水中砷含量显著。地下水地球化学的另一个显著的特征是,Mg2+浓度普遍较高,尤其在盆地中心地下水中。Mg富集被认为是矿物风化(如白云石、菱镁矿),人为输入(如化肥)和微生物的活动(如细菌作用的硫酸根还原)的综合作用。大同盆地沉积物中富含有机质,旺盛的细菌代谢过程影响着含水层中主要溶质,包括Mg, Ca, SO4, HCO3的含量。相比盐渍化过程,氧化还原条件对地下水中砷的富集有着更加决定性的作用。地下水中砷与氯没有发现明显的相关性。由此进一步推断,蒸发作用对砷的迁移不存在控制性的影响。富砷地下水中氧化还原指标测定表明砷上要富集在还原性环境中。地下水中检测到的S2-和NH4+可作为微生物活动的信号,如细菌作用的硫酸盐还原和反硝化过程。硫酸根还原作用引起的砷的迁移和固定可能同时存在于含水层中,而这两个进程的优先级被由Fe2+和S2-浓度决定。因为相关的硫化物溶解度的控制其与砷的共沉淀过程。
     水同位素(δ18O-H2O和δD)比值揭示了大同盆地地下水的降水来源。δ18O和δD相对于当地降水线的偏移是由孔隙水蒸发,垂直补给以及地下水的混合的综合作用导致。深层地地下水相对均一的δ18O值反映沿着地下水流径的混合作用。地下水同位素组成上要控制因素有：(1)降雨；(2)蒸发作用;(3)与不同同位素组成的灌溉回水的混合作用。
     老的深层地下水从深层含水层被抽取出并与相对年轻的地下水混合导致了地下水中氚浓度与深度的非相关关系。砷浓度在不同年龄的地下水中跨度较大。地下水滞留年龄与砷的富集没有直接的关联。但是比较而言,年轻的地下水中砷的浓度相对较高。通过从不同深度地下水氚浓度的解译,不同年龄和不同砷浓度的的灌溉地下水之间的混合过程对含水层中砷的分布有着重大影响。
     微生物的代谢过程涉及许多重要的地球化学过程,包括氧化/还原反应,沉淀/溶解和吸附/解吸过程,这些过程都能显著的影响砷的地球化学的命运。为了揭示氮循环过程对砷的影响,对地下水中硝酸盐氮同位素(δ15N-N03)进行了检测。氮同位素研究表明地下水中较高的615N-N03值(高达+28‰)可能来源于动物粪便的点输入。奶牛及羊畜牧业是大同盆地重要产业。硝酸盐浓度和δ15N-N03比值之间的负相关关系表明氮同位素明显经历了显著的反硝化过程作用所致同位素分馏。在一定条件下,含水层中反硝化过程可以由黄铁矿氧化驱动。反硝化引起的铁的(氢)氧化物转化(氧化/还原溶解),可促进吸附在其表而的砷向地下水中的释放。大同盆地地下水中,砷的浓度与(δ15,N-N03存在不明显的的正相关关系,表明反硝化过程及其引起的铁的化合物的溶解会引起砷在地下水中的富集。
     为了更好地理解硫的生物地球化学循环的对砷迁移的影响,对地下水中硫酸盐和硫化物的同位素特征进行了分析。大同盆地地下水中硫酸根高δ34S-S04比值伴随着高的δ18O-s04值可能来源于细菌参与的硫酸盐还原生物硫循环(BSR)和BSR中间产物的再氧化。相对高的δ34S值表明地下水中的硫酸根不太可能来源于硫化物氧化。另一方而,碳酸盐+硫酸盐(CAS)蒸发盐可能为潜在的硫酸根源。普遍偏高的δ18O-so4值,偏离于CAS蒸发和肥料的氧同位素值,可能源于来自氮循环中的硝化、反硝化和硫化物的氧化过程,将较高的δt8O大气中的氧纳入S042-。不同δ34S-So4和δ18O-so4值的灌溉水的混合也在地下水硫酸盐同位素组成控制起着重要作用。较大的硫同位素分馏Δ34Ssulfide-S04与砷的浓度成正相关。含水层沉积物中砷释放到地下水的机制过程可以解释为：由BSR产生的硫化物氧化与反硝化过程相互影响；NO3-消耗导致铁的(氢)氧化物的还原溶解(例如,针铁矿)进而释放吸附的砷。
     本研究首次报道了地下水中溶解Mo同位素组成((δ98/95Mo)。大同盆地地下水中钼同位素范围为-0.12‰～+2.17%o,平均比值为+1.1‰。桑干河水中(δ98Mo(+0.72‰)与文献记录的平均河流δ98Mo值相当。相比于静海相环境,地下水中的硫化物浓度显著偏低。然而,S2-检测结果显示Mo-Fe-S化合物可能缓慢形成于特定条件下,这可能会导致可以别的钼同位素分馏。S2-和δ08Mo呈现出正相关,原因可能由于在一些地下水环境中,轻Mo同位素优先沉淀形成的钼的硫化物导致溶液中的钼同位素升高。相比于锰,地下水中δ98Mo与铁的相关性更紧密。地下水δ98Mo比值的增加并伴随着钼含量的降低可能是由于铁化合物的还原溶解及对钼的再吸附循环过程。砷浓度与δ98Mo比值呈现出弱正相关,表明铁的还原溶解导致砷为释放到地下水中,而钼同位素分馏可以作为此过程的间接指示。此外,根据钼同位素分析,本论文提出了一个新的砷活化机制：由于砷和钼具有相似的形成条件,钼在硫化物的共沉淀过程中与砷形成竞争,从而促进砷向地下水中的释放。
Elevated levels of arsenic (As) in groundwater has caused worldwide attention due to the risk of As toxicity from drinking water sources. In Datong Basin for this study, naturally occurring arsenic (As) in Holocene aquifers has undermined the success of supplying the residents with safe drinking water. Diverse mechanisms governing arsenic mobilization in natural environments have been scrutinized by worldwide scholars to contribute profound perspectives and detailed reacting models of arsenic geochemical behavior. As concentrations in groundwater is predominantly managed by the redox conditions, presence of metal oxides/hydroxides and related biogeochemical processes, which are governed by the geological attributes of the aquifers. More recently, anthropogenic influences, such as agricultural irrigation, has caught increasingly greater attention to the As enrichment in groundwater systems.
     The research work contained within this dissertation serves to shed light onto the occurrence of high levels of As and the hydrogeological. geochemical and biogeochemical processes which affect As mobility within groundwater system in Datong Basin. An integrated approach by combining multiple isotopes with hydrogeochemistry of groundwater was tested to improve the understanding of governing redox reactions and adsorption/desorption as well as biogeochemical process. The explanatory variables included oxygen isotope (δ18O-H2O) and hdrogen isotopes (δD and3H), nitrogen isotope of nitrate (δ15N-NO3), sulfur isotopes of sulfate and sulfide (δ34S-SO4and δ34S-Sulfide), oxygen isotope of sulfate (δ18O-SO4) and molybdenum isotope (δ98Mo). Integrated interpretation of multiple isotopes proves to be useful to provide effective evidences about As release and sequestration resulting from shifts in redox conditions and subsequent redox reactions.
     Detailed investigation on the hydrogeochemistry of groundwater in Datong basin indicates that the groundwater can be divided into four main groundwater types:Na-HCO3water, Ca+Mg-HCO3water. Na-Cl water and Na-Cl+SO4water. The study reveals that the local and regional scale variations in groundwater composition, and the levels of As concentrations are generally low in the groundwater abstracted from the basin's marginal areas where Ca+Mg-HCC3water prevails. High As groundwater is commonly Na-HCO3water. Another remarkable characteristic of the groundwater geochemistry is that the Mg2-concentration is commonly high, especially that in the central basin. The Mg enrichment was considered as a result of coupled processes of minerals weathering (such as dolomite and magnesites). anthropogenic (such as fertilizer application) and microbial activities (such as BSR). In the organic rich sediment in Datong Basin, major chemicals including Mg2+,Ca2+,SO42-and HCO3-contents relied on vigorous bacterial metabolisms. As enrichment was revealed fatally related to the redox conditions in groundwater other than the salinization process since no clear correlation was observed between As and CI'. To enlarge this sequitur, evapotranspiration may not be a significant controlling factor of As mobilization. Redox proxies determinations from the arsenic enriched groundwaters indicated that high arsenic groundwater mainly occurs in the reducing environment. Detectable S2-and NH4+in groundwater were further considered as markers for the contribution of bacteria such as sulfate reducing bacteria and denitrifying bacteria. Both As mobilization and immobilization caused by BSR were present in the aquifer in Datong Basin, while the priority of these processes was circumstantially controlled by the Fe2+and S2-concentrations which were related to the Fe-sulfides solubilities.
     Water isotope (δ18O-H2O and δD) data indicate a local precipitation origin of groundwater. Shifting of δ18O and δD apart from the LMWL was proposed as a result of the mixing of direct vertical recharge and evaporation of shallow groundwater which can lead to a parallel shift away from the LMWL. The relatively homogenized δ18O values in deep groundwater reflect the effect of mixing of groundwater along the flow path. The primary factors affecting groundwater isotopic compositions are:(1) precipitation;(2) evapotranspiration;(3) mixing of groundwaters with various isotopes signatures with irrigation return water. Non-linear correlation between tritium concentration (3H) and depth might result from pumping of aged deep groundwaters from deep aquifers. Generally, arsenic concentrations in groundwaters with different ages ranged widely. Groundwater residence time showed neglectful control on arsenic enrichment. Relatively higher As contents occurred in the young groundwaters. As interpreted by the3H concentrations of groundwater from different depths, mixing of irrigation groundwaters with various ages and As concentrations played important role in arsenic distribution in the aquifer.
     Microorganisms' metabolisms involve many important geochemical processes including reduction/oxidation, precipitation/dissolution, and adsorption/desorption which significantly modify the geochemical fate of As. To gain insights into nitrogen cycling influencing arsenic mobility, nitrogen isotope of nitrate (δ15N-NO3) was detected. Nitrogen isotope investigation suggested that the highest δ15N-NO3values in groundwater (up to+28.0%o) might be contributed from point input of animal manure since cow and sheep husbandry are important industries in Datong basin. Negatively correlated nitrate concentration and δ15N-NO3ratio suggested that N isotope of nitrate has experienced significant isotopic fractionation from denitrification. Pyrite oxidation driving denitrification might be present in the aquifer. Co-precipitated As onto the Fe-oxyhydroxides might desorbed into groundwater due to Fe transformations during denitrification process. The weak positive correlation between As and δ15N-NO3ratio within the groundwaters carrying moderate δ15N-NO3values was consistent with this assumption.
     In an effort to better understand sulfur biogeochemical cycling affecting As mobilization, isotope signatures of dissolved sulfate and sulfide were analyzed. High δ34S-SO4, along with elevated δ18O-SO4of dissolved sulfate in groundwater in Datong Basin was considered to result from biological sulfur cycling of bacteria sulfate reduction (BSR) and re-oxidation of sulfide and the intermediates produced by BSR. Relatively high δ34S-Sulfide values excluded the sulfate contribution from sulfide oxidation. On the other hand, CAS evaporites were proposed to be a potential sulfate source. High δ18O-SO4values, which deviated from both CAS evaporites and fertilizers, may derive from nitrogen cycling involving nitrification, denitrification and sulfide oxidation, as atmospheric oxygen with comparatively high δ18O was incorporated into SO42-Mixing of irrigation water with different δ34S-SO4and δ18O-SO4values may also play important roles in governing isotopic compositions of sulfate in groundwater. Larger sulfur isotope fractionations△34SSulfide-SO4are associated with high As concentrations. Mechanisms of As release from the aquifer sediments into groundwater could be explained as:oxidation of sulfide produced by BSR could fuel denitrification; with the consumption of NO3-, reductive dissolution of Fe-oxyhydroxides (e.g., goethite) was facilitated; consequently, arsenic was desorbed into groundwater.
     An effort was made for the first time to validate the correlation between As concentration and Mo isotope of groundwater. Isotopic composition of dissolved Mo in groundwater (δ98/95Mo) was first reported in this study, ranging from-0.12‰to+2.17‰. with an average ratio of+1.1‰, displaying a relatively heavier ratios than those in freshwaters. Sanggan River was detected with a comparable δ98Mo ratio of+0.72‰to the documented mean riverine898Mo value of+0.7‰. Compared to the euxinic environment, sulfide concentrations in groundwater were significantly lower. However, S2-measured data demonstrated that a slowed formation of Mo-Fe-S might take place in Datong Basin, which might cause notable Mo fractionation. The partially positively correlated S2-and δ98Mo in some groundwaters might result from the preferential precipitation of light Mo by the formation of thiomolybdates.δ98Mo in groundwater was more related to Fe than Mn. The elevated δ98Mo in groundwater accompanied with progressive Mo decrease was considered as a consequence of reductive ferrihydrite dissolution and re-adsorption of Mo. This process is depicted as re-adsorption of isotopically light Mo from the groundwater. Arsenic concentration was found weakly positively correlated with δ98Mo ratio in Datong Basin, indicating that large Mo fractionation resulted from reductive dissolution of Fe oxyhydroxides could be used as a signal of As release into groundwater. In addition, a new mechanism controlling arsenic mobility was proposed in this study, based on the results of Mo isotopic data interpretation:Mo played as a competitor with As in co-precipitation with Fe-sulfides. The similarity of formation conditions for As-Fe-S and Mo-Fe-S could be delineated as the dynamo of this mechanism.

引文

[1]. Dilda, PJ and PJ Hogg, Arsenical-based cancer drugs. Cancer Treatment Reviews,2007.33(6): p.542-564.
    [2]. Sinha, D, J Biswas, and A Bishayee, Nrf2-mediated redox signaling in arsenic carcinogenesis: a review. Archives of Toxicology',2013.87(2):p.383-396.
    [3]. Tchounwou, PB, JA Centeno, and AK Patlolla, Arsenic toxicity, mutagenesis, and carcinogenesis a health risk assessment and management approach. Molecular and Cellular Biochemistry,2004.255(1-2):p.47-55.
    [4]. WHO, Guidelines for Drinking Water Quality, WHO, Editor 2004, WHO Press:Switzerland. p. 145-196.
    [5]. Smedley, PL, DG Kinniburgh, DMJ Macdonald, et al., Arsenic associations in sediments from the loess aquifer of La Pampa, Argentina Applied Geochemistry,2005.20(5):p.989-1016.
    [6]. Bibi, MH, F Ahmed, and H Ishiga, Geochemical study of arsenic concentrations in groundwater of the Meghna River Delta, Bangladesh. Journal of Geochemical Exploration, 2008.97(2-3):p.43-58.
    [7]. Kim, YT, HO Yoon, C Yoon, et al., Arsenic species in ecosystems affected by arsenic-rich spring water near an abandoned mine in Korea Environmental Pollution,2009.157(12):p. 3495-3501.
    [8]. Yoshizuka, K, S Nishihama, and H Sato, Analytical survey of arsenic in geothermal waters from sites in Kyushu, Japan, and a method for removing arsenic using magnetite. Environmental Geochemistry and Health,2010.32(4):p.297-302.
    [9]. Thakur, JK, RK Thakur, AL Ramanathan, et al., Arsenic Contamination of Groundwater in Nepal-An Overview. Water,2011.3(1):p.1-20.
    [10]. Casentini, B, SJ Hug, and NP Nikolaidis, Arsenic accumulation in irrigated agricultural soils in Northern Greece. Science of the Total Environment,2011.409(22):p.4802-4810.
    [11]. Aiuppa, A, W D'Alessandro, C Federico, et al., The aquatic geochemistry of arsenic in volcanic groundwaters from southern Italy. Applied Geochemistry,2003.18(9):p.1283-1296.
    [12]. Bundschuh, J, MI Litter, F Parvez, et al., One century of arsenic exposure in Latin America:A review of history and occurrence from 14 countries. Science of the Total Environment,2012. 429:p.2-35.
    [13]. He, J and L Charlet, A review of arsenic presence in China drinking water. Journal of Hydrology,2013.492:p.79-88.
    [14]. Rodriguez-Lado, L, G Sun, M Berg, et al., Groundwater Arsenic Contamination Throughout China Science,2013.341(6148):p.866-868.
    [15]. Cullen, WR and KJ Reimer, Arsenic Speciation in the Environment. Chemical Reviews,1989. 89(4):p.713-764.
    [16]. Simon, S, H Tran, F Pannier, et al., Simultaneous determination of twelve inorganic and organic arsenic compounds by liquid chromatography-ultraviolet irradiation-hydride generation atomic fluorescence spectrometry. Journal of Chromatography A,2004.1024(1-2): p.105-113.
    [17]. Terlecka, E, Arsenic speciation analysis in water samples:A review of the hyphenated techniques. Environmental Monitoring and Assessment,2005.107(1-3):p.259-284.
    [18]. Komorowicz, I and D Baralkiewicz, Arsenic and its speciation in water samples by high performance liquid chromatography inductively coupled plasma mass spectrometry-Last decade review. Talanta,2011.84(2):p.247-261.
    [19]. Burguera, M and JL Burguera, Analytical methodology for speciation of arsenic in environmental and biological samples. Talanta,1997.44(9):p.1581-1604.
    [20]. Latva, S, M Hurtta, S Peraniemi, et al., Separation of arsenic species in aqueous solutions and optimization of determination by graphite furnace atomic absorption spectrometry. Analytica Chimica Acta,2000.418(1):p.11-17.
    [21]. Fitz, WJ and WW Wenzel, Arsenic transformations in the soil-rhizosphere-plant system: fundamentals and potential application to phytoremediation. Journal of Biotechnology,2002. 99(3):p.259-278.
    [22]. Baig, JA, TG Kazi, AQ Shah, et al., Speciation and evaluation of Arsenic in surface water and groundwater samples:A multivariate case study. Ecotoxicology and Environmental Safety, 2010.73(5):p.914-923.
    [23]. Marin, AR, PH Masscheleyn, and WH Patrick, The Influence of Chemical Form and Concentration of Arsenic on Rice Growth and Tissue Arsenic Concentration. Plant and Soil, 1992.139(2):p.175-183.
    [24]. Meharg, AA and J Hartley-Whitaker, Arsenic uptake and metabolism in arsenic resistant and nonresistant plant species. New Phytologist,2002.154(1):p.29-43.
    [25]. Abedin, MJ, J Feldmann, and AA Meharg, Uptake kinetics of arsenic species in rice plants. Plant Physiology,2002.128(3):p.1120-1128.
    [26]. Abernathy, CO, YP Liu, D Longfellow, et al., Arsenic:Health effects, mechanisms of actions, and research issues. Environmental Health Perspectives,1999.107(7):p.593-597.
    [27]. Lubin, JH, LEB Freeman, and KP Cantor, Inorganic arsenic in drinking water:An evolving public health concern. Journal of the National Cancer Institute,2007.99(12):p.906-907.
    [28]. Smith, AH and CM Steinmaus, Health Effects of Arsenic and Chromium in Drinking Water: Recent Human Findings, Annual Review of Public Health.2009. p.107-122.
    [29]. Ng, JC, JP Wang, and A Shraim, A global health problem caused by arsenic from natural sources. Chemosphere,2003.52(9):p.1353-1359.
    [30]. Halim, MA, RK Majumder, SA Nessa, et al., Groundwater contamination with arsenic in Sherajdikhan, Bangladesh:geochemical and hydrological implications. Environmental Geology,2009.58(1):p.73-84.
    [31]. Kim, Y and B-K Lee, Association between urinary arsenic and diabetes mellitus in the Korean general population according to KNH ANES 2008. Science of the Total Environment,2011. 409(19):p.4054-4062.
    [32]. Smith, AH, C Hopenhaynrich, MN Bates, et al., CANCER RISKS FROM ARSENIC IN DRINKING-WATER. Environmental Health Perspectives,1992.97:p.259-267.
    [33]. Mead, MN, Arsenic:In search of an antidote to a global poison. Environmental Health Perspectives,2005.113(6):p. A378-A386.
    [34]. Navas-Acien, A, EK Silbergeld, R Pastor-Barriuso, et al., Arsenic exposure and prevalence of type 2 diabetes in US adults. Jama-Journal of the American Medical Association,2008.300(7): p.814-822.
    [35]. Kozul, CD, KH Ely, RI Enelow, et al., Low-Dose Arsenic Compromises the Immune Response to Influenza A Infection in Vivo. Environmental Health Perspectives,2009.117(9):p. 1441-1447.
    [36]. Chen, KP, HY Wu, and TC Wu, Epidemiologic studies on Blackfoot Disease (BFD) in Taiwan 3:physicochemical characteristics of drinking water in endemic BFD areas. Mem Coll Med Nat Taiwan Univ 1962.8:p.115-29.
    [37]. De Vizcaya-Ruiz, A, O Barbier, R Ruiz-Ramos, et al., Biomarkers of oxidative stress and damage in human populations exposed to arsenic. Mutation Research-Genetic Toxicology and Environmental Mutagenesis,2009.674(1-2):p.85-92.
    [38]. Rahman, MM, JC Ng, and R Naidu, Chronic exposure of arsenic via drinking water and its adverse health impacts on humans. Environmental Geochemistry and Health,2009.31:p. 189-200.
    [39]. States, JC, S Srivastava, Y Chen, et al., Arsenic and Cardiovascular Disease. Toxicological Sciences,2009.107(2):p.312-323.
    [40]. Mandal, BK, Y Ogra, and KT Suzuki, Identification of dimethylarsinous and monomethylarsonous acids in human urine of the arsenic-affected areas in West Bengal, India. Chemical Research in Toxicology,2001.14(4):p.371-378.
    [41]. Marchiset-Ferlay, N, C Savanovitch, and MP Sauvant-Rochat, What is the best biomarker to assess arsenic exposure via drinking water? Environment International,2012.39(1):p. 150-171.
    [42]. Hopenhayn-Rich, C, SR Browning, I Hertz-Picciotto, et al.. Chronic arsenic exposure and risk of infant mortality in two areas of Chile. Environmental Health Perspectives,2000.108(7):p. 667-673.
    [43]. Hopenhayn, C, B Huang, J Christian, et al., Profile of urinary arsenic metabolites during pregnancy. Environmental Health Perspectives,2003.111(16):p.1888-1891.
    [44]. Hopenhayn, C, C Ferreccio, SR Browning, et al., Arsenic exposure from drinking water and birth weight. Epidemiology,2003.14(5):p.593-602.
    [45]. McClintock, TR, Y Chen, J Bundschuh, et al., Arsenic exposure in Latin America:Biomarkers, risk assessments and related health effects. Science of the Total Environment,2012.429:p. 76-91.
    [46]. Mondal, D. M Banerjee. M Kundu, et al., Comparison of drinking water, raw rice and cooking of rice as arsenic exposure routes in three contrasting areas of West Bengal, India. Environmental Geochemistry and Health,2010.32(6):p.463-477.
    [47]. Nordstrom, DK, Public health-Worldwide occurrences of arsenic in ground water. Science, 2002.296(5576):p.2143-2145.
    [48]. Wade, TJ, Y Xia, K Wu, et al., Increased Mortality Associated with Weil-Water Arsenic Exposure in Inner Mongolia, China. International Journal of Environmental Research and Public Health,2009.6(3):p.1107-1123.
    [49]. Argos, M, T Kalra, PJ Rathouz, et al., Arsenic exposure from drinking water, and all-cause and chronic-disease mortalities in Bangladesh (HEALS):a prospective cohort study. Lancet,2010. 376(9737):p.252-258.
    [50]. Ahsan, H, Y Chen, F Parvez, et al., Health Effects of Arsenic Longitudinal Study (HEALS): Description of a multidisciplinary epidemiologic investigation. Journal of Exposure Science and Environmental Epidemiology,2006.16(2):p.191-205.
    [51]. Meacher, DM, DB Menzel, MD Dillencourt, et al., Estimation of multimedia inorganic arsenic intake in the US population. Human and Ecological Risk Assessment,2002.8(7):p. 1697-1721.
    [52]. Schoof, RA, LJ Yost, E Crecelius, et al., Dietary arsenic intake in Taiwanese districts with elevated arsenic in drinking water. Human and Ecological Risk Assessment,1998.4(1):p. 117-135.
    [53]. Zhao, FJ, YG Zhu, and AA Meharg, Methylated Arsenic Species in Rice:Geographical Variation, Origin, and Uptake Mechanisms. Environmental Science & Technology,2013.47(9): p.3957-3966.
    [54]. Sahoo, PK and K Kim, A review of the arsenic concentration in paddy rice from the perspective of geoscience. Geosciences Journal,2013.17(1):p.107-122.
    [55]. Li, G, GX Sun, PN Williams, et al., Inorganic arsenic in Chinese food and its cancer risk. Environment International,2011.37(7):p.1219-1225.
    [56]. 李筱薇,高俊全,王永芳,et al.,2000年中国总膳食研究—膳食砷摄入量.卫生研究,2006(01)：p.63-66.
    [57]. Meharg, AA, PN Williams, E Adomako, et al., Geographical Variation in Total and Inorganic Arsenic Content of Polished (White) Rice. Environmental Science & Technology,2009.43(5): p.1612-1617.
    [58]. Zavala, YJ and JM Duxbury, Arsenic in rice:I. Estimating normal levels of total arsenic in rice grain. Environmental Science & Technology,2008.42(10):p.3856-3860.
    [59]. Mondal, D and DA Polya, Rice is a major exposure route for arsenic in Chakdaha block, Nadia district, West Bengal, India:A probabilistic risk assessment. Applied Geochemistry,2008. 23(11):p.2987-2998.
    [60]. Islam, MR, M Jahiruddin, and S Islam, Assessment of arsenic in the water-soil-plant systems in Gangetic oodplains of Bangladesh. Asian Journal of Plant Science,2004.3:p.489-493.
    [61]. Bhattacharya, P, AC Samal, J Majumdar, et al., Accumulation of arsenic and its distribution in rice plant (Oryza sativa L.) in gangetic West Bengal, India Paddy and Water Environment, 2010.8:p.63-70.
    [62]. Sun, GX, PN Williams, AM Carey, et al., Inorganic arsenic in rice bran and its products are an order of magnitude higher than in bulk grain. Environmental Science & Technology,2008. 42(19):p.7542-7546.
    [63]. Adomako, EE, PN Williams, C Deacon, et al., Inorganic arsenic and trace elements in Ghanaian grain staples. Environmental Pollution,2011.159(10):p.2435-2442.
    [64]. Lee, JS, SW Lee, HT Chon, et al., Evaluation of human exposure to arsenic due to rice ingestion in the vicinity of abandoned Myungbong Au-Ag mine site, Korea. Journal of Geochemical Exploration,2008.96(2-3):p.231-235.
    [65]. Meharg, AA, PN Williams, E Adomako, et al., Geographical Variation in Total and Inorganic Arsenic Content of Polished (White) Rice. Environmental Science & Technology,2009.43(5): p.1612-1617.
    [66]. Williams, PN, MR Islam, EE Adomako, et al., Increase in rice grain arsenic for regions of Bangladesh irrigating paddies with elevated arsenic in groundwaters. Environmental Science & Technology,2006.40(16):p.4903-4908.
    [67]. Williams, PN, AH Price, A Raab, et al., Variation in arsenic speciation and concentration in paddy rice related to dietary exposure. Environmental Science & Technology,2005.39(15):p. 5531-5540.
    [68]. Williams, PN, A Villada, C Deacon, et al., Greatly enhanced arsenic shoot assimilation in rice leads to elevated grain levels compared to wheat and barley. Environmental Science & Technology,2007.41(19):p.6854-6859.
    [69]. Xia, YJ and J Liu, An overview on chronic arsenism via drinking water in FIR China. Toxicology,2004.198(1-3):p.25-29.
    [70]. Guo, XJ, Y Fujino, JS Chai, et al., The prevalence of subjective symptoms after exposure to arsenic in drinking water in Inner Mongolia, China. Journal of Epidemiology,2003.13(4):p. 211-215.
    [71]. Guo, H, S Yang, X Tang, et al., Groundwater geochemistry and its implications for arsenic mobilization in shallow aquifers of the Hetao Basin, Inner Mongolia Science of Total Environment,2008.393(1):p.131-44.
    [72]. Guo, H, X Tang, S Yang, et al., Effect of indigenous bacteria on geochemical behavior of arsenic in aquifer sediments from the Hetao Basin, Inner Mongolia:Evidence from sediment incubations. Applied Geochemistry,2008.23(12):p.3267-3277.
    [73]. Guo, H, B Zhang, and Y Zhang, Control of organic and iron colloids on arsenic partition and transport in high arsenic groundwaters in the Hetao basin. Inner Mongolia. Applied Geochemistry,2011.26(3):p.360-370.
    [74], Guo, HM, YX Wang, GM Shpeizer, et al., Natural occurrence of arsenic in shallow groundwater, Shanyin, Datong Basin, China. Journal of Environmental Science and Health Part a-Toxic/Hazardous Substances & Environmental Engineering,2003.38(11):p. 2565-2580.
    [75]. Xie. X, Y Wang, A Ellis, et al., Multiple isotope (O, S and C) approach elucidates the enrichment of arsenic in the groundwater from the Datong Basin, northern China. Journal of Hydrology.2013.498(0):p.103-112.
    [76]. Xie, X, TM Johnson, Y Wang, et al., Mobilization of arsenic in aquifers from the Datong Basin, China:Evidence from geochemical and iron isotopic data Chemosphere,2013.90(6):p. 1878-1884.
    [77]. Xie, XJ, YX Wang, A Ellis, et al., Delineation of groundwater flow paths using hydrochemical and strontium isotope composition:A case study in high arsenic aquifer systems of the Datong basin, northern China Journal of Hydrology,2013.476:p.87-96.
    [78]. Bian, J, J Tang, L Zhang, et al., Arsenic distribution and geological factors in the western Jilin province, China. Journal of Geochemical Exploration,2012.112:p.347-356.
    [79]. Liu, C-p, C-l Luo, Y Gao, et al., Arsenic contamination and potential health risk implications at an abandoned tungsten mine, southern China Environmental Pollution,2010.158(3):p. 820-826.
    [80]. Zhang, CS and LJ Wang, Multi-element geochemistry of sediments from the Pearl River system, China Applied Geochemistry,2001.16(9-10):p.1251-1259.
    [81]. Zhang, HH, HX Yuan, YG Hu, et al., Spatial distribution and vertical variation of arsenic in Guangdong soil profiles, China Environmental Pollution,2006.144(2):p.492-499.
    [82]. Fendorf, S, HA Michael, and A van Geen, Spatial and Temporal Variations of Groundwater Arsenic in South and Southeast Asia. Science,2010.328(5982):p.1123-1127.
    [83]. Cheng, HF, YN Hu, J Luo, et al., Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems. Journal of Hazardous Materials, 2009.165(1-3):p.13-26.
    [84]. Welch, AH, DB Westjohn, DR Helsel, et al., Arsenic in ground water of the United States: Occurrence and geochemistry. Ground Water,2000.38(4):p.589-604.
    [85]. Fernandez-Martinez, A, G Roman-Ross, GJ Cuello, et al., Arsenic uptake by gypsum and calcite:Modelling and probing by neutron and X-ray scattering. Physica B-Condensed Matter, 2006.385-86:p.935-937.
    [86]. Roman-Ross, G, GJ Cuello, X Turrillas, et al., Arsenite sorption and co-precipitation with calcite. Chemical Geology,2006.233(3-4):p.328-336.
    [87]. Xie, X, A Ellis, Y Wang, et al., Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China Science of the Total Environment,2009.407(12):p.3823-3835.
    [88]. Nordstrom, DK and G Southam, Geomicrobiology of sulfide mineral oxidation. Geomicrobiology:Interactions between Microbes and Minerals,1997.35:p.361-390.
    [89]. Nordstrom, DK and CN Alpers, Negative pH, efflorescent mineralogy, and consequences for environmental restoration at the Iron Mountain Superfund site, California Proceedings of the National Academy of Sciences of the United States of America,1999.96(7):p.3455-3462.
    [90]. Neil, CW, YJ Yang, and YS Jun, Arsenic mobilization and attenuation by mineral-water interactions:implications for managed aquifer recharge. Journal of Environmental Monitoring, 2012.14(7):p.1772-1788.
    [91]. Charlet, L and DA Polya, Arsenic in shallow, reducing groundwaters in southern Asia:An environmental health disaster. Elements,2006.2(2):p.91-96.
    [92]. Oremland, RS. TR Kulp, JS Blum, et al., A microbial arsenic cycle in a salt-saturated. extreme environment. Science,2005.308(5726):p.1305-1308.
    [93]. Yin, X, X Liu, L Sun, et al., A 1500-year record of lead, copper, arsenic, cadmium, zinc level in Antarctic seal hairs and sediments. Science of The Total Environment.2006.371(1-3):p. 252-257.
    [94]. Krachler, M, JC Zheng, D Fisher, et al., Global atmospheric As and Bi contamination preserved in 3000 year old Arctic ice. Global Biogeochemical Cycles,2009.23.
    [95]. Polizzotto, ML, BD Kocar, SG Benner, et al., Near-surface wetland sediments as a source of arsenic release to ground water in Asia Nature,2008.454(7203):p.505-508.
    [96]. Breit, G and HM Guo, Geochemistry of arsenic during low-temperature water-rock interaction Preface. Applied Geochemistry,2012.27(11):p.2157-2159.
    [97]. Violante, A and M Pigna, Competitive sorption of arsenate and phosphate on different clay minerals and soils. Soil Science Society of America Journal,2002.66(6):p.1788-1796.
    [98]. Jain, A and RH Loeppert, Effect of competing anions on the adsorption of arsenate and arsenite by ferrihydrite. Journal of Environmental Quality,2000.29(5):p.1422-1430.
    [99]. Waychunas, G, B Gilbert, and CS Kim, FUEL 67-Investigation of mercury distribution behavior in ash-free coal manufacturing process. Abstracts of Papers of the American Chemical Society,2007.233.
    [100]. Zhang, Q, L Rodriguez-Lado, CA Johnson, et al., Predicting the risk of arsenic contaminated groundwater in Shanxi Province, Northern China. Environmental Pollution,2012.165:p. 118-123.
    [101]. Li, JH and XL Qian, The Early Precambrian Crustal Evolution of Hengshan Metamorphic Terrain, North China Craton. Vol.1-116.1994:Shanxi Science and Technology Press, China. 116.
    [102]. Yang, J, Quaternary geology and geomorphology of Eastern Datong basin. Acta Sciencetiarum Naturalum Universitis Pekineis,1961.1:p.87-100.
    [103]. Guo, HM and YX Wang, Geochemical characteristics of shallow groundwater in Datong basin, northwestern China. Journal of Geochemical Exploration,2005.87(3):p.109-120.
    [104]. Zhang, Z, Hydrogeological characteristics of Cenozoic Graben basin in Shanxi platform. Hydrogeol. Eng. Geol.,1960.3:p.10-12.
    [105]. Xie, X, Y Wang, C Su, et al., Influence of irrigation practices on arsenic mobilization: Evidence from isotope composition and Cl/Br ratios in groundwater from Datong Basin, northern China. Journal of Hydrology,2012.424:p.37-47.
    [106]. Cheng, SP, LC You, YG Zhi, et al., Differentiating Pleistocene tectonically driven and climate-related fluvial incision; the Sanggan River, Datong Basin, north China Geological Magazine 2006.143(3):p.393-410.
    [107]. Wang, YX, SL Shvartsev, and CL Su. Genesis of arsenic/fluoride-enriched soda water:A case study at Datong, northern China. Applied Geochemistry.2009.24(4):p.641-649.
    [108]. Xie, XJ, A Ellis, YX Wang, et al., Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China Science of the Total Environment,2009.407(12):p.3823-3835.
    [109]. 连镜清,山西省大同盆地盐碱区农业综合开发项目可行性研究.国土与自然资源研究,1995(01)：p.16-20.
    [110]. Sun, ZY, R Ma, and YX Wang, Using Landsat data to determine land use changes in Datong basin, China Environmental Geology,2009.57(8):p.1825-1837.
    [111]. Xie, XJ, YX Wang, JX Li, et al., Hydrogeochemical and Isotopic Investigations on Groundwater Salinization in the Datong Basin, Northern China. Journal of the American Water Resources Association,2013.49(2):p.402-414.
    [112]. Wang, Y, SL Shvartsev, and C So, Genesis of arsenic/fluoride-enriched soda water:A case study at Datong, northern China Applied Geochemistry,2009.24(4):p.641-649.
    [113]. Xie, X, Y Wang, and C Su, Hydrochemical and Sediment Biomarker Evidence of the Impact of Organic Matter Biodegradation on Arsenic Mobilization in Shallow Aquifers of Datong Basin, China. Water Air and Soil Pollution,2012.223(2):p.483-498.
    [114]. Li, J, Y Wang, X Xie, et al., Hierarchical cluster analysis of arsenic and fluoride enrichments in groundwater from the Datong basin, Northern China Journal of Geochemical Exploration, 2012.118:p.77-89.
    [115]. Xie, X, Y Wang, M Duan, et al., Sediment geochemistry and arsenic mobilization in shallow aquifers of the Datong basin, northern China Environmental Geochemistry and Health,2009. 31(4):p.493-502.
    [116].王敬华,赵伦山,吴悦斌,山西山阴、应县一带砷中毒区砷的环境地球化学研究.现代地质,1998(02)：p.94-99.
    [117]. Xie, X, Y Wang, A Ellis, et al., The sources of geogenic arsenic in aquifers at Datong basin, northern China:Constraints from isotopic and geochemical data. Journal of Geochemical Exploration,2011.110(2):p.155-166.
    [118]. Wang, Y, T Ma, BN Ryzhenko, et al., Model for the formation of arsenic contamination in groundwater.1. Datong Basin, China Geochemistry International,2009.47(7):p.713-724.
    [119]. Xie, X, Y Wang, C Su, et al., Arsenic mobilization in shallow aquifers of Datong Basin: Hydrochemical and mineralogical evidences. Journal of Geochemical Exploration,2008. 98(3):p.107-115.
    [120]. Wang, Y, C Su, X Xie, et al., The genesis of high arsenic groundwater:a case study in Datong basin. Geology of China,2010.37(3):p.771-780.
    [121]. Yang, Z, J Dong, and Z Bao, EVALUATION OF PROCESSES CONTROLLING THE ENRICHMENT OF ARSENIC IN GROUNDWATER FROM THE DATONG BASIN, NORTHERN CHINA. Fresenius Environmental Bulletin,2012.21(11C):p.3489-3499.
    [122]. Harvey, CF, CH Swartz, ABM Badruzzaman, et al., Arsenic mobility and groundwater extraction in Bangladesh. Science,2002.298(5598):p.1602-1606.
    [123]. Xie, XJ, YX Wang, CL Su, et al., Effects of Recharge and Discharge on delta H-2 and delta 0-18 Composition and Chloride Concentration of High Arsenic/Fluoride Groundwater from the Datong Basin, Northern China Water Environment Research,2013.85(2):p.113-123.
    [124]. XIE, Zuoming, Y Wang, M Duan et al., Arsenic release by indigenous bacteria Bacillus cereus from aquifer sediments at Datong Basin.northern China Frontiers of Earth Science,2011.5(1): p.37-44.
    [125]. Gao, X, Y Wang, Q Hu. et al., Effects of anion competitive adsorption on arsenic enrichment in groundwater. Journal of Environmental Science and Health Part a-Toxic/Hazardous Substances & Environmental Engineering,2011.46(5):p.471-479.
    [126]. Xie, X, Y Wang, M Duan, et al., Provenance and paleoenvironment impact on arsenic accumulation in aquifer sediments from the Datong Basin, China:implications from element geochemistry, in Proceedings of the Fourteenth International Symposium on Water-Rock Interaction, Wri 14, R. Hellmann and H. Pitsch, Editors.2013. p.904-907.
    [127]. Smedley, PL and DG Kinniburgh, A review of the source, behaviour and distribution of arsenic in natural waters. Applied Geochemistry,2002.17(5):p.517-568.
    [128]. Deutsch, WJ and M Pavish, In Situ Arsenic Remediation Complicated by Carbonate. Procedia Earth and Planetary Science,2013.7(0):p.211-214.
    [129]. Neuberger, CS and GR Helz. Arsenic(Ⅲ) carbonate complexing. Applied Geochemistry,2005. 20(6):p.1218-1225.
    [130]. Chakraborty, S, F Bardelli, M Mullet, et al., Spectroscopic studies of arsenic retention onto biotite. Chemical Geology,2011.281 (1-2):p.83-92.
    [131]. Goldberg, S, Competitive adsorption of arsenate and arsenite on oxides and clay minerals. Soil Science Society of America Journal,2002.66(2):p.413-421.
    [132]. Holm, T. Effects of carbonate/bicarbonate, silica, and phosphate on arsenic sorption to hydrous ferric oxide. J. Am. Water Works Assoc,2002.94(4):p.174-181.
    [133]. Wang, S and CN Mulligan, Occurrence of arsenic contamination in Canada:sources, behavior and distribution. Science of the Total Environment,2006.366(2):p.701-721.
    [134]. Bauer, M and C Blodau, Mobilization of arsenic by dissolved organic matter from iron oxides, soils and sediments. Science of the Total Environment,2006.354(2):p.179-190.
    [135]. Bauer, M and C Blodau, Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron. Geochimica et Cosmochimica Acta,2009.73(3):p.529-542.
    [136]. Garrels, RM and FT Mackenzie, Evolution of sedimentary rocks. Vol.577.1971:Norton New York.
    [137]. Drever, Jl, The geochemistry of natural waters:surface and groundwater environments.1997.
    [138]. Adams, S, R Titus, K Pietersen. et al., Hydrochemical characteristics of aquifers near Sutherland in the Western Karoo, South Africa Journal of Hydrology,2001.241(1-2):p. 91-103.
    [139]. Warren, JK, Evaporites through time:Tectonic, climatic and eustatic controls in marine and nonmarine deposits. Earth-Science Reviews,2010.98(3-4):p.217-268.
    [140]. Warren, JK, Evaporites:sediments, resources and hydrocarbons. Vol.1035.2006:Springer Berlin.
    [141]. Visscher, PT, RP Reid, BM Bebout, et al., Formation of lithified micritic laminae in modern marine stromatolites (Bahamas):The role of sulfur cycling. American Mineralogist,1998. 83(11-12):p.1482-1493.
    [142]. Guo, H, B Zhang, Y Li, et al., Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia. Environmental Pollution,2011.159(4):p.876-883.
    [143]. Mukherjee, A, BR Scanlon, AE Fryar, et al., Solute chemistry and arsenic fate in aquifers between the Himalayan foothills and Indian craton (including central Gangetic plain): Influence of geology and geomorphology. Geochimica et Cosmochimica Acta,2012.90:p. 283-302.
    [144]. Rai, SK, SK Singh, and S Krishnaswami, Chemical weathering in the plain and peninsular sub-basins of the Ganga:Impact on major ion chemistry and elemental fluxes. Geochimica et Cosmochimica Acta,2010.74(8):p.2340-2355.
    [145]. Cronin, BT, K GUrbUz, A Hurst, et al., Vertical and lateral organization of a carbonate deep-water slope marginal to a submarine fan system, Miocene, southern Turkey. Sedimentology, 2000.47(4):p.801-824.
    [146]. Mayo, AL and MD Loucks, Solute and Isotopic Geochemistry and Ground-Water Flow in the Central Wasatch Range, Utah. Journal of Hydrology,1995.172(1-4):p.31-59.
    [147]. Wu, Y, R Versteeg, L Slater, et al., Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions. Journal of contaminant Hydrology, 2009.106(3):p.131-143.
    [148]. Jankowski, J, R Acworth, and S Shekarforoush. Reverse ion exchange in a deeply weathered porphyritic dacite fractured aquifer system, Yass. in New South Wales, Australia, In Arehord GB & Hulston. R.(eds.) Proceeding of 9th International Symposium on Water Rock Interaction, Taupo, New Zealand, Rotterdam:Balkema.1998.
    [149]. McLean, W, J Jankowski, and N Lavitt, Groundwater quality and sustainability in an alluvial aquifer, Australia Groundwater, past achievements and future challenges. A Balkema, Rotterdam,2000:p.567-573.
    [150]. Warren, J, Dolomite:occurrence, evolution and economically important associations. Earth-Science Reviews,2000.52(1-3):p.1-81.
    [151]. Sanchez-Roman, M, C Vasconcelos, T Schmid, et al., Aerobic microbial dolomite at the nanometer scale:Implications for the geologic record. Geology,2008.36(11):p.879.
    [152]. Vasconcelos, C, JA McKenzie, R Warthmann, et al., Calibration of the δ18O paleothermometer for dolomite precipitated in microbial cultures and natural environments. Geology,2005.33(4): p.317.
    [153]. Deng, S, H Dong, G Lv, et al., Microbial dolomite precipitation using sulfate reducing and halophilic bacteria:Results from Qinghai Lake, Tibetan Plateau, NW China. Chemical Geology,2010.278(3-4):p.151-159.
    [154]. Sanchez-Roman, M, JA McKenzie, A de Luca Rebello Wagener, et al., Experimentally determined biomediated Sr partition coefficient for dolomite:Significance and implication for natural dolomite. Geochimica et Cosmochimica Acta,2011.75(3):p.887-904.
    [155]. Rivadeneyra, MA, G Delgado, M Soriano, et al., Precipitation of carbonates by Nesterenkonia halobia in liquid media. Chemosphere,2000.41(4):p.617-624.
    [156]. Gussone, N, F Bohm. A Eisenhauer, et al. Calcium isotope fractionation in calcite and aragonite. Geochimica et Cosmochimica Acta,2005.69(18):p.4485-4494.
    [157]. Obst, M, JJ Dynes, JR Lawrence, et al., Precipitation of amorphous CaCO3 (aragonite-like) by cyanobacteria:A STXM study of the influence of EPS on the nucleation process. Geochimica Et Cosmochimica Acta,2009.73(14):p.4180-4198.
    [158]. Etchanchu, D and JL Probst, Evolution of the Chemical-Composition of the Garonne River Water during the Period 1971-1984. Hydrological Sciences Journal-Journal Des Sciences Hydrologiques,1988.33(3):p.243-256.
    [159]. Semhi, K, PA Suchet, N Clauer, et al., Impact of nitrogen fertilizers on the natural weathering-erosion processes and fluvial transport in the Garonne basin. Applied Geochemistry,2000.15(6):p.865-878.
    [160]. Rivett, MO, SR Buss, P Morgan, et al., Nitrate attenuation in groundwater:A review of biogeochemical controlling processes. Water Research,2008.42(16):p.4215-4232.
    [161]. Szynkiewicz, A, JC Witcher, M Modelska, et al., Anthropogenic sulfate loads in the Rio Grande, New Mexico (USA). Chemical Geology,2011.283(3-4):p.194-209.
    [162]. Murray, JW, V Grundmanis, and WM Smethie, Interstitial water chemistry in the sediments of Saanich Inlet. Geochimica et Cosmochimica Acta,1978.42(7):p.1011-1026.
    [163]. Appelo, C and D Postma, Redox processes. Geochemistry, groundwater and pollution,2005:p. 415-487.
    [164]. Savage, KS, TN Tingle, PA O'Day, et al., Arsenic speciation in pyrite and secondary weathering phases, Mother Lode Gold District, Tuolumne County, California. Applied Geochemistry,2000.15(8):p.1219-1244.
    [165]. Blanchard, M, M Alfredsson, J Brodholt, et al., Arsenic incorporation into FeS(2) pyrite and its influence on dissolution:A DFT study. Geochimica Et Cosmochimica Acta,2007.71(3):p. 624-630.
    [166]. Zhu, WY, LY Young, N Yee, et al., Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite. Geochimica Et Cosmochimica Acta,2008.72(21):p.5243-5250.
    [167]. O'Day, PA, D Vlassopoulos, R Root, et al., The influence of sulfur and iron on dissolved arsenic concentrations in the shallow subsurface under changing redox conditions. Proc Natl Acad Sci USA,2004.101(38):p.13703-8.
    [168]. Burton, ED, SG Johnston, and B Planer-Friedrich, Coupling of arsenic mobility to sulfur transformations during microbial sulfate reduction in the presence and absence of humic acid. Chemical Geology,2013.343:p.12-24.
    [169]. Kao, YH, SW Wang, CW Liu, et al., Biogeochemical cycling of arsenic in coastal salinized aquifers:Evidence from sulfur isotope study. Science of Total Environment,2011.409(22):p. 4818-30.
    [170]. Cherry, J, A Shaikh, D Tallman, et al., Arsenic species as an indicator of redox conditions in groundwater. Journal of Hydrology.1979.43(1):p.373-392.
    [171]. Holm, TR and CD Curtiss, A comparison of oxidation-reduction potentials calculated from the As (Ⅴ)/As (Ⅲ) and Fe (Ⅲ)/Fe (Ⅱ) couples with measured platinum-electrode potentials in groundwater. Journal of contaminant hydrology,1989.5(1):p.67-81.
    [172]. Mukherjee, A, AE Fryar, and WA Thomas, Geologic, geomorphic and hydrologic framework and evolution of the Bengal basin, India and Bangladesh. Journal of Asian Earth Sciences, 2009.34(3):p.227-244.
    [173]. Fendorf, S, Y Masue, B Kocar, et al., Biogeochemically induced mineral transformaitons controlling the fate of arsenic. Geochimica Et Cosmochimica Acta,2010.74(12):p. A285-A285.
    [174]. Di Benedetto, F, P Costagliola, M Benvenuti, et al., Arsenic incorporation in natural calcite lattice:evidence from electron spin echo spectroscopy. Earth and Planetary Science Letters, 2006.246(3):p.458-465.
    [175]. Horneman, A, A Van Geen, DV Kent, et al., Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part 1:Evidence from sediment profiles. Geochimica Et Cosmochimica Acta,2004.68(17):p.3459-3473.
    [176]. Liger, E, L Charlet, and P Van Cappellen, Surface catalysis of uranium (Ⅵ) reduction by iron (Ⅱ). Geochimica et Cosmochimica Acta,1999.63(19):p.2939-2955.
    [177]. Appelo, C, M Van der Weiden, C Toumassat, et al., Surface complexation of ferrous iron and carbonate on ferrihydrite and the mobilization of arsenic. Environmental Science & Technology,2002.36(14):p.3096-3103.
    [178]. Cavalcanti de Albuquerque, R, Hydrogeochemical evolution and arsenic mobilization in confined aquifers formed within glaciomarine sediments,2011, Science:Department of Earth Sciences.
    [179]. Rozanski, K, L Araguasaraguas, and R Gonfiantini, RELATION BETWEEN LONG-TERM TRENDS OF O-18 ISOTOPE COMPOSITION OF PRECIPITATION AND CLIMATE. Science,1992.258(5084):p.981-985.
    [180]. Araguas-Araguas, L, K Froehlich, and K Rozanski, Deuterium and oxygen-18 isotope composition of precipitation and atmospheric moisture. Hydrological Processes,2000.14(8): p.1341-1355.
    [181]. Jouzel, J, G Hoffmann, RD Koster, et al., Water isotopes in precipitation:data/model comparison for present-day and past climates. Quaternary Science Reviews,2000.19(1-5):p. 363-379.
    [182]. Rumble, D and TF Yui, The Qinglongshan oxygen and hydrogen isotope anomaly near Donghai in Jiangsu Province, China. Geochimica Et Cosmochimica Acta,1998.62(19-20):p. 3307-3321.
    [183]. Xing, LN, HM Guo, and YH Zhan, Groundwater hydrochemical characteristics and processes along flow paths in the North China Plain. Journal of Asian Earth Sciences,2013.70-71:p. 250-264.
    [184]. Barnes, CJ and GB Allison, TRACING OF WATER-MOVEMENT IN THE UNSATURATED ZONE USING STABLE ISOTOPES OF HYDROGEN AND OXYGEN. Journal of Hydrology,1988.100(1-3):p.143-176.
    [185]. Warner, N, Z Lgourna, L Bouchaou, et al., Integration of geochemical and isotopic tracers for elucidating water sources and salinization of shallow aquifers in the sub-Saharan Draa Basin, Morocco. Applied Geochemistry,2013.34:p.140-151.
    [186]. Wang, P, JJ Yu, YC Zhang, et al., Groundwater recharge and hydrogeochemical evolution in the Ejina Basin, northwest China Journal of Hydrology,2013.476:p.72-86.
    [187]. Jin, L, DI Siegel, LK Lautz, et al., Identifying streamflow sources during spring snowmelt using water chemistry and isotopic composition in semi-arid mountain streams. Journal of Hydrology,2012.470:p.289-301.
    [188]. Arslan, H, B Cemek, and Y Demir, Determination of Seawater Intrusion via Hydrochemicals and Isotopes in Bafra Plain, Turkey. Water Resources Management,2012.26(13):p. 3907-3922.
    [189]. Carucci, V, M Petitta, and R Aravena, Interaction between shallow and deep aquifers in the Tivoli Plain (Central Italy) enhanced by groundwater extraction:A multi-isotope approach and geochemical modeling. Applied Geochemistry,2012.27(1):p.266-280.
    [190]. Zheng, YF, B Fu, YL Xiao, et al., Hydrogen and oxygen isotope evidence for fluid-rock interactions in the stages of pre-and post-UHP metamorphism in the Dabie Mountains. Luthos, 1999.46(4):p.677-693.
    [191]. Bindeman, IN, CC Lundstrom, C Bopp, et al., Stable isotope fractionation by thermal diffusion through partially molten wet and dry silicate rocks. Earth and Planetary Science Letters,2013. 365:p.51-62.
    [192]. O'Neil, JR, Hydrogen and oxygen isotope fractionation between ice and water. The Journal of Physical Chemistry,1968.72(10):p.3683-3684.
    [193]. Lloyd, RM, Oxygen isotope enrichment of sea water by evaporation. Geochimica et Cosmochimica Acta,1966.30(8):p.801-814.
    [194]. Craig, H, L Gordon, and Y Horibe, Isotopic exchange effects in the evaporation of water:1. Low-temperature experimental results. Journal of Geophysical Research,1963.68(17):p. 5079-5087.
    [195]. Cappa, CD, MB Hendricks, DJ DePaolo, et al., Isotopic fractionation of water during evaporation. Journal of Geophysical Research,2003.108(D16):p.4525.
    [196]. O'Neil, JR and HP Taylor, The oxygen isotope and cation exchange chemistry of feldspars. American Mineralogist,1967.52:p.1414-1437.
    [197]. Clayton, RN, JR O'Neil, and TK Mayeda, Oxygen isotope exchange between quartz and water. Journal of Geophysical Research,1972.77(17):p.3057-3067.
    [198]. Bottinga, Y and M Javoy, Comments on oxygen isotope geothermometry. Earth and Planetary Science Letters,1973.20(2):p.250-265.
    [199]. Lloyd, RM, Oxygen isotope behavior in the Sulfate-Water System. Journal of Geophysical Research,1968.73(18):p.6099-6110.
    [200]. O'Neil, JR and YK Kharaka, Hydrogen and oxygen isotope exchange reactions between clay minerals and water. Geochimica et Cosmochimica Acta,1976.40(2):p.241-246.
    [201]. Buttle. J, Isotope hydrograph separations and rapid delivery of pre-event water from drainage basins. Progress in Physical Geography,1994.18(1):p.16-41.
    [202], Gazis, C and X Feng, A stable isotope study of soil water:evidence for mixing and preferential flow paths. Geoderma,2004.119(1):p.97-111.
    [203]. Sun, S-S and P Eadington, Oxygen isotope evidence for the mixing of magmatic and meteoric waters during tin mineralization in the Mole Granite, New South Wales, Australia Economic Geology,1987.82(1):p.43-52.
    [204]. Gat, JR, OXYGEN AND HYDROGEN ISOTOPES IN THE HYDROLOGIC CYCLE. Annual Review of Earth and Planetary Sciences,1996.24(1):p.225-262.
    [205]. Edmunds, WM and PL Smedley, Residence time indicators in groundwater:the East Midlands Triassic sandstone aquifer. Applied Geochemistry,2000.15(6):p.737-752.
    [206]. Maduabuchi, C, S Faye, and P Maloszewski, Isotope evidence of palaeorecharge and palaeoclimate in the deep confined aquifers of the Chad Basin, NE Nigeria Science of the Total Environment,2006.370(2-3):p.467-479.
    [207]. Stute, M, Y Zheng, P Schlosser, et al., Hydrological control of As concentrations in Bangladesh groundwater. Water Resources Research,2007.43(9).
    [208]. Klump, S, R Kipfer, OA Cirpka, et al., Groundwater Dynamics and Arsenic Mobilization in Bangladesh Assessed Using Noble Gases and Tritium. Environmental Science & Technology, 2005.40(1):p.243-250.
    [209]. Clark, I and P Fritz, Environmental isotopes in hydrology,1997, Lewis Publishers, Boca Raton, Fla.
    [210]. Craig, H and D Lal, The Production Rate of Natural Tritium. Tellus,1961.13(1):p.85-105.
    [211]. Fetter, C, Applied hydrogeology.4th,2001, Prentice Hall, Columbus, Ohio.
    [212]. IAEA/WMO, Global Network of Isotopes in Precipitation. The GNIP Database.,2007.
    [213]. Neumann, RB, AP St Vincent, LC Roberts, et al., Rice field geochemistry and hydrology:an explanation for why groundwater irrigated fields in Bangladesh are net sinks of arsenic from groundwater. Environmental Science & Technology,2011.45(6):p.2072-8.
    [214]. Yoo, S-H, W-J Choi, and GH Han, An investigation of the sources of nitrate contamination in the Kyonggi province groundwater by isotope ratios analysis of nitrogen. Korea Society of fertilizers,1999.32(1):p.47-56.
    [215]. Kendall, C, Tracing nitrogen sources and cycling in catchments. Isotope tracers in catchment hydrology,1998.1:p.519-576.
    [216]. Feast, NA, KM Hiscock, PF Dennis, et al., Nitrogen isotope hydrochemistry and denitrification within the Chalk aquifer system of north Norfolk, UK. Journal of Hydrology, 1998.211(1-4):p.233-252.
    [217]. Wells, ER and NC Krothe, Seasonal Fluctuation in Delta-N-15 of Groundwater Nitrate in a Mantled Karst Aquifer Due to Macropore Transport of Fertilizer-Derived Nitrate. Journal of Hydrology,1989.112(1-2):p.191-201.
    [218]. Flipse, WJ and FT Bonner, Nitrogen-Isotope Ratios of Nitrate in Ground-Water under Fertilized Fields, Long-Island, New-York. Ground Water,1985.23(1):p.59-67.
    [219]. Iqbal, MZ, NC Krothe, and RF Spalding, Nitrogen isotope indicators of seasonal source variability to groundwater. Environmental Geology.1997.32(3):p.210-218.
    [220]. Choi, WJ. SM Lee. HM Ro, et al., Natural N-15 abundances of maize and soil amended with urea and composted pig manure. Plant and Soil,2002.245(2):p.223-232.
    [22]. Mariotti, A, J Germon, P Hubert, et al., Experimental determination of nitrogen kinetic isotope fractionation:some principles; illustration for the denitrification and nitrification processes. Plant and soil.1981.62(3):p.413-430.
    [222]. Delwiche, CC and PL Steyn, Nitrogen isotope fractionation in soils and microbial reactions. Environmental Science & Technology,1970.4(11):p.929-935.
    [223]. Xue, DM, J Botte, B De Baets, et al., Present limitations and future prospects of stable isotope methods for nitrate source identification in surface-and groundwater. Water Research,2009. 43(5):p.1159-1170.
    [224]. Choi, E, H Park, and D Rhu, Phosphorus removal from SBR with controlled denitrification for weak sewage. Water Science and Technology,2001.43(3):p.159-165.
    [225]. Naqvi, SWA, H Naik, A Pratihary, et al., Coastal versus open-ocean denitrification in the Arabian Sea. Biogeosciences,2006.3(4):p.621-633.
    [226]. Voss, M, JW Dippner, and JP Montoya, Nitrogen isotope patterns in the oxygen-deficient waters of the Eastern Tropical North Pacific Ocean. Deep-Sea Research Part I-Oceanographic Research Papers,2001.48(8):p.1905-1921.
    [227]. Brandes, JA, NZ Boctor, GD Cody, et al., Abiotic nitrogen reduction on the early Earth. Nature, 1998.395(6700):p.365-367.
    [228]. Sigman, DM, PJ DiFiore, MP Hain, et al., Sinking organic matter spreads the nitrogen isotope signal of pelagic denitrification in the North Pacific. Geophysical Research Letters,2009.36.
    [229]. Lehmann, MF, P Reichert, SM Bernasconi, et al., Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone. Geochimica et Cosmochimica Acta,2003.67(14):p.2529-2542.
    [230]. Baker, MA, HM Valett, and CN Dahm, Organic carbon supply and metabolism in a shallow groundwater ecosystem. Ecology,2000.81(11):p.3133-3148.
    [231]. Hedin, LO, JC von Fischer, NE Ostrom, et al., Thermodynamic constraints on nitrogen transformations and other biogeochemical processes at soil-stream interfaces. Ecology,1998. 79(2):p.684-703.
    [232]. Knowles, R, Denitrification. Microbiological reviews,1982.46(1):p.43.
    [233]. Sebilo, M, G Billen, B Mayer, et al., Assessing nitrification and denitrification in the seine river and estuary using chemical and isotopic techniques. Ecosystems,2006.9(4):p.564-577.
    [234]. Fukada, T, KM Hiscock, PF Dennis, et al., A dual isotope approach to identify denitrification in groundwater at a river-bank infiltration site. Water Research,2003.37(13):p.3070-3078.
    [235]. Mayer, B, EW Boyer, C Goodale, et al., Sources of nitrate in rivers draining sixteen watersheds in the northeastern US:Isotopic constraints. Biogeochemistry,2002.57(1):p. 171-197.
    [236]. Sebilo, M, G Billen, M Grably, et al., Isotopic composition of nitrate-nitrogen as a marker of riparian and benthic denitrification at the scale of the whole Seine River system. Biogeochemistry,2003.63(1):p.35-51.
    [237]. Smith, RL, BL Howes, and JH Duff, Denitrification in Nitrate-Contaminated Groundwater-Occurrence in Steep Vertical Geochemical Gradients. Geochimica Et Cosmochimica Acta, 1991.55(7):p.1815-1825.
    [238]. Robinson, SR, Changes in the cellular distribution of glutamine synthetase in Alzheimer's disease. Journal of Neuroscience Research,2001.66(5):p.972-980.
    [239]. Mayer, B, SM Bollwerk, T Mansfeldt, et al., The oxygen isotope composition of nitrate generated by nitrification in acid forest floors. Geochimica Et Cosmochimica Acta,2001. 65(16):p.2743-2756.
    [240]. Andersson, KK and AB Hooper, O2 and H2O Are Each the Source of One O in No2- Produced from Nh3 by Nitrosomonas-N-15-Nmr Evidence. Febs Letters,1983.164(2):p.236-240.
    [241]. Aleem, M, G Hoch, and J Varner, Water as the source of oxidant and reductant in bacterial chemosynthesis. Proceedings of the National Academy of Sciences of the United States of America,1965.54(3):p.869.
    [242]. Exner, M and R Spalding, N-15 identification of nonpoint sources of nitrate contamination beneath cropland in the Nebraska Panhandle:two case studies. Applied Geochemistry,1994. 9(1):p.73-81.
    [243]. Finlay, JC, RW Sterner, and S Kumar, Isotopic evidence for in-lake production of accumulating nitrate in lake superior. Ecological Applications,2007.17(8):p.2323-2332.
    [244]. Silva, SR, C Kendall, DH Wilkison, et al., A new method for collection of nitrate from fresh water and the analysis of nitrogen and oxygen isotope ratios. Journal of Hydrology,2000. 228(1-2):p.22-36.
    [245]. Handley, L and J Raven, The use of natural abundance of nitrogen isotopes in plant physiology and ecology. Plant, Cell & Environment,1992.15(9):p.965-985.
    [246]. Min, DH, R Leep, C Kapp, et al., Effects of dairy manure application rates on herbage yield, forage quality, and soil nitrate nitrogen and phosphorus. American Forage and Grassland Council, Vol 11, Proceedings,2002.11:p.18-18.
    [247]. Wassenaar, LI, Evaluation of the origin and fate of nitrate in the Abbotsford Aquifer using the isotopes of 15N and 18O in NO3-. Applied geochemistry,1995.10(4):p.391-405.
    [248]. Kerley, SJ and SC Jarvis, Preliminary studies of the impact of excreted N on cycling and uptake of N in pasture systems using natural abundance stable isotopic discrimination. Plant andSoil,1996.178(2):p.287-294.
    [249]. Choi, WJ, SM Lee, and HM Ro, Evaluation of contamination sources of groundwater NO3-using nitrogen isotope data:A review. Geosciences Journal,2003.7(1):p.81-87.
    [250]. Heaton, T, Sources of the nitrate in phreatic groundwater in the western Kalahari. Journal of Hydrology,1984.67:p.249-259.
    [251]. Zhang, LM, HW Hu, JP Shen, et al., Ammonia-oxidizing archaea have more important role than ammonia-oxidizing bacteria in ammonia oxidation of strongly acidic soils. Isme Journal, 2012.6(5):p.1032-1045.
    [252]. Otero, N, C Torrento, A Soler, et al., Monitoring groundwater nitrate attenuation in a regional system coupling hydrogeology with multi-isotopic methods:The case of Plana de Vic (Osona, Spain). Agriculture Ecosystems & Environment,2009.133(1-2):p.103-113.
    [253]. Postma, D, Kinetics of nitrate reduction by detrital Fe (Ⅱ)-silicates. Geochimica et Cosmochimica Acta,1990.54(3):p.903-908.
    [254]. Straub, KL, M Benz, B Schink, et al., Anaerobic, nitrate-dependent microbial oxidation of ferrous iron. Applied and Environmental Microbiology,1996.62(4):p.1458-1460.
    [255]. S(?)rensen, J, Nitrate reduction in marine sediment:Pathways and interactions with iron and sulfur cycling. Geomicrobiology Journal,1987.5(3-4):p.401-421.
    [256]. Benz, M, A Brune, and B Schink, Anaerobic and aerobic oxidation of ferrous iron at neutral pH by chemoheterotrophic nitrate-reducing bacteria. Archives of Microbiology,1998.169(2): p.159-165.
    [257]. Cao, YJ, CY Tang, XF Song, et al., Characteristics of nitrate in major rivers and aquifers of the Sanjiang Plain, China Journal of Environmental Monitoring,2012.14(10):p.2624-2633.
    [258]. Yasuhiko, K, T Masanosuke, and Y Masuro, Participation of iron in denitrification in waterlogged soil. Soil Biology and Biochemistry,1978.10(1):p.21-26.
    [259]. Kulp, TR, SE Hoeft, and RS Oremland, Redox transformations of arsenic oxyanions in periphyton communities. Applied and environmental Microbiology,2004.70(11):p. 6428-6434.
    [260]. Beek, CGEM, Redox Processes Active in Denitrification, in Redox, J. Schuring, et al., Editors. 2000, Springer Berlin Heidelberg, p.152-160.
    [261]. Rhine, ED, CD Phelps, and LY Young, Anaerobic arsenite oxidation by novel denitrifying isolates. Environmental Microbiology,2006.8(5):p.899-908.
    [262]. Oremland, RS, SE Hoeft, JA Santini, et al., Anaerobic oxidation of arsenite in Mono Lake water and by facultative, arsenite-oxidizing chemoautotroph, strain MLHE-1. Applied and Environmental Microbiology,2002.68(10):p.4795-4802.
    [263]. Dowdle, PR, AM Laverman, and RS Oremland, Bacterial Dissimilatory Reduction of Arsenic (Ⅴ) to Arsenic (Ⅲ) in Anoxic Sediments. Applied and environmental microbiology,1996. 62(5):p.1664-1669.
    [264]. Bostick, BC and S Fendorf, Arsenite sorption on troilite (FeS) and pyrite (FeS2). Geochimica et Cosmochimica Acta,2003.67(5):p.909-921.
    [265]. Dellwig, O, ME Bottcher, M Lipinski, et al., Trace metals in Holocene coastal peats and their relation to pyrite formation (NW Germany). Chemical Geology,2002.182(2):p.423-442.
    [266]. Wolthers, M, L Charlet, CH Van der Weijden, et al., Arsenic mobility in the ambient sulfidic environment:Sorption of arsenic(Ⅴ) and arsenic(Ⅲ) onto disordered mackinawite. Geochimica Et Cosmochimica Acta,2005.69(14):p.3483-3492.
    [267]. Farquhar, ML. JM Charnock, FR Livens, et al., Mechanisms of arsenic uptake from aqueous solution by interaction with goethite, lepidocrocite, mackinawite. and pyrite:An X-ray absorption spectroscopy study. Environmental Science & Technology,2002.36(8):p. 1757-1762.
    [268]. Wilkin, RT and RG Ford, Arsenic solid-phase partitioning in reducing sediments of a contaminated wetland. Chemical Geology,2006.228(1-3):p.156-174.
    [269]. O'Day, PA, D Vlassopoulos, R Root, et al., The influence of sulfur and iron on dissolved arsenic concentrations in the shallow subsurface under changing redox conditions. Proceedings of the National Academy of Sciences of the United States of America,2004. 101(38):p.13703-13708.
    [270]. Sullivan, K and R Aller, Diagenetic cycling of arsenic in Amazon shelf sediments. Geochimica et Cosmochimica Acta,1996.60(9):p.1465-1477.
    [271]. Korom, SF, Natural Denitrification in the Saturated Zone-a Review. Water Resources Research,1992.28(6):p.1657-1668.
    [272]. Couture, RM and P Van Cappellen, Reassessing the role of sulfur geochemistry on arsenic speciation in reducing environments. Journal of Hazardous Materials,2011.189(3):p. 647-52.
    [273]. Burton, ED, SG Johnston, and RT Bush, Microbial sulfidogenesis in ferrihydrite-rich environments:Effects on iron mineralogy and arsenic mobility. Geochimica Et Cosmochimica Acta,2011.75(11):p.3072-3087.
    [274]. Balci, N, WC Shanks, B Mayer, et al., Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite. Geochimica Et Cosmochimica Acta, 2007.71(15):p.3796-3811.
    [275]. Canfield, DE, Isotope fractionation by natural populations of sulfate-reducing bacteria Geochimica et Cosmochimica Acta,2001.65(7):p.1117-1124.
    [276]. Bottcher, ME, B Thamdrup, and TW Vennemann, Oxygen and sulfur isotope fractionation during anaerobic bacterial disproportionation of elemental sulfur. Geochimica Et Cosmochimica Acta,2001.65(10):p.1601-1609.
    [277]. Habicht, KS, DE Canfield, and J Rethmeier, Sulfur isotope fractionation during bacterial reduction and disproportionation of thiosulfate and sulfite. Geochimica Et Cosmochimica Acta, 1998.62(15):p.2585-2595.
    [278]. Kao, Y-H, S-W Wang, SK Maji, et al., Hydrochemical, mineralogical and isotopic investigation of arsenic distribution and mobilization in the Guandu wetland of Taiwan. Journal of Hydrology,2013.498(0):p.274-286.
    [279]. Kao, YH, SW Wang, CW Liu, et al., Biogeochemical cycling of arsenic in coastal salinized aquifers:Evidence from sulfur isotope study. Science of the Total Environment,2011.409(22): p.4818-4830.
    [280]. Taylor, BE, MC Wheeler, and DK Nordstrom, Isotope Composition of Sulfate in Acid-Mine Drainage as Measure of Bacterial Oxidation. Nature,1984.308(5959):p.538-541.
    [281]. Kroopnick, P, R Weiss, and H Craig, Total CO2,13C, and dissolved oxygen-l8O at Geosecs 11 in the North Atlantic. Earth and Planetary Science Letters,1972.16(1):p.103-110.
    [282]. Lloyd, R, Oxygen isotope behavior in the sulfate-water system. Journal of Geophysical Research,1968.73(18):p.6099-6110.
    ]283]. Farquhar, J, DE Canfield, A Masterson, et al., Sulfur and oxygen isotope study of sulfate reduction in experiments with natural populations from Faellestrand, Denmark. Geochimica Et Cosmochimica Acta.2008.72(12):p.2805-2821.
    [284]. Fritz, P, GM Bashannal, RJ Drimmie, et al., Oxygen Isotope Exchange between Sulfate and Water during Bacterial Reduction of Sulfate. Chemical Geology,1989.79(2):p.99-105.
    [285]. Zumft, WG, Cell biology and molecular basis of denitrification. Microbiology and Molecular Biology Reviews,1997.61(4):p.533-616.
    [286]. Otero, N, C Torrento, A Soler, et al., Monitoring groundwater nitrate attenuation in a regional system coupling hydrogeology with multi-isotopic methods:The case of Plana de Vic (Osona, Spain). Agriculture, Ecosystems & Environment,2009.133(1):p.103-113.
    [287]. Aravena, R and WD Robertson, Use of multiple isotope tracers to evaluate denitrification in ground water:Study of nitrate from a large- flux septic system plume. Ground Water,1998. 36(6):p.975-982.
    [288]. Postma, D, C Boesen, H Kristiansen, et al., Nitrate reduction in an unconfined sandy aquifer: water chemistry, reduction processes, and geochemical modeling. Water Resources Research, 1991.27(8):p.2027-2045.
    [289]. Pauwels, H, M Pettenati, and C Greffie, The combined effect of abandoned mines and agriculture on groundwater chemistry. Journal of Contaminant Hydrology,2010.115(1-4):p. 64-78.
    [290]. Hoefs, J, Stable isotope geochemistry.2009:Springer.
    [291]. Bottrell, SH and RJ Newton, Reconstruction of changes in global sulfur cycling from marine sulfate isotopes. Earth-Science Reviews,2006.75(1-4):p.59-83.
    [292]. Vitoria, L, N Otero, A Soler, et al., Fertilizer characterization:Isotopic data (N, S, O, C, and Sr). Environmental Science & Technology,2004.38(12):p.3254-3262.
    [293]. Knoller, K, R Trettin, and G Strauch, Sulphur cycling in the drinking water catchment area of Torgau-Mockritz (Germany):insights from hydrochemical and stable isotope investigations. Hydrological Processes,2005.19(17):p.3445-3465.
    [294]. Mayer, B, P Fritz, J Prietzel, et al., The Use of Stable Sulfur and Oxygen-Isotope Ratios for Interpreting the Mobility of Sulfate in Aerobic Forest Soils. Applied Geochemistry,1995. 10(2):p.161-173.
    [295]. Thomazo, C, DL Pinti, V Busigny, et al., Biological activity and the Earth's surface evolution: Insights from carbon, sulfur, nitrogen and iron stable isotopes in the rock record. Comptes Rendus Palevol, 2009.8(7):p.665-678.
    [296]. Johnson, CA, P Emsbo. FG Poole, et al., Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits. Geochimica Et Cosmochimica Acta,2009.73(1):p.133-147.
    [297]. Habicht, KS and DE Canfield, Sulphur isotope fractionation in modern microbial mats and the evolution of the sulphur cycle. Nature,1996.382(6589):p.342-343.
    [298]. Ryu, JH, RA Zierenberg, RA Dahgren, et al., Sulfur biogeochemistry and isotopic fractionation in shallow groundwater and sediments of Owens Dry Lake, California. Chemical Geology, 2006.229(4):p.257-272.
    [299]. Philippot, P, M Van Zuilen, K Lepot, et al., Early Archaean microorganisms preferred elemental sulfur, not sulfate. Science,2007.317(5844):p.1534-1537.
    [300]. Kohl, I and HM Bao, Triple-oxygen-isotope determination of molecular oxygen incorporation in sulfate produced during abiotic pyrite oxidation (pH=2-11). Geochimica Et Cosmochimica Acta,2011.75(7):p.1785-1798.
    [301]. Ottley, CJ, W Davison, and WM Edmunds, Chemical catalysis of nitrate reduction by iron(Ⅱ). Geochimica Et Cosmochimica Acta,1997.61(9):p.1819-1828.
    [302]. Wille, M, O Nebel, MJ Van Kranendonk, et al., Mo-Cr isotope evidence for a reducing Archean atmosphere in 3.46-2.76 Ga black shales from the Pilbara, Western Australia. Chemical Geology,2013.340:p.68-76.
    [303]. Pearce, CR, AS Cohen, AL Coe, et al., Molybdenum isotope evidence for global ocean anoxia coupled with perturbations to the carbon cycle during the early Jurassic. Geology,2008.36(3):p. 231-234.
    [304]. Dahl, TW, DE Canfield, MT Rosing, et al., Molybdenum evidence for expansive sulfidic water masses in similar to 750 Ma oceans. Earth and Planetary Science Letters,2011.311(3-4):p. 264-274.
    [305]. Wille, M, JD Kramers, TF Nagler, et al., Evidence for a gradual rise of oxygen between 2.6 and 2.5 Ga from Mo isotopes and Re-PGE signatures in shales. Geochimica Et Cosmochimica Acta, 2007.71(10):p.2417-2435.
    [306]. Glass, JB, RP Axler, S Chandra, et al., Molybdenum limitation of microbial nitrogen assimilation in aquatic ecosystems and pure cultures. Frontiers in microbiology,2012.3. 10. Collier, RW, Molybdenum in the Northeast Pacific-Ocean. Limnology and Oceanography, 1985.30(6):p.1351-1354.
    [307]. Morford, JL, WR Martin, LH Kalnejais, et al., Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA. Geochimica et Cosmochimica Acta,2007.71(4):p.895-917.
    [308]. Crusius, J, S Calvert, T Pedersen, et al., Rhenium and molybdenum enrichments in sediments as indicators of oxic, suboxic and sulfidic conditions of deposition. Earth and Planetary Science Letters,1996.145(1-4):p.65-78.
    [309]. Zheng, Y, RF Anderson, A van Geen, et al., Authigenic molybdenum formation in marine sediments:A link to pore water sulfide in the Santa Barbara Basin. Geochimica Et Cosmochimica Acta,2000.64(24):p.4165-4178.
    [310]. Shimmield, GB and NB Price, The Behavior of Molybdenum and Manganese during Early Sediment Diagenesis-Offshore Baja-California, Mexico. Marine Chemistry,1986.19(3):p. 261-280.
    [311]. Kashiwabara, T, Y Takahashi, and M Tanimizu, A XAFS study on the mechanism of isotopic fractionation of molybdenum during its adsorption on ferromanganese oxides. Geochemical Journal,2009.43(6):p. E31-E36.
    [312]. Erickson, BE and GR Helz, Molybdenum(Ⅵ) speciation in sulfidic waters:Stability and lability of thiomolybdates. Geochimica Et Cosmochimica Acta,2000.64(7):p.1149-1158.
    [313]. Bostick, BC, S Fendorf, and GR Helz, Differential adsorption of molybdate and tetrathiomolybdate on pyrite (FeS2). Environmental Science & Technology,2003.37(2):p. 285-291.
    [314]. Helz, GR, TP Vorlicek, and MD Kahn, Molybdenum scavenging by iron monosulfide. Environmental Science & Technology,2004.38(16):p.4263-4268.
    [315]. Vorlicek, TP, MD Kahn, Y Kasuya, et al., Capture of molybdenum in pyrite-form ing sediments: Role of ligand-induced reduction by polysulfides. Geochimica Et Cosmochimica Acta,2004. 68(3):p.547-556.
    [316]. Helz. GR, E Bura-Nakic, N Mikac, et al., New model for molybdenum behavior in euxinic waters. Chemical Geology,2011.284(3-4):p.323-332.
    [317]. Tribovillard, N, A Riboulleau, T Lyons, et al., Enhanced trapping of molybdenum by sulfurized marine organic matter of marine origin in Mesozoic limestones and shales. Chemical Geology, 2004.213(4):p.385-401.
    [318]. Dahl, TW, A Chappaz, JP Fitts, et al., Molybdenum reduction in a sulfidic lake:Evidence from X-ray absorption fine-structure spectroscopy and implications for the Mo paleoproxy. Geochimica Et Cosmochimica Acta,2013.103:p.213-231.
    [319]. Zopfi, J, TG Ferdelman, BB J(?)rgensen, et al., Influence of water column dynamics on sulfide oxidation and other major biogeochemical processes in the chemocline of Mariager Fjord (Denmark). Marine Chemistry,2001.74(1):p.29-51.
    [320]. Wang, FY and A Tessier, Zero-Valent Sulfur and Metal Speciation in Sediment Porewaters of Freshwater Lakes. Environmental Science & Technology,2009.43(19):p.7252-7257.
    [321]. Dahl, TW, AD Anbar, GW Gordon, et al., The behavior of molybdenum and its isotopes across the chemocline and in the sediments of sulfidic Lake Cadagno, Switzerland. Geochimica Et Cosmochimica Acta,2010.74(1):p.144-163.
    [322]. Bertine, KK. and KK Turekian, Molybdenum in marine deposits. Geochimica et Cosmochimica Acta,1973.37(6):p.1415-1434.
    [323]. Scott, C, T Lyons, A Bekker, et al., Tracing the stepwise oxygenation of the Proterozoic ocean. Nature,2008.452(7186):p.456-459.
    [324]. Scheiderich, K, GR Helz. and RJ Walker, Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay). Earth and Planetary Science Letters,2010.289(1-2):p.189-197.
    [325]. Scranton, MI, Y Astor, R Bohrer, et al., Controls on temporal variability of the geochemistry of the deep Cariaco Basin. Deep Sea Research Part I:Oceanographic Research Papers,2001. 48(7):p.1605-1625.
    [326]. Francois, R, A Study on the Regulation of the Concentrations of Some Trace-Metals (Rb, Sr, Zn, Pb, Cu, V, Cr, Ni, Mn and Mo) in Saanich Inlet Sediments. British-Columbia, Canada. Marine Geology,1988.83(1-4):p.285-308.
    [327]. Emerson. SR and SS Huested, Ocean Anoxia and the Concentrations of Molybdenum and Vanadium in Seawater. Marine Chemistry,1991.34(3-4):p.177-196.
    328. Calvert, SE and TF Pedersen, Geochemistry of Recent Oxic and Anoxic Marine-Sediments Implications for the Geological Record. Marine Geology.1993.113(1-2):p.67-88.
    [329]. Helz, GR, CV Miller, JM Charnock, et al., Mechanism of molybdenum removal from the sea and its concentration in black shales:EXAFS evidence. Geochimica Et Cosmochimica Acta, 1996.60(19):p.3631-3642.
    [330]. Algeo, TJ and TW Lyons, Mo-total organic carbon covariation in modern anoxic marine environments:Implications for analysis of paleoredox and paleohydrographic conditions. Paleoceanography,2006.21(1).
    [331]. Wang, DL, RC Aller, and SA Sanudo-Wilhelmy, Redox speciation and early diagenetic behavior of dissolved molybdenum in sulfidic muds. Marine Chemistry,2011.125(1-4):p.101-107.
    [332]. Anbar, AD, Molybdenum stable isotopes:Observations, interpretations and directions. Reviews in Mineralogy and Geochemistry,2004.55(1):p.429-454.
    [333]. Wieser, M, Atomic weights of the elements 2005. Journal of physical and chemical reference data,2007.36:p.485.
    [334]. Coplen, TB, Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results. Rapid Communications in Mass Spectrometry,2011.25(17):p. 2538-2560.
    [335]. Siebert, C, TF Nagler, F von Blanckenburg, et al., Molybdenum isotope records as a potential new proxy for paleoceanography. Earth and Planetary Science Letters,2003.211(1-2):p. 159-171.
    [336]. Barling, J, GL Arnold, and AD Anbar, Natural mass-dependent variations in the isotopic composition of molybdenum. Earth and Planetary Science Letters,2001.193(3-4):p.447-457.
    [337]. Archer, C and D Vance, The isotopic signature of the global riverine molybdenum flux and anoxia in the ancient oceans. Nature Geoscience,2008.1(9):p.597-600.
    [338]. McManus, J, TF Nagler, C Siebert, et al., Oceanic molybdenum isotope fractionation: Diagenesis and hydrothermal ridge-flank alteration. Geochemistry Geophysics Geosystems, 2002.3.
    [339]. Malinovsky, D, D Hammarlund, B llyashuk, et al., Variations in the isotopic composition of molybdenum in freshwater lake systems. Chemical Geology,2007.236(3-4):p.181-198.
    [340]. Tossell, JA, Calculating the partitioning of the isotopes of Mo between oxidic and sulfidic species in aqueous solution. Geochimica Et Cosmochimica Acta,2005.69(12):p.2981-2993.
    [341]. Wasylenki, LE, CL Weeks, JR Bargar, et al., The molecular mechanism of Mo isotope fractionation during adsorption to birnessite. Geochimica Et Cosmochimica Acta,2011.75(17): p.5019-5031.
    [342]. Goldberg, T, C Archer, D Vance, et al., Controls on Mo isotope fractionations in a Mn-rich anoxic marine sediment, Gullmar Fjord, Sweden. Chemical Geology,2012.296:p.73-82.
    [343]. Pearce, CR, KW Burton, PAE Pogge von Strandmann, et al., Molybdenum isotope fractionation accompanying weathering, riverine transport and estuarine mixing. Geochimica Et Cosmochimica Acta,2008.72(12):p. A730-A730.
    [344]. Dickson, AJ, AS Cohen, and AL Coe, Seawater oxygenation during the Paleocene-Eocene Thermal Maximum. Geology,2012.40(7):p.639-642.
    [345]. Voegelin, AR, TF Nagler, NJ Beukes, et al., Molybdenum isotopes in late Archean carbonate rocks:Implications for early Earth oxygenation. Precambrian Research,2010.182(1-2):p. 70-82.
    [346]. Duan, Y, AD Anbar, GL Arnold, et al., Molybdenum isotope evidence for mild environmental oxygenation before the Great Oxidation Event. Geochimica Et Cosmochimica Acta,2010. 74(23):p.6655-6668.
    [347]. Pearce, CR, KW Burton, PAE Pogge von Strandmann, et al., Molybdenum isotope behaviour accompanying weathering and riverine transport in a basaltic terrain. Earth and Planetary Science Letters,2010.295(1-2):p.104-114.
    [348]. Voegelin, AR, TF Nagler, T Pettke, et al., The impact of igneous bedrock weathering on the Mo isotopic composition of stream waters:Natural samples and laboratory experiments. Geochimica Et Cosmochimica Acta,2012.86:p.150-165.
    [349]. Greber, ND, BA Hofmann, AR Voegelin, et al., Mo isotope composition in Mo-rich high-and low-T hydrothermal systems from the Swiss Alps. Geochimica Et Cosmochimica Acta,2011. 75(21):p.6600-6609.
    [350]. Mathur, R, S Brantley, A Anbar, et al., Variation of Mo isotopes from molybdenite in high-temperature hydrothermal ore deposits. Mineralium Deposita,2010.45(1):p.43-50.
    [351]. Zerkle, AL, K Scheiderich, JA Maresca, et al., Molybdenum isotope fractionation by cyanobacterial assimilation during nitrate utilization and N-2 fixation. Geobiology,2011.9(1):p. 94-106.
    [352]. Goldberg, T, C Archer, D Vance, et al., Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides. Geochimica Et Cosmochimica Acta,2009.73(21):p.6502-6516.
    [353]. Neubert, N, TF Nagler, and ME Bottcher, Sulfidity controls molybdenum isotope fractionation into euxinic sediments:Evidence from the modern Black Sea. Geology,2008.36(10):p. 775-778.
    [354]. Nagler, TF, N Neubert, ME Bottcher, et al., Molybdenum isotope fractionation in pelagic euxinia:Evidence from the modern Black and Baltic Seas. Chemical Geology,2011.289(1-2):p. 1-11.
    [355]. Siebert, C, J McManus, A Bice, et al., Molybdenum isotope signatures in continental margin marine sediments. Earth and Planetary Science Letters,2006.241(3-4):p.723-733.
    [356]. Poulson, RL, J Mcmanus, C Siebert, et al., Molybdenum isotopes in modern marine sediments: Unique signatures of authigenic processes. Geochimica Et Cosmochimica Acta,2006.70(18):p. A501-A501.
    [357]. Reitz, A, M Wille, TF Nagler, et al., Atypical Mo isotope signatures in eastern Mediterranean sediments. Chemical Geology,2007.245(1-2):p.1-8.
    [358]. Brucker, RLP, J McManus, S Severmann, et al., Molybdenum behavior during early diagenesis: Insights from Mo isotopes. Geochemistry Geophysics Geosystems,2009.10(6):p. Q06010.
    [359]. Albarede, F and B Beard, Analytical methods for non-traditional isotopes. Geochemistry of Non-Traditional Stable Isotopes,2004.55:p.113-152.
    [360]. Wieser, M, J De Laeter, and M Varner, Isotope fractionation studies of molybdenum. International Journal of Mass Spectrometry,2007.265(I):p.40-48.
    [361]. Nagler, TF, C Siebert, H Luschen, et al., Sedimentary Mo isotope record across the Holocene fresh-brackish water transition of the Black Sea. Chemical Geology,2005.219(1-4):p.283-295.
    [362]. Xu, N, C Christodoulatos, and W Braida, Adsorption of molybdate and tetrathiomolybdate onto pyrite and goethite:Effect of pH and competitive anions. Chemosphere,2006.62(10):p. 1726-1735.
    [363]. Herrmann, AD, B Kendall, TJ Algeo, et al., Anomalous molybdenum isotope trends in Upper Pennsylvanian euxinic facies:Significance for use of delta Mo-98 as a global marine redox proxy. Chemical Geology,2012.324:p.87-98.
    [364]. Bibak, A and OK Borggard, Molybdenum Adsorption by Aluminum and Iron-Oxides and Humic-Acid. Soil Science,1994.158(5):p.323-328.
    [365]. Goldberg, S and HS Forster, Factors affecting molybdenum adsorption by soils and minerals. Soil Science,1998.163(2):p.109-114.
    [366]. Gustafsson, JP, Modelling molybdate and tungstate adsorption to ferrihydrite. Chemical Geology, 2003.200(1-2):p.105-115.
    [367]. Thamdrup, B, Bacterial manganese and iron reduction in aquatic sediments. Advances in Microbial Ecology, Vol 16,2000.16:p.41-84.
    [368]. Poulton, SW and R Raiswell, The low-temperature geochemical cycle of iron:From continental fluxes to marine sediment deposition. American Journal of Science,2002.302(9):p.774-805.
    [369]. Wasylenki, LE, BA Rolfe, CL Weeks, et al., Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides. Geochimica Et Cosmochimica Acta,2008.72(24):p.5997-6005.
    [370]. Morford, JL and S Emerson, The geochemistry of redox sensitive trace metals in sediments. Geochimica Et Cosmochimica Acta,1999.63(11-12):p.1735-1750.
    [371]. McManus, J, WM Berelson, S Severmann, et al., Molybdenum and uranium geochemistry in continental margin sediments:Paleoproxy potential. Geochimica Et Cosmochimica Acta,2006. 70(18):p.4643-4662.
    [372]. Barling, J and AD Anbar, Molybdenum isotope fractionation during adsorption by manganese oxides. Earth and Planetary Science Letters,2004.217(3-4):p.315-329.
    [373]. McManus, J, TF Nagler, C Siebert, et al., Oceanic molybdenum isotope fractionation: Diagenesis and hydrothermal ridege-flank alteration. Geochimica Et Cosmochimica Acta,2002. 66(15A):p.A503-A503.
    [374]. Kawakubo, S, S Hashi, and M Iwatsuki, Physicochemical speciation of molybdenum in rain water. Water Research,2001.35(10):p.2489-2495.
    [375]. Wedepohl, K, The chlorine and sulfur crustal cycle-abundance of evaporites. Rodrigues--Clemente, R., Tardy, Y (Eds),. Geochemistry and Mineral Formation in the Earth Surface", Centre National de la Recherche Scientifique. Madrid,1987:p.3-27.
    [376]. Neubert, N, AR Heri, AR Voegelin, et al., The molybdenum isotopic composition in river water: Constraints from small catchments. Earth and Planetary Science Letters,2011.304(1-2):p. 180-190.