Simultaneous Quantitative Analysis of Multiple Methylthiolated Arsenates in Geothermal Water
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摘要: 地热水中的砷含量常远超过其他类型天然水体，其形态分析具有重要环境地球化学意义；甲基硫代砷酸盐在特定水环境条件下可能成为砷的一种不可忽视的形态，但其环境地球化学研究几为空白.本研究合成了甲基硫代砷酸盐标准，建立了可同时定量测试天然水中多种甲基硫代砷酸盐（包括一甲基一硫代砷酸盐、一甲基二硫代砷酸盐、一甲基三硫代砷酸盐、二甲基一硫代砷酸盐、二甲基二硫代砷酸盐）及砷的其他常见形态的离子色谱‒电感耦合等离子体质谱联用系统（IC-ICP-MS）及其方法，并分析了典型地热水样品中砷的形态分布，可为今后不同类型水环境中甲基硫代砷酸盐的地球化学研究奠定分析方法基础.Abstract: Geothermal waters generally have far higher arsenic concentrations than other types of natural waters, and analysis of arsenic speciation in geothermal waters is of great environmental geochemical significance. Methylthiolated arsenates are non-negligible arsenic species under special aqueous environmental conditions, while little environmental geochemical studies of methylthiolated arsenates have been done so far. In this work, various methylthiolated arsenates standards were synthesized, and an ion chromatography coupled to inductively coupled plasma-mass spectrometry, capable of determining concentrations of common arsenic species as well as methylthiolated arsenates in natural waters including monomethylmonothioarsenate (MMMTA), monomethyldithioarsenate (MMDTA), monomethyltrithioarsenate (MMTTA), dimethylmonothioarsenate (DMMTA), and dimethyldithioarsenate (DMDTA), was set up. Furthermore, the arsenic speciation in a typical geothermal water sample was analyzed. The efforts made in this study produced an analytical method basis for future geochemical studies of methylthiolated arsenates in aqueous environments.
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图 1 三种甲基硫代砷酸盐合成产物溶液的ESI-HR-MS谱图
Fig. 1. Analytical ESI-HR-MS results of the solution samples of three synthetic solid methylthiolated arsenates
图 2 甲基/无机硫代砷酸盐合成产物溶液的IC-ICP-MS谱图
黑色倒三角为目标砷形态色谱峰；灰色倒三角为商业标准砷形态色谱峰
Fig. 2. Analytical IC-ICP-MS results of the solution samples of synthetic solid methylated and inorganic thioarsenates
图 3 高初始S/As比条件下MMA(Ⅴ)巯基化最终产物的IC-ICP-MS谱图
初始S/As摩尔比为20；pH为3；反应时间为4 h；实线为产物谱图，虚线为砷或硫的标准物质在本测试方法下的谱图
Fig. 3. Analytical IC-ICP-MS results of final products of MMA(Ⅴ) thiolation at a high initial S/As ratio
图 4 高初始S/As比条件下MMA(Ⅴ)巯基化反应最终产物的ESI-HR-MS谱图
初始S/As摩尔比为20；pH为3；反应时间为4 h
Fig. 4. Analytical ESI-HR-MS results of final products of MMA(Ⅴ) thiolation at a high initial S/As ratio
图 5 四种标准砷形态测试标准曲线
Fig. 5. Calibration curves for quantitative analysis of four standard arsenic species
图 6 龙陵邦腊掌代表性地热水样品中甲基硫代砷酸盐形态分析结果
Fig. 6. Analytical results of methylthiolated arsenates in a typical geothermal water sample collected from the Banglazhang hydrothermal area, Longling
表 1 各种甲基硫代砷酸盐及其脱质子产物的理论质荷比
Table 1. Theoretic mass to charge ratios of various methylthiolated arsenates and their deprotonated products
砷形态 化学结构式 理论m/z 一甲基一硫代砷酸盐（MMMTA） H2AsS(CH3)O2 - HAsS(CH3)O2- 154.915 3 AsS(CH3)O22- 76.954 0 二甲基一硫代砷酸盐（DMMTA） HAsS(CH3)2O - AsS(CH3)2O- 152.936 1 二甲基二硫代砷酸盐（DMDTA） HAsS2(CH3)2 - AsS2(CH3)2- 168.913 2 
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