高温富硫化物热泉中硫代砷化物存在形态的地球化学模拟:以云南腾冲热海水热区为例

天然水环境中地质成因砷的存在是世界范围内对人类威胁极大的环境问题之一.在高温富硫化物地热水中,硫代砷化物是砷的主要存在形态之一.在国内尚无硫代砷化物定量检测方法的背景下,以云南腾冲地热带的热海水热区为典型研究区,基于不同类型硫代砷化物的最新化学热力学数据wateq4f.dat,利用水文地球化学模拟软件PHREEQC开展了不同类型热泉中砷的存在形态的地球化学模拟.结果表明,热海热泉中砷的主要形态是硫代砷酸盐,砷酸盐和亚砷酸盐次之,硫代亚砷酸盐则含量极低;在各类硫代砷酸盐中,按平均百分含量降序依次为:一硫代砷酸盐→三硫代砷酸盐→四硫代砷酸盐→二硫代砷酸盐.pH、Eh和总硫化物含量是热泉中砷的形态分布的控制性因素.在酸性条件下,砷以硫代砷酸盐和亚砷酸盐为主要存在形式;而在中性/偏碱性条件下,砷的形态则以硫代砷酸盐为主,砷酸盐次之.偏还原环境和高硫化物含量是硫代砷化物、特别是三硫代砷酸盐和四硫代砷酸盐稳定存在的有利条件.      

腾冲热泉中砷的甲基化和巯基化过程

为了研究热泉中砷的形态及其分布、转化规律,针对云南腾冲热泉各种砷形态进行了IC-ICP-MS测试和水文地球化学分析.在91处热泉中检出了11种砷形态,包括(亚)砷酸盐、无机硫代砷和甲基(硫代)砷.其中(亚)砷酸盐含量>无机硫代砷含量>甲基砷含量.热泉中无机硫代砷含量及其巯基化程度与硫/砷比正相关.甲基砷含量低是富硫化物...     

腾冲热海地热田高温热泉中的硫代砷化物及其地球化学成因

以我国大陆范围内典型的岩浆热源型水热系统——云南腾冲热海为研究区,在国内首次对热泉中硫代砷化物含量及其地球化学成因进行了分析.研究采用的在野外对富硫化物水样进行快速冷冻处理、而后在实验室进行砷的形态分离和测试的方法明显优于当前通用的水样砷含量及其形态分析的预处理和测试方法.主要原因为后者在采样现场对水样的酸化处理可使样品中三硫代砷酸盐以非定形态硫砷化合物的形式沉淀,且用常规阴离子交换柱在野外无法实现硫代砷酸盐的完全回收及其与砷酸盐的分离.受岩浆流体输入和热储内高温条件下强烈流体-岩石相互作用的控制,热海水热系统排泄的中性-偏碱性热泉中富集硫化物和砷,为热泉中硫代砷化物的形成提供了必要条件.热海热泉中检出的硫代砷化物包括一硫代砷酸盐、二硫代砷酸盐和三硫代砷酸盐,在总砷中所占比例最高分别可达26.7%、43.3%和33.7%.热海地热田的2个子区(硫磺塘和澡塘河) 的热泉沿不同断裂带出露,地热水升流过程中经历的冷却方式也不同,使硫磺塘热泉具有相对较高的总硫化物含量和总砷含量,并导致其中各类硫代砷酸盐具有更高的含量范围.      

西藏搭格架高温热泉中钨的水文地球化学异常

西藏搭格架水热区的热泉含异常高浓度的钨,其钨/钼比也远高于常见天然水.开展了搭格架典型热泉的地球化学研究,发现中性热泉的钨浓度显著高于偏酸性热泉:前者是深部母地热流体经绝热冷却、传导冷却等过程后排出地表而形成,其中的钨主要来自岩浆水的贡献;而后者为中性地热水和蒸汽加热型强酸性水的混合产物,贫钨蒸汽加热型水的稀释使其钨浓度不同程度降低.在地热水中,钨与典型保守组分氯相似,不易自液相沉淀或被热储介质吸附;但地热水含硫化物时,钼则极易以辉钼矿的形式沉淀,导致搭格架热泉的钨/钼比偏高.虽然搭格架地热水中存在硫化物,但钨在水中主要以钨酸盐的形式存在,少量硫代钨酸盐的形成对钨的水文地球化学过程影响不大.      

地热水中竞争巯基化影响下的砷、锑形态分布：以西藏阿里典型水热区为例

砷、锑是地热水中的典型有害组分,受地热水独特水化学条件影响,常呈现与其他类型天然水体相异的形态分布特征。本文以西藏阿里的朗久、曲色涌巴、门士、莫落江等地热区为研究区,分析了含硫化物地热水中砷、锑在竞争巯基化过程影响下的形态分布特征。受富砷、锑岩浆流体输入或高温条件下热储围岩加强淋滤的影响,上述地热区排泄的地热水中砷、锑浓度范围分别可达5 833～20 750μg/L和579～2 129μg/L。地热水中砷以亚砷酸盐和砷酸盐为主要存在形态,但同时存在占总砷百分比在0.1%～55.1%之间的硫代砷酸盐;与砷的情况不同,地热水中锑检测出的形态均为亚锑酸盐和/或锑酸盐,所有样品中均未检出硫代锑酸盐。考虑到相当一部分地热水样品的S/Sb摩尔比在理论上满足硫代锑酸盐的形成条件,且所有样品中砷的富集程度均不同程度高于锑,我们认为地热水中锑的含氧络阴离子的巯基化过程受到了共存砷的强烈抑制。在硫化物相对于砷、锑总量并不充分盈余的情况下,砷的竞争巯基化是控制地热水中硫代锑酸盐形成的最重要因素。本工作及其研究结果有助于深入理解西藏地热水环境中砷、锑的环境地球化学行为。     

硫代砷化合物的合成及其在地下水中的赋存特征: 以大同盆地为例

硫代砷酸盐作为富硫地下水中砷的重要赋存形态,在其迁移转化过程中起着十分重要的作用,但现有硫代砷酸盐的标准合成方法流程复杂、操作繁琐,限制了对地下水中硫代砷酸盐赋存规律的研究。为此,首先改进了硫代砷酸盐标准物质的合成方法,采用操作简便的水热法合成了硫代砷化合物标准物质,建立了基于HPLC-ICPMS的硫代砷化合物分析方法,该方法检出限为0.01μg/L;探讨了不同保存条件对硫代砷化合物稳定性的影响,发现干冰速冻-20℃是地下水硫代砷酸盐样品的最佳保存条件。应用上述方法对大同盆地地下水中的硫代砷酸盐进行了取样分析,结果表明40%的水样中均检出硫代砷酸盐,最高质量浓度可达209.90μg/L;弱碱性还原条件有利于硫代砷酸盐的赋存,且硫化物质量浓度对硫代砷酸盐的生成有重要控制作用。对地下水中硫代砷酸盐的深入研究有助于揭示富硫地下水中砷的迁移转化规律,丰富和完善高砷地下水成因理论。     

硫酸盐还原作用调控下砷的环境地球化学行为

<正>天然环境中砷的形态转化与环境的化学条件和生物条件密切关联,铁与硫是影响砷环境行为的重要元素,尤其微生物硫酸还原作用对砷的形态转化具有重要的调控作用。本研究以淹水土壤为例研究了厌氧微生物作用下砷,铁,硫元素的环境行为,及次生产物的相互作用下砷的再分配过程,重点考察硫酸盐还原作用对砷环境行为的影响。研究发现在加硫和无硫添加体系中微生物还原作用都造成了体系中85%以上砷酸盐被转化为亚砷酸盐。在无硫添加体系中微生物促进了砷的释放,释放的砷以是亚砷酸盐为主要形态,在培养     

厌氧环境中硫代亚砷在水——矿物界面的吸附行为研究

<正>近几年,砷污染已经引起人们的广泛关注,环境中砷的形态直接影响砷的地球化学循环及其生态效应。在地下热泉等含硫水环境中硫代亚砷酸盐是非常重要的一种砷形态,硫代砷在环境中的迁移转化过程、在水—矿物界面的吸附反应过程及其相关机理一直缺乏研究。笔者选取水环境中常见的两种铁矿物:磁铁矿和硫化亚铁作为吸附剂,对于p H中性条件下一定硫代程度的硫代亚砷酸盐进行了吸附动力学研究。研究表明,两种矿物对硫代亚砷酸盐的吸附量都低于亚砷酸钠。p H值对吸附过程具有重要影响,在     

典型高温热泉中锑的形态分布及其地球化学成因

锑为典型有害元素,地热成因锑是天然水环境中溶解态锑的重要来源,富锑热泉排泄的负面环境效应不容忽视.本文在藏南和滇西选择典型地热区,分析了热泉中锑的形态分布及其地球化学成因.总体上,研究区排泄的地热水具有远高于天然水环境背景值的锑含量,最高可达2 128.7μg/L.水文地球化学计算表明热泉中锑的主要存在形态为锑酸盐和亚锑酸盐,但部分热泉样品中硫代锑占总锑百分比可高达35%.硫化物浓度、S（-Ⅱ）/Sb摩尔比,以及砷锑之间的竞争巯基化作用是影响热泉中硫代锑含量的关键因素.在本研究所涉及地热系统中,西藏玛旁雍错曲色涌巴、门士、莫落江为岩浆热源型地热系统,其地热水中锑源自高温条件下热储围岩淋滤和作为热源的岩浆房所释出流体的输入,西藏曲卓木、朗久与云南邦腊掌则属于非岩浆热源型地热系统,其热泉中的锑主要来源于地热水-围岩矿物相互作用.     

地下水环境中的硫代砷研究进展

硫代砷是富硫化物地下水中砷的重要形态,对环境和人类健康有潜在威胁。目前硫代砷研究程度尚低,本次主要针对国内外地下水（地热水）中硫代砷的存在形态,水文—生物—环境地球化学过程,样品保存,定量检测方法等方面进行研究。结论如下:pH, 氧化还原电位,硫化物含量和微生物作用等是影响地下水中硫代砷稳定存在和形态分布的重要因素。含铁矿物能与水中的硫代砷形成配位键对其进行吸附,吸附性普遍弱于（亚）砷酸盐,因此,地下水中硫代砷可能表现出更强的迁移性。用于硫代砷检测的自然水样在采集中可采取过滤,速冻,厌氧和低温短期保存的操作流程,以减缓该形态的转化甚至消失。色谱联用ICP-MS系统可用于自然水样中硫代砷的分离定量检测,紫外—可见分光光度法和X射线吸收光谱法在不同场景下也可对硫代砷进行定量和表征分析。地热水和浅层地下水中均可能存在硫代砷,由于水样中硫代砷的不稳定性,室内检测和分析难以准确反映现场过程,因此,野外样品保存技术和现场检测方法的更新可能在未来有更大研究空间,值得进一步探索。     

Thermodynamic Modeling of Thioarsenic Species Distribution in High As Groundwater in Hetao Plain*

Thioarsenic has gained increasing attention as a newly identified arsenic species. This paper selected Hetao Plain as the study area. Based on the field survey data and the thermodynamic reaction equation, the distribution characteristics of thioarsenic speciation in high-arsenic groundwater were simulated and analyzed. The results show that the major of arsenic speciation is arsenite, followed by thioarsenate and arsenate, and thethioarsenite concentrations are extremely low. Among them, monothioarsenate and trithioarsenate are the predominant thioarsnate species, with monothioarsenite being the dominant thioarsenite. In the buried depth of the range of 5~40 m, the content of various arsenic species does not change significantly with increasing depth. In the range of 40~80 m buried depth, the content of arsenite decreases with the increase of depth, and the content of thioarsenite increases with depth. Sulfide concentration has a significant effect on the distribution of arsenic species. When the concentration of sulfide is less than 5 μg/L, the various arsenic species do not change regularly with the increase of sulfide concentration. When the sulfide concentration is more than 5 μg/L, the content of arsenite and arsenate decreases with the increase of sulfide concentration, and the content of thioarsenate and thioarsenite tends to increase, and mutual transformation happens between different thioarsenite and thioarsenate species.     

Mineralogical and Geochemical Constraints on Arsenic Mobility in a Philippine Geothermal Field

Arsenic is usually associated with sulphide minerals formed in the geothermal environment. However, sulphide minerals are prone to dissolution after contact with meteoric water under surface oxidizing conditions. Secondary precipitates that form from the dissolution of the primary sulfides exert a greater influence on arsenic mobility in the geothermal environment. Fe-hydroxides have very good affinity with dissolved arsenate and are stable under most surface oxidizing conditions. Both amorphous silica directly precipitated from geothermal fluids and possibly a kaolinite alteration can host a small significant amount of arsenic. These silicates are also more stable under a wide range of pH and redox conditions.     

Arsenic Speciation in a Contaminated Gold Processing Tailings Dam

Gold recovery in ores containing arsenopyrite releases significant amounts of arsenic into the environment due to mineral processing and oxidation during storage. The extent of arsenic weathering in a tailings dam has been investigated. Speciation of As in surface and pore waters and pond sediments showed that for gold tailings in the dam, As enrichment took place in the pore water relative to the surface water. In pond sediments As was predominantly present as residual arsenopyrite and partly as a substance co-precipitated with iron hydroxide. The arsenic release from the sediment results from a reductive dissolution of the arsenopyrite and Fe oxides. In the surface water, arsenate and arsenite are the main arsenic species (arsenate is dominant), but in the pore waters methylation processes play a significant role. Arsenic transport is accompanied by the transformation of As into the less toxic compounds (methylated species) co-existing with the most toxic species (arsenite).     

Arsenic speciation in Mono Lake, California: Response to seasonal stratification and anoxia

Mono Lake is a closed-basin, alkaline, hypersaline lake located at the western edge of the Great Basin in eastern California. We studied the distribution of arsenic (As) species in the water column of Mono Lake between February and November, 2002. This period captured the seasonal progression from winter mixing, through summer thermal stratification, to autumn overturn. Arsenic speciation was determined by ion chromatography-inductively coupled-plasma-mass spectrometry of samples preserved in the field by flash-freezing in liquid nitrogen. We found that arsenic speciation was dominated (>90%) by arsenate when oxygen was detectable. Once levels fell below 6 μmol/L O₂, arsenic speciation shifted to dominance by reduced species. Arsenate and arsenite co-occurred in a transition zone immediately below the base of the oxycline and low but significant concentrations of arsenate were occasionally detected in sulfidic hypolimnion samples. Thio-arsenic species were the dominant form of As found in sulfidic waters. Maxima of thio-arsenic species with stoichiometries consistent with mono-, di- and trithio-arsenic occurred in succession as sulfide concentration increased. A compound with a stoichiometry consistent with trithio-arsenic was the dominant As species (∼50% of total As) in high sulfide (2 mmol/L) bottom water. Lower concentrations of total As in bottom water relative to surface water suggest precipitation of As/S mineral phases in response to sulfide accumulation during prolonged anoxia.     

煤中砷的赋存状态

砷是煤中常见的有害微量元素,由于其丰度较低,定量研究其赋存状态一直很困难。近年来,采用逐级化学提取实验方法对煤中不同赋存状态的砷进行了定量研究,综合分析这些研究可得出以下结论：①煤中砷的赋存状态包括硫化物态砷、有机态砷、砷酸盐态砷、硅酸盐态砷、水溶态和可交换态砷。总体上,硫化物态砷＞有机态砷＞砷酸盐态砷＞硅酸盐态砷＞水溶态和可交换态砷,但在不同的煤样品中,也表现出较大的差异性。②一般而言,煤中大部分砷存在于含砷黄铁矿中,含砷黄铁矿中的砷含量与黄铁矿的成因或类型有关。煤中的砷酸盐态砷主要与铁氧化物和氢氧化物共生;硅酸盐态砷主要进入粘土矿物晶格。③在砷含量较低的煤样品中,有机态砷含量较高,其中在褐煤和低煤级烟煤中,可提取出与腐殖酸和富里酸结合的砷。当前还难以确认有机态砷的化学结构。④贵州特高砷煤中砷的赋存状态较为复杂,在某些样品中与氧结合的有机态砷为主要的赋存状态。