煤矿酸性“老窑水”低Ca/Mg成因机制

石维芝; 赵春红; 梁永平; 韩占涛; 谢浩; 唐春雷

doi:10.11932/karst2022y10

煤矿酸性“老窑水”低Ca/Mg成因机制

doi: 10.11932/karst2022y10

石维芝^{1, 2,},
赵春红¹,
梁永平^1, ,,
韩占涛³,
谢浩¹,
唐春雷¹

1.
中国地质科学院岩溶地质研究所/自然资源部、广西岩溶动力学重点实验室, 广西桂林 541004
2.
中国地质大学(北京), 北京 100083
3.
生态环境部土壤与农业农村生态环境监管技术中心, 北京 100012

基金项目: 中国地质调查局地质调查项目 (DD20190334, DD20221758)；国家自然科学基金项目（41902256）

详细信息

作者简介:
石维芝（1996－），女，硕士研究生，研究方向：水文地质学。E-mail：1786908274@ qq.com

通讯作者:
梁永平( 1962－)，男，研究员，从事北方岩溶水调查研究。E-mail：lyp0261@ karst.ac.cn

中图分类号: P641.1；X752
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出版历程
- 收稿日期: 2022-01-10
- 刊出日期: 2022-08-31

Genetic mechanism analysis of low Ca/Mg value of acid goaf water in coal mine drainage

1.
Institute of Karst Geology, CAGS/Key Laboratory of Karst Dynamics, MNR&GZAR, Guilin,Guangxi 541004, China
2.
China University of Geosciences(Beijing), Beijing 100083, China
3.
Technical Centre for Soil, Agriculture and Rural Ecology and Environment, Ministry of Ecology and Environment, Beijing 100012, China

摘要

摘要: 山西省阳泉市山底河煤矿“老窑水”循环系统多年水质监测数据计算结果显示，煤矿酸性“老窑水”的Ca/Mg值普遍偏低，且存在Ca/Mg值随酸化程度的增强（SO₄²⁻含量增加或pH减小）而减小的规律。针对这一问题，结合研究区的地球化学物源条件，通过室内试验以及野外监测水样的石膏、方解石、白云石矿物饱和指数与pH变化关系，分析煤矿酸性“老窑水”低Ca/Mg值的成因机制。研究表明：区内石炭系－二叠系的煤系地层中碳酸盐岩夹层、分散状态分布的菱镁矿、黄铁矿是“老窑水”中Ca²⁺、Mg²⁺、SO₄²⁻的物质来源；在黄铁矿氧化水解形成的以硫酸根为主导的酸性溶液中（pH为2.0~4.5），代表硫酸对石膏、方解石、白云石可溶解性的饱和指数排序为石膏>方解石>白云石，受石膏在高浓度硫酸活性降低并发生沉淀、方解石溶解受Ca²⁺同离子效应抑制和饱和状态的平衡调节的综合影响，使Ca²⁺相对含量减少，由于MgSO₄溶度积大于CaSO₄，故Mg²⁺含量未受上述约束（或较低），脱白云岩化反应可因Ca²⁺含量随石膏沉淀而继续进行，加之区内有菱镁矿的溶解，使得Mg²⁺相对含量增加，最终出现了镁矿酸性“老窑水” Ca/Mg值低的结果。Ca/Mg值可作为煤矿酸性“老窑水”的污染特征指标，应用于环境影响评价。
- 山底河 /
- 煤矿酸性“老窑水” /
- 低钙镁比值特征指标 /
- 成因机制
Abstract: The calculation results of water quality monitoring of the acid mine drainage circulation system of Shandi river in Yangquan City, Shanxi Province for many years show that the Ca/Mg value of the acid goaf water in coal mine drainage is generally low. The average value of 257 groups of acid mine drainage samples was 1.14, the average value of 69 samples of mine drainage in the study area during the same period was 3.73, and the average value of 206 samples of karst groundwater was 5.30, and there is a law that the Ca/Mg value decreased with the increase of acidification degree (increases of SO₄²⁻ content or decreases of pH value). In response to this problem,combined with the geochemical source conditions of the study area, this paper analyzes the relationship between the saturation index of gypsum, calcite and dolomite minerals and pH value changes in laboratory tests and field monitoring water samples, so as to reveal the genetic mechanism of low Ca/Mg values of acid goaf water in coal mine drainage. The research results show that the scattered magnesite and pyrite in the carbonate interlayers in the Carboniferous-Permian coal measure strata in the study area are the material sources of Ca²⁺, Mg²⁺ and SO₄²⁻ in the goaf water; In the sulfate-dominated acidic solution formed by the oxidative hydrolysis of pyrite (pH value is in the range of 2.0 to 4.5), the saturation index representing the solubility of sulfuric acid to gypsum, calcite and dolomite is in the order of gypsum>calcite>dolomite,at the same time, with the increase of pH value, gypsum will occur in the precipitation reaction, the relative content of Ca²⁺ would decrease, and the relative content of Mg²⁺ would increase, which will eventually lead to the decrease of Ca/Mg value in the solution. Its chemical mechanism is, (1) When the pH value is in the range of 2 to 3, the dissolution of gypsum is inhibited by high concentration sulfuric acid, the solubility decreased rapidly with the increase of pH value, gypsum precipitation may occur,which have been confirmed in laboratory tests, and the content of Ca²⁺ decreased;When the pH value is in the range of 3 to 4.5, the gypsum in the samples is in a reaction equilibrium state with a slight change in the saturation index near zero. A slight increase in pH value will lead to the formation of gypsum precipitation from Ca²⁺ dissolved from calcite and dolomite. The content of Ca²⁺ cannot continue to increase, and the relative content of Mg²⁺ increases. (2) In the pH range of 2 to 4.5, the calcite is affected by the co-ion effect of Ca²⁺ and the ion-pair balance when the gypsum is saturated, the saturation index of all samples was maintained at about −4.4, irrespective of pH decrease. (3) However, the dissolution of dolomite was not affected by the above inhibition (the solubility of MgSO₄ in sulfuric acid solution is greater than that of CaSO₄), the Mg²⁺ and SO₄²⁻ content of the monitored samples have a significant positive correlation (the linear correlation coefficient reached 0.83). While dolomite forms gypsum precipitation with Ca²⁺ in the solution, de-dolomitization reaction occured sustainably, and there is dissolution of magnesite, which eventually increased the content of Mg²⁺ in acid water relative to the content of Ca²⁺, and the Ca/Mg value decreased. The Ca/Mg value can be used as an indicator of pollution characteristics of acid goaf water in coal mine drainage and applied to environmental impact assessment.
- Shandi river basin /
- acid goaf water in coal mine drainage /
- characteristic index of low Ca/Mg ratio /
- genetic mechanism.

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图 1 各监测点Ca/Mg值动态

Figure 1. Dynamic state of Ca/Mg value at each monitoring point

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图 2 各监测点Ca/Mg值与酸化程度关系

Figure 2. Relationship between Ca/Mg value and SO₄^2- at each monitoring point

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图 3 山底河流域地质略图与监测点分布图

1.二叠系下石合子组砂页岩, 2.二叠系山西组砂页岩及煤层, 3.石炭系上统太原组砂页岩夹灰岩及煤层, 4.石炭系中统本溪组铝土质泥岩、砂岩及铁矿; 5.中奥陶统碳酸盐岩, 6.钻孔, 7.小沟露天矿投影线, 8.地下水位线, 9.老窑水出流点, 10.地下水流向

Figure 3. Geological sketch map and distribution map of monitoring points inShandi river basin

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图 4 碳酸盐矿物在不同pH硫酸溶液中Ca²⁺、Mg²⁺含量变化曲线

Figure 4. Variation curves of Ca²⁺ and Mg²⁺ content of carbonate minerals in sulfuric acid solutions with different pH values

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图 5 水质监测样品的石膏、方解石、白云石饱和指数与pH关系图

Figure 5. Relationship between gypsum, calcite, dolomite saturation index and pH value in monitoring water samples

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图 6 野外样品的pH与SO₄^2-、HCO₃⁻、Ca²⁺、Mg²⁺的含量关系图

Figure 6. Relationship between pH value and SO₄^2-, HCO₃⁻, Ca²⁺, Mg²⁺ content of field water samples

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图 7 河底镇、跃进煤矿岩溶井Ca/Mg动态曲线

Figure 7. Dynamic curves of Ca/Mg of karst wells in Hedi town and Yuejin coal mine

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表 1 研究区煤矿“老窑水”及岩溶水相关水化学特征组分含量绘制表

Table 1. Relevant hydrochemical characteristic components of goaf water in acid mine drainage and karst water in the study area

样品类型	样品数/组	特征项	pH	Ca²⁺	Mg²⁺	SO₄²⁻	HCO₃⁻	Ca/Mg
样品类型	样品数/组	特征项		/mg·L⁻¹				Ca/Mg
煤矿“老窑水”	257	平均	3.64	394.51	592.28	7 707.64	86.29	1.14
		最大	8.02	1 817.00	2340.00	33 248.00	1 283.00	4.12
		最小	2.03	20.50	24.10	59.90	0.00	0.14
现采煤矿排水	69	平均	7.43	326.89	89.85	1 549.09	222.75	3.73
		最大	8.73	545.00	187.00	2 476.00	388.00	5.31
		最小	3.38	163.00	48.10	717.00	0.00	2.14
岩溶水	206	平均	7.44	290.92	59.56	729.26	269.95	5.30
		最大	8.29	517.00	115.00	1 248.00	316.00	19.19
		最小	6.51	79.10	18.50	140.00	172.00	2.14

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表 2 试验结束时各组合的Ca²⁺、Mg²⁺含量（单位：mg·L⁻¹）及Ca/Mg值

Table 2. Ca²⁺ and Mg²⁺ content (unit:mg·L⁻¹) and Ca/Mg value in each group at the end of the test

项目	菱镁矿			菱镁矿+方解石+白云石			菱镁矿+白云石
项目	pH=2	pH=4	pH=6	pH=2	pH=4	pH=6	pH=2	pH=4	pH=6
Mg	71.66	8.75	3.35	123.25	5.84	3.67	154.52	8.37	2.17
Ca	0.00	10.75	8.95	6.03	6.43	5.63	0.00	8.64	5.23
Ca-Mg	71.66	−2.00	−5.60	117.22	−0.59	−1.96	154.52	−0.27	−3.06
Ca/Mg	0.00	1.23	2.67	0.05	1.10	1.54	0.00	1.03	2.41

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