地下水系统中砷活化的钼同位素地球化学指示

砷在天然环境中的迁移富集与氧化还原状态密切相关.盆地环境地下水中砷的活化迁移机制主要为沉积物中铁/锰氢氧化物由氧化还原条件变化导致发生还原性溶解进而释放吸附在其表面的砷.钼及钼同位素为氧化还原环境的重要指示参数,且铁/锰氢氧化物对钼同位素分馏有着重要的控制作用.将地下水的钼同位素应用于砷的活化迁移规律研究.大同盆地地下水中钼同位素比值(δ98 Mo)范围为-0.12‰~+2.17‰,相比于淡水中钼同位素组成偏重.桑干河河水的δ98 Mo为+0.72‰,与文献报道的河水平均钼同位素比值+0.7‰相当.大同盆地地下水中δ98 Mo与硫化物之间存在正相关关系,表明MoFe-S复合物可能形成于特定条件下,并优先利用水溶液中轻的钼使地下水中δ98 Mo比值升高.砷浓度与钼浓度之间的微弱负相关以及砷浓度与钼同位素之间的正相关说明,Mo-Fe-S的形成过程可能与同环境中As-Fe-S的复合物的形成存在竞争关系,进而使得地下水中砷富集.地下水中相对偏高的δ98 Mo可能来源于铁的氢氧化物对溶液中轻的钼的吸附速率高于先前吸附在铁的氢氧化物的钼的释放,且铁的氢氧化物对水溶液中钼的再吸附这一循环过程会导致地下水中钼浓度降低及钼同位素比值的升高.钼同位素指示的循环性的铁的氢氧化物的还原溶解及再氧化过程对砷的富集也有重要影响.     

钼及钼同位素地球化学——同位素体系、测试技术及在地质中的应用

多接收电感耦合等离子体质谱(MC-ICP-MS)的广泛应用使过渡金属元素同位素地球化学的研究近年来获得蓬勃发展.利用元素双稀释剂法对钼同位素值进行校正,目前可以获得±0.1‰(2σ)的测试精度.自然界中钼同位素分馏δ98/95Mo可达～3‰,其分馏机制与环境的氧化-还原状态有关.在氧化环境下钼以MoO2/4-的形式与锰...     

古海洋氧化还原地球化学指标研究新进展

古海洋氧化还原条件的恢复一直是地学界的研究热点。许多指标可以用来指示古海洋沉积岩(物)的氧化还原条件。其中地球化学和矿物学方法历来是研究古海洋氧化还原条件的主要手段,前人工作主要集中在单个种类指标(沉积学、矿物学、地球化学等)的单方面研究,缺乏系统研究。但沉积物中的氧化还原指标受很多因素的影响,用单个指标来指示水体的氧化还原条件存在不确定性。主要通过主量元素(总有机碳TOC、有机碳和磷的摩尔比Corg∶P),氧化还原敏感的微量元素(U、V、Mo),黄铁矿类型和草莓状黄铁矿粒径分布以及同位素(黄铁矿硫同位素δ34Spyrite、钼同位素δ98 Mo、铀同位素δ238 U)等指标的综合运用来区分硫化、缺氧、次氧化以及氧化等水体条件。在硫化水体中,氧化还原敏感元素和TOC含量均大量富集,尤其是Mo的富集系数(MoEF)比U的富集系数(UEF)更大(MoEFUEF),有机碳和磷的摩尔比(Corg∶P)也呈现高值;黄铁矿几乎全部呈草莓状,很少出现自形晶,草莓状黄铁矿平均粒径小(常小于5μm)且变化不大,δ34Spyrite值偏负,δ98 Mo值和海水同位素值接近,约为+2.3‰,δ238 U值为+0.2‰,高于海水的同位素值(-0.41‰)。水体环境为氧化的条件下,氧化还原敏感的元素和TOC的量都很缺乏,有机碳和磷的摩尔比(Corg∶P)出现低值,黄铁矿很少,且主要以自形晶的形式出现,平均粒径很大,黄铁矿中的δ34Spyrite值偏正,δ98 Mo值偏负,为-0.7‰,δ238 U值为-0.65‰。在缺氧和次氧化水体环境中,各种指标介于硫化和氧化环境之间,氧化还原敏感元素和TOC含量适中,U相对比Mo富集(UEFMoEF),黄铁矿以草莓状为主,有部分的自形晶出现,黄铁矿平均粒径较大,而且变化范围较大,黄铁矿中的δ34Spyrite值、δ98 Mo值以及δ238 U值均介于氧化和硫化环境之间。最后,还提出在分析古海洋的氧化还原条件时,要综合考虑多种影响因素,清晰认识到每个指标的适用性和局限性,并指出了存在的问题和不足。     

灌溉活动对大同盆地表层土壤中砷迁移的影响

大同盆地是我国原生高砷地下水典型分布区。高砷地下水常被用作灌溉水源,灌溉回流对表层土壤中砷迁移和富集有着重要影响,但具体机制尚不清晰。通过场地灌溉模拟试验,并结合室内分析,探讨了灌溉活动对表层土壤中砷迁移转化的影响机制。结果表明,灌溉回流不仅导致地表土壤载砷量显著增加,而且引起潜水位快速上升。近地表还原性环境的强化使得含砷铁氧化物还原溶解增强,从而导致了砷的释放。此外,土壤孔隙水离子强度增加促进了离子交换态砷的迁移。灌溉停止后,伴随潜水位回落,氧化环境的增强有利于结晶态铁氧化物的形成,水砷通过吸附和共沉淀作用重新被铁氧化物固定。因此,高砷地下水灌溉通过改变近地表氧化还原环境可促进砷的迁移,砷和铁的输入最终导致表层土壤总砷和铁含量增加。     

河套平原西部地下水砷富集机制研究

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

大同盆地地下水中碳硫同位素组成特征及其对碘迁移富集的指示

为深入探究地下水系统中影响碘迁移转化的主控水文生物地球化学过程,对大同盆地典型高碘地下水区完成样品采集,分析地下水样品基础理化性质及碳硫同位素组成特征.结果表明,大同盆地地下水碘含量变化范围为14.40~1 030.00 μg/L,高碘地下水（I>100 μg/L）主要分布在盆地中心排泄区.地下水中溶解性无机碳的δ13C_DIC值变化范围为-12.11‰~-9.79‰,硫酸盐δ34S_SO4值介于4.04‰~16.63‰.δ13C_DIC和DOC之间存在较明显的正相关关系,表明有机质的微生物降解过程是区域地下水无机碳的重要来源之一.同时,δ13C_DIC与δ34S_SO4一定的负相关关系表明硫酸盐是有机质微生物降解过程中潜在电子受体之一,且地下水水环境以偏还原环境为主.高碘地下水表现出低δ13C_DIC、高δ34S_SO4的同位素特征,表明有机质的微生物降解过程是控制地下水中碘迁移释放的主要过程之一,与该过程相伴而生的碘形态转化进一步促使碘以碘离子的形式在偏还原的地下水环境中发生富集.      

四川广元上寺剖面不同地史时期沥青的钼同位素组成及意义

对四川广元地区寒武纪、二叠纪和石炭纪部分海相碳酸盐岩地层中沥青的Mo同位素和微量元素进行了测定.结果表明,该区不同时期沥青的δ98Mo有较大的变化范围(+0.34‰～+1.71‰),总体上,接近缺氧沉积岩δ98Mo的范围.寒武纪海相地层中沥青具有明显的δEu正异常(0.75～1.68),其Mo、Ni、V等氧化还原敏感元...     

中元古代增氧事件：来自华北克拉通燕辽地区铁岭组的地球化学证据

氧气是生命演化的重要因素。近期的一些研究表明,元古宙两次大氧化事件之间的平静期存在多次幕式增氧事件,尤其是14亿年前后大气和海水的氧气水平有着很大程度的提高。但是,目前对于14亿年之前的表生环境氧化还原状态的研究仍存在不足。本次研究通过分析华北克拉通燕辽盆地中元古代～14.4亿年铁岭组绿色页岩的钼同位素组成、氧化还原敏感元素和稀土元素特征,发现绿色页岩的Fe含量和Mn含量较高,并显示富集轻的钼同位素组成(-1.00±0.07‰～-0.49±0.06‰)特征。Fe-Mn-Mo三者相关性表明,轻的Mo同位素主要以吸附共沉淀的形式进入铁锰(氢)氧化物,造成富铁的沉积物富集轻Mo同位素,而海水中Mo同位素偏重,指示绿色页岩沉积于氧化的水体之中。同时,氧化还原敏感元素含量及比值也指示铁岭组绿色页岩沉积时水体为氧化环境。研究结果表明,～14.4亿年前后发生了一次显著的增氧事件,使得当时海水氧化面积扩大,为早期生命演化提供了物质基础。     

大型水系δ~(98/95)Mo季节变化特征及控制机理

正钼(Mo)同位素作为非常热门的反演古海洋缺氧历史指标是建立在一个有争议的假设之上,即认为在地质历史时期,陆源输入的δ~(98/95)Mo与地壳岩石平均值(0.0‰)一致,且长期稳定不变。根据现代河流数据显示,河水δ~(98/95)Mo在空间尺度上变化明显(0.15‰~2.40‰),且重于地壳岩石平均组成。而目前,关于河水δ~(98/95)Mo在时间尺度上变化特征的工作几乎没有。同时,对河水δ~(98/95)Mo偏重于地壳     

钼的稳定同位素体系及其地质应用

近年来多接收杯电感耦合等离子体质谱仪(MC-ICP-MS)的广泛应用,大大提高了Mo同位素分析方法的精度和效率,使Mo同位素地球化学成为当前地学研究领域中的一个前沿方向.本文综述了Mo稳定同位素的最新研究进展及其地质应用.自然界中的Mo同位素(δ98/95Mo)的一般变化范围是-1.35‰～2.60‰.Mo同位素分馏在充氧环境下取决于Mn氧化物的吸附或共沉淀,贫氧一缺氧环境下受控于水溶液中的[H2S].沉积物中的Mo同位素既能指示古沉积环境的氧化还原条件,也能够指示与之相关的古海洋地理环境,因此,Mo同位素是了解局域至区域沉积环境的氧化还原条件、硫和碳地球化学循环及古海洋化学演化等的强有力工具.随着其分馏机理的进一步阐明和应用范围的拓展,Mo同位素将在地球与环境科学研究中得到广泛的应用.     

含水层中砷活化迁移的水化学与DOM三维荧光证据

为了认识高砷地下水中砷活化迁移的生物地球化学机制,对江汉平原地下水氧化还原敏感元素的水化学特征及溶解性有机物(DOM)三维荧光信息进行了研究.水化学研究显示,地下水中的砷与铁的还原和有机质的氧化分解过程有密切关系.水样DOM的三维荧光分析表明,地下水中存在微生物介导下氧化还原过程的反应性有机物组分,其中醌类腐殖质与铁、硫酸盐等的还原反应过程联系紧密.还原、氧化醌类及易降解DOM组分与还原产物、砷的关系进一步显示,砷的活化与微生物介导下的铁氧化物的还原过程联系在一起.在这一过程中,易降解有机物充当电子供体的角色并被消耗,而还原醌与氧化醌则很可能扮演了电子飞行过程中的电子飞行物,"催化"了砷活化的氧化还原过程.      

大同盆地高砷地下水稀土元素特征及其指示意义

对大同盆地典型高砷地下水开展了稀土元素地球化学研究.研究表明: 高砷地下水具有低∑REE含量及富集重稀土(HREEs)特征.地下水中低含量∑REE与含水层沉积物中Fe-Mn氧化物/氢氧化物对REEs的吸附有关.地下水中重稀土元素相对于轻稀土元素的富集可能是吸附作用和碳酸根离子同REEs发生络合作用的共同结果.采用平均大陆上地壳标准化的地下水稀土元素分布表现出显著的Ce及Eu正异常.地下水Ce/Ce*值及Eu含量与Fe+Mn具有显著相关性, 表明铁锰氧化物还原性溶解是控制Ce/Ce*值及Eu含量特征的主要因素.Ce/Ce*值及Eu含量与As浓度的关系表明, Ce异常及Eu含量特征能对地下水中As的富集进行有效指示.      

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.     

Mo isotopic variations of a Cambrian sedimentary profile in the Huangling area,South China: Evidence for redox environment corresponding to the Cambrian Explosion

The radiation of macroscopic animals in the Early Cambrian, commonly be called as ‘Cambrian explosion’, had a close relationship with Earth oxygenation. These macrofossils are widely preserved within the Early Cambrian in the northern and western Yangtze Craton. In order to show the casual relationship between animal evolution and Earth redox environment, Mo content and isotopic composition analyses have been conducted on dolomites of the Tianzhushan Formation and the black shales of the Shuijingtuo Formation from the lowermost Cambrian profile in the eastern Huangling dome, northern Yangtze Craton. The calcitic dolostones from the Tianzhushan Formation display lower concentrations of Mo contents (0.055–0.666 ppm) than that of the black silty shales from the Shuijingtuo Formation (6.0–172 ppm). This magnitude difference is most likely related to the different lithologies due to Mo enrichment in shales. The Mo isotope values (δ^98/95Mo) of the calcitic dolostones for the Tianzhushan Formation vary from −0.73‰ to 0.41‰. In comparison, the black sandy shales from the Shuijingtuo Formation exhibit δ^98/95Mo of −1.04–1.84‰, including 5 samples from the earliest Shuijingtuo Formation displaying systematically higher δ^98/95Mo values (0.09–1.84‰) than those of the other 5 samples from upper layers (δ^98/95Mo = −1.04 to −0.19‰). These geochemical data suggest that the redox environment of the early Cambrian is fluctuating, and the peak oxygenation of the ocean had already reached a level similar to modern environments. According to the Mo concentrations and δ^98/95Mo data, the sedimentary succession can be divided into five intervals, which are closely correlated to the episodic evolution of early life in the Cambrian. Together with the available published data from other profiles in the Yangtze Craton, our new data reveal that the higher oxidation environment had a positive effect on the evolution of early life.     

新疆焉耆盆地水环境氢氧同位素特征及其指示作用

根据焉耆盆地开都河水及其两岸地下水中的氢氧稳定同位素资料及氘过量参数(d)值,分析了焉耆盆地内不同水体的δ(D)、δ(18O)和d值的分布规律,并得到地下水的主要补给来源及其与开都河水的相互作用关系;地下水的δ(D)在-87.60‰～-61.82‰间,δ(18O)在-10.90‰～-9.73‰间;开都河水的δ(D)在-71.95‰～-58.58‰间,δ(18O)在-9.57‰～-8.64‰间。结果表明:焉耆盆地内地下水和地表水同源于山区的降水和冰雪融水,且经历了较强的蒸发作用;地下水与地表水之间的直接水力联系较弱,深层地下水主要接受开都河水在洪积扇区的入渗补给,浅层地下水主要接受河流引水灌溉入渗;不同深度地下水之间的水力联系较为密切,为统一的地下水系统。     

Molybdenum Mass Fractions and Stable Isotope Compositions of Sedimentary Carbonate and Silicate Reference Materials

A double‐spike method in combination with MC‐ICP‐MS was applied to obtain molybdenum (Mo) mass fractions and stable isotope compositions in a suite of sedimentary silicate (marine, lake, stream, estuarine, organic‐rich sediment, shales, slate, chert) and carbonate reference materials (coral, dolomite, limestones, carbonatites), and a manganese nodule reference material, poorly characterised for stable Mo isotope compositions. The Mo contents vary between 0.076 and 364 μg g^?1, with low‐Mo mass fractions (< 0.29 μg g^?1) found almost exclusively in carbonates. Intermediate Mo contents (0.73–2.70 μg g^?1) are reported for silicate sediments, with the exception of chert JCh‐1 (0.24 μg g^?1), organic‐rich shale SGR‐1b (36.6 μg g^?1) and manganese nodule NOD‐A‐1 (364 μg g^?1). The Mo isotope compositions (reported as δ⁹⁸Mo relative to NIST SRM 3134) range from ?1.77 to 1.03‰, with the intermediate precision varying between ± 0.01 and ± 0.12‰ (2s) for most materials. Low‐temperature carbonates show δ⁹⁸Mo values ranging from 0.21 to 1.03‰ whereas δ⁹⁸Mo values of ?1.77 and ?0.17‰ were obtained for carbonatites CMP‐1 and COQ‐1, respectively. Silicate materials have δ⁹⁸Mo values varying from ?1.56 to 0.73‰. The range of δ⁹⁸Mo values in reference materials may thus reflect the increasingly important relevance of Mo isotope investigations in the fields of palaeoceanography, weathering, sedimentation and provenance, as well as the magmatic realm.     

Proposal for an International Molybdenum Isotope Measurement Standard and Data Representation

Molybdenum isotopes are increasingly widely applied in Earth Sciences. They are primarily used to investigate the oxygenation of Earth's ocean and atmosphere. However, more and more fields of application are being developed, such as magmatic and hydrothermal processes, planetary sciences or the tracking of environmental pollution. Here, we present a proposal for a unifying presentation of Mo isotope ratios in the studies of mass‐dependent isotope fractionation. We suggest that the δ^98/95Mo of the NIST SRM 3134 be defined as +0.25‰. The rationale is that the vast majority of published data are presented relative to reference materials that are similar, but not identical, and that are all slightly lighter than NIST SRM 3134. Our proposed data presentation allows a direct first‐order comparison of almost all old data with future work while referring to an international measurement standard. In particular, canonical δ^98/95Mo values such as +2.3‰ for seawater and ?0.7‰ for marine Fe–Mn precipitates can be kept for discussion. As recent publications show that the ocean molybdenum isotope signature is homogeneous, the IAPSO ocean water standard or any other open ocean water sample is suggested as a secondary measurement standard, with a defined δ^98/95Mo value of +2.34 ± 0.10‰ (2s).     

Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

江汉平原高砷地下水中DOM三维荧光特征及其指示意义

水体中溶解性有机质(dissolved organic matter, DOM)是含水层中砷释放的主控因素之一.江汉平原河湖众多、沟渠广布,地表水体与浅层地下水的交互作用使得DOM的组分特征及其强度有显著差异.为查明江汉平原地下水中溶解性有机质在砷迁移转化过程中的作用,对江汉平原地表水和浅层地下水进行三维荧光光谱分析,使用平行因子分析法提取水体中有机质的分子组成、功能特点和荧光特征,并分析各组分相对含量与地下水中砷与铁的关联.江汉平原水体中DOM包括3种主要组分,组分C1、C2为类腐殖质,C2是生物降解过程中产生的小分子,C3为类蛋白物质.地下水DOM以类腐殖质组分C1、C2为主,地表水以类蛋白类物质C3和小分子腐殖质C2为主.高砷地下水中DOM以陆源为主,主要通过两种途径促进As的迁移转化:(1) DOM的腐殖质组分充当微生物群落的电子运输工具,促进微生物作用下的有机质氧化和铁氧化物的还原,并伴随As的释放及大量溶解性有机碳(dissolved organic carbon, DOC)和HCO₃-的产生;(2) As以铁等金属阳离子为桥接物与腐殖质结合,通过形成As-Fe-DOM络合物,导致地下水中砷的迁移.