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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

赵欣 孙书堂 谢先军

赵欣, 孙书堂, 谢先军. 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[J]. 地质科技通报, 2021, 40(2): 131-137. doi: 10.19509/j.cnki.dzkq.2021.0141
引用本文: 赵欣, 孙书堂, 谢先军. 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[J]. 地质科技通报, 2021, 40(2): 131-137. doi: 10.19509/j.cnki.dzkq.2021.0141
Zhao Xin, Sun Shutang, Xie Xianjun. Synthesis of thioarsenate compounds and their occurrence characteristics in groundwater: A case study of Datong Basin[J]. Bulletin of Geological Science and Technology, 2021, 40(2): 131-137. doi: 10.19509/j.cnki.dzkq.2021.0141
Citation: Zhao Xin, Sun Shutang, Xie Xianjun. Synthesis of thioarsenate compounds and their occurrence characteristics in groundwater: A case study of Datong Basin[J]. Bulletin of Geological Science and Technology, 2021, 40(2): 131-137. doi: 10.19509/j.cnki.dzkq.2021.0141

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

doi: 10.19509/j.cnki.dzkq.2021.0141
基金项目: 

国家自然科学基金项目 41807203

详细信息
    作者简介:

    赵欣(1979—),男,博士,主要从事环境与安全工程相关领域的研究工作。E-mall:841143698@qq.com

    通讯作者:

    谢先军(1979—),男,教授,博士生导师,主要从事地下水污染与修复、同位素水文学、同位素测试分析方面的研究工作。E-mall:xjxie@cug.edu.cn

  • 中图分类号: X143

Synthesis of thioarsenate compounds and their occurrence characteristics in groundwater: A case study of Datong Basin

  • 摘要: 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0.01 μg/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209.90 μg/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。

     

  • 图 1  硫代砷酸盐HPLC-ICPMS色谱图

    Figure 1.  HPLC-ICPMS chromatogram of thioarsenate

    图 2  常规法及水热法合成硫代砷酸盐对比图

    Figure 2.  Comparison of conventional and hydrothermal synthesis of thioarsenate

    图 3  硫代砷化合物保存测试

    Figure 3.  Preservation test of thioarsenate

    图 4  大同盆地地下水中的砷形态

    Figure 4.  Arsenic speciation in groundwater of the Datong Basin

    图 5  大同盆地地下水硫代砷酸盐赋存规律

    Figure 5.  Occurrence of thioarsenate in groundwater of the Datong Basin

    表  1  HPLC-ICPMS测试硫代砷酸盐的参数条件

    Table  1.   Parameters of HPLC-ICPMS thioarsenate test method

    液相色谱参数 电感耦合等离子体质谱条件
    流动相A:0.1 mol/L NaOH 等离子射频功率:1 400 W
    流动相B:超纯水 雾化器气体流量:1.00 L/min
    0~7 min:20% A As监测质荷比:m/z=75
    7~17 min:20% A→100% A S监测质荷比:m/z=32
    17~25 min:100% A 采集时间:28 min
    25~28 min:100% A→20% A
    注:上述流动相均经脱气处理
    下载: 导出CSV

    表  2  大同盆地地下水的水化学组成及砷形态

    Table  2.   Water chemistry composition and arsenic speciation of the groundwater in Datong Basin

    样品编号 总砷 亚砷酸盐 砷酸盐 一硫代砷酸盐 二硫代砷酸盐 三硫代砷酸盐 四硫代砷酸盐 其他砷物种 硫化物ρB/(μg·L-1) pH Eh/mV
    ρB/(μg·L-1)
    sy-1 4.47 3.31 1.16 ND ND ND ND 0.00 9 7.77 90.0
    sy-3 0.64 0.06 0.58 ND ND ND ND 0.00 3 7.73 126.1
    sy-4 693.22 642.41 48.45 2.36 ND ND ND 0.00 13 8.00 -98.5
    sy-5 197.78 2.16 195.62 ND ND ND ND 0.00 ND 8.63 113.6
    sy-6 318.75 125.89 168.65 21.14 1.55 ND ND 1.52 32 8.42 -36.2
    sy-7 117.73 2.31 112.51 1.02 ND ND ND 1.89 33 8.74 69.7
    sy-8 384.31 0.35 383.76 ND ND ND ND 0.00 20 8.85 126.2
    sy-9 3.34 0.24 3.10 ND ND ND ND 0.00 25 7.56 73
    sy-10 37.00 4.36 32.64 ND ND ND ND 0.00 5 7.81 -47.6
    sy-13 26.32 0.46 25.86 ND ND ND ND 0.00 3 7.88 39.5
    sy-21 133.38 88.66 36.18 5.71 2.83 ND ND 0.00 33 8.18 -113.6
    sy-25 88.69 35.78 31.28 15.96 4.23 ND ND 1.44 199 8.33 -104.6
    sy-27 614.66 343.67 60.25 82.33 125.79 1.78 ND 0.85 1 137.5 8.02 -129.2
    sy-32 4.35 1.11 3.24 ND ND ND ND 0.00 3 7.51 47.7
    sy-38 102.36 0.64 101.35 ND ND ND ND 0.37 6 8.05 52.5
    注:ND为未检出;①色谱分离后得到的未知砷形态
    下载: 导出CSV
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  • 收稿日期:  2020-04-23

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