地下水硫酸盐溯源的进展、问题和发展趋势

靳孟贵; 张结; 张志鑫; 曹明达; 黄鑫

doi:10.19509/j.cnki.dzkq.2022.0161

地下水硫酸盐溯源的进展、问题和发展趋势

doi: 10.19509/j.cnki.dzkq.2022.0161

中国地质大学环境学院, 武汉 430078

基金项目:

国家自然科学基金项目 41877192

中国地质大学(武汉)中央高校基本科研业务费专项资金资助项目 CUGDCJJ202212

中国地质大学(武汉)中央高校基本科研业务费专项资金资助项目 CUGDCJJ202213

详细信息

作者简介:
靳孟贵(1957—)，男，教授，博士生导师，主要从事地下水与环境的教学和科研工作。E-mail: mgjin@cug.edu.cn

中图分类号: X141
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出版历程
- 收稿日期: 2021-12-07
- 网络出版日期: 2022-11-10

A review on source identification of dissolved sulfate in groundwater: Advances, problems and development trends

School of Environmental Studies, China University of Geosciences(Wuhan), Wuhan 430078, China

摘要

摘要:
识别地下水溶解性硫酸盐来源及其生物地球化学循环过程是保障饮用水安全和水生态安全的重要前提, 对于地下水资源的管理和保护具有重要的意义。在广泛查阅文献的基础上, 总结了不同地下水硫酸盐来源δ³⁴S_SO₄和δ¹⁸O_SO₄值域范围; 综述了地下水硫酸盐溯源及硫生物地球化学循环过程解析的研究进展, 指出了存在问题和发展趋势。地下水硫酸盐来源识别方法经历了水化学方法→单同位素→双同位素→多同位素和多示踪剂定性识别→定量评估的发展历程; 因特定地域来源的硫、氧同位素差异和生物地球化学转化过程等因素的影响, 地下水硫酸盐溯源尚存在较大的不确定性。建议在地下水流系统框架上结合土地利用分布, 布置采样点采集污染源和地下水样品, 测定水化学和硫酸盐的硫氧同位素值及其他辅助性示踪剂同位素值或浓度, 利用多学科、多方法充分融合研究区水文地球化学、渗流场、土地利用等信息, 解析地下水硫酸盐的来源及其贡献, 以支撑地下水资源保护和污染防治的科学实施。
- 地下水 /
- 硫酸盐 /
- 硫氧同位素 /
- 源解析
Abstract:
Effective identification of the sources and biogeochemical processes of dissolved sulfate in groundwater is an important prerequisite for ensuring drinking water safety and aquatic ecological security and is of significance to manage and protect groundwater resources. In this review, the sources of groundwater sulfate and the typical range ofδ³⁴S andδ¹⁸O isotope from different sulfate sources are summarized by reviewing the literature; the identification of sulfate sources and S biogeochemical cycles byδ³⁴S andδ¹⁸O isotope in sulfate is reviewed, and the existing problems and development trends are proposed. The source apportionment of groundwater sulfate sources has gone through the processes of hydrochemistry analysis→δ³⁴S isotope→dual isotope→qualitative identification of multiple isotopes and tracers→quantitative evaluation. Due to the differences in sulfur and oxygen isotopes and the biogeochemical transformation processes in a specific region, there is still a larger uncertainty in the determination of groundwater sulfate sources.It is proposed to arrange the sampling points for collecting pollution sources and groundwater samples on the framework of groundwater flow systems and land use distributions and to analyze the hydrochemical components and the sulfur and oxygen isotope values of sulfate and other complementary tracer isotope values and/or concentrations in a specific area. The sources and their contributions of groundwater sulfate are analyzed using multidisciplinary and multi-methods based on the full integration of hydrogeochemistry, seepage field, land use and other information in a study area for the scientific implementation of groundwater resource protection and pollution prevention.
- groundwater /
- sulfate /
- δ³⁴S_SO₄ and δ¹⁸O_SO₄ isotopes /
- source apportionment

HTML全文

图 1 不同SO₄^2-来源的特征值范围(据文献[3, 6, 14, 24-26, 29, 37-41])

黑色点虚线表示细菌异化SO₄^2-还原过程中硫和氧的分馏比值，该分馏比介于1.4:1和4:1之间^{[16, 36]}

Figure 1. Range of characteristic values of different SO₄^2- sources

下载: 全尺寸图片幻灯片

图 2 溶解硫酸盐的δ¹⁸O_SO₄与水的δ¹⁸O_H₂O的关系

a. Van Stempvoort等^[78]定义了硫化物氧化生成硫酸盐的实验区；b.根据Taylor等^[79]提出的硫化物氧化过程中水中的氧参与的百分比

Figure 2. Relationship between δ¹⁸O_SO₄ of dissolved sulfate and δ¹⁸O_H₂O of water

下载: 全尺寸图片幻灯片

图 3 微生物介导硫循环示意图^[96]

Figure 3. Schematic diagram of microbial-mediated sulfur cycling

下载: 全尺寸图片幻灯片

表 1 地下水SO₄²来源及识别方法

Table 1. Sources of SO₄^2- in groundwater and identification methods

时间	研究区	含水层类型	来源识别或定量方法	SO₄²来源	文献
2002	西班牙东北部	碎屑岩裂隙含水层	水化学和δ³⁴S	蒸发岩, 采矿废水和化肥	[12]
2016	山东枣庄市	岩溶含水层	水化学和δ³⁴S	石膏, 黄铁矿, 化肥和工业污水	[11]
1993	加拿大南萨斯喀彻温省	砂页岩裂隙含水层	水化学, δ³⁴S/δ¹⁸O	蒸发岩石膏	[49]
2015	河南焦作市	岩溶含水层孔隙含水层	水化学, δ³⁴S/δ¹⁸O	岩溶水: 降水, 石膏和原始土壤矿山废水: 石膏和硫化物; 孔隙水: 污水/污染土壤渗透	[24]
2018	贵州草海流域	岩溶含水层	水化学, δ³⁴S/δ¹⁸O	硫化物氧化	[19]
2013	波兰西里西亚	岩溶含水层	水化学, δ³⁴S/δ¹⁸O, 质量平衡混合模型	大气沉降, 硫化物氧化和蒸发岩溶解	[53]
2019	山东济南泉域	岩溶含水层	水化学, δ³⁴S/δ¹⁸O, 质量平衡混合模型	大气降水, 污水和土壤硫酸盐	[54]
2019	贵州黔西南州	岩溶含水层	水化学, δ³⁴S/δ¹⁸O, 质量平衡混合模型	黄铁矿氧化	[18]
2016	贵州织金八步	岩溶含水层	水化学, δ²H/δ¹⁸O, δ³⁴S/δ¹⁸O, 质量平衡混合模型	煤层硫化物氧化和石膏溶解	[50]
2020	华北平原	孔隙含水层	水化学, δ²H/δ¹⁸O, δ³⁴S/δ¹⁸O, SIAR	硫化物氧化和污水	[6]
2021	山东济南泉域	岩溶含水层	水化学, δ²H/δ¹⁸O, δ³⁴S/δ¹⁸O, Simmr	土壤硫酸盐, 污水和粪肥	[10]
2015	广西河池里湖	岩溶含水层	水化学, δ¹⁵N/δ¹⁸O, δ³⁴S, δ¹³C_DIC	工业和家庭燃煤燃烧	[17]
2005	德国南部	岩溶含水层	δ³⁴S/δ¹⁸O, ³H, δ¹³C_DIC	新水: 大气沉降和碳键S矿化; 老水: 岩溶含水层孔隙基质细菌硫酸盐还原	[55]
2010	菲律宾马尼拉	孔隙含水层	水化学, δ²H/δ¹⁸O, δ³⁴S/δ¹⁸O, ⁸⁷Sr/⁸⁶Sr	农业化肥和合成洗涤剂	[56]
2011	华北平原	孔隙含水层	水化学, δ²H/δ¹⁸O, δ³⁴S/δ¹⁸O, ¹⁴C	浅层地下水: 硫酸盐溶解和硫化物氧化; 深层地下水: 降水和有机S降解	[57]
2013	西班牙东北部	孔隙含水层	水化学, δ¹⁵N/δ¹⁸O, ³⁴S/δ¹⁸O, δ¹³C_DIC	猪粪和合成化肥	[31]
2017	西班牙东北部	岩溶含水层	水化学, δ²H/δ¹⁸O, δ¹⁵N/δ¹⁸O, δ³⁴S/δ¹⁸O, δ¹¹B, δ¹³C_DIC	污水和矿物肥料	[58]
2020	墨西哥蒙特雷	岩溶含水层	水化学, δ²H/δ¹⁸O, δ¹⁵N/δ¹⁸O, δ³⁴S/δ¹⁸O, HCA/PCA分析, MixSIAR	大气沉降, 蒸发岩溶解和污水	[14]
2021	墨西哥东北部	海岸含水层	SOM法, δ¹⁵N/δ¹⁸O, δ³⁴S/δ¹⁸O, MixSIAR	海水入侵和土壤硫酸盐	[26]
2021	山西晋祠泉域	岩溶含水层	水化学, δ²H/δ¹⁸O, δ³⁴S, ¹⁴C, δ¹³C_DIC, 微生物群落分析	煤矿排水和生活污水	[45]
2022	比利牛斯山东南	岩溶含水层	δ¹⁵N/δ¹⁸O, δ³⁴S/δ¹⁸O, 反向地球化学模拟, Simmr	石膏溶解	[20]

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