湘西南典型煤矿区地表水和地下水水化学特征及控制因素

许真; 郑杰; 戴亮亮; 李腾

doi:10.11932/karst2026y006

湘西南典型煤矿区地表水和地下水水化学特征及控制因素

doi: 10.11932/karst2026y006

许真^1,,
郑杰¹,
戴亮亮¹,
李腾^1, ,

中国地质调查局长沙自然资源综合调查中心, 湖南长沙 410600

基金项目: 中国地质调查局项目（DD20230480，DD20251300118， DD202605101604）

详细信息

作者简介:
许真（1988－），男，高级工程师，硕士，研究方向为地下水环境；E-mail：845735915@qq.com

通讯作者:
李腾（1986－），男，高级工程师，硕士，研究方向为水工环方面；E-mail：503201333@qq.com。

中图分类号: P641.3
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- 被引次数: 0
出版历程
- 收稿日期: 2025-05-29
- 录用日期: 2025-12-05
- 修回日期: 2025-11-27
- 网络出版日期: 2026-03-26

Hydrochemical Characteristics and Control Factors of Surface Water and Groundwater in a Typical Coal Mining Area of Southwestern Hunan

XU Zhen^1
,,
ZHEN Jie¹,
DAI Liangliang¹,
LI Teng^{1
, ,}

Changsha General Survey of Natural Resources Centre, China Geological Survey, Changsha, Hunan 410600, China

摘要

摘要: 为探究湘西南典型煤矿区地表水和地下水水化学特征和控制因素，采集13组地下水（含4组矿井水）和16组地表水样品，采用数理统计方法、Piper三线图、Gibbs图以及离子比例系数等多元分析手段，对湘西南典型煤矿区地表水和地下水的水文地球化学特征进行了系统分析，并探讨了其水化学特征的空间演变特征。结果表明，湘西南典型煤矿区地表水和地下水呈弱碱性，水化学主导类型为HCO₃·SO₄−Ca型水。研究区地表水系主要水化学指标呈现石桥溪（北支）＞石燕溪（下游）＞石井溪（南支）的空间分布格局，而pH和${\rm{HCO}}_3^{-}$浓度则呈相反趋势。分析表明，南支石井溪未受到矿井水明显影响，水化学类型为HCO₃·SO₄−Ca型。北支石桥溪受矿井水影响明显，水化学类型为SO₄−Ca型。岩石风化溶解作用和人类活动两大因素控制着研究区水化学演化。水岩作用以碳酸盐矿物的溶解为主，碳酸盐岩的溶解制约Ca²⁺、Mg²⁺和${\rm{HCO}}_3^{-}$等离子的变化，${\rm{SO}}_4^{2-}$主要来源于石炭系梓门桥组灰岩层石膏夹层溶解和煤系地层中硫铁矿氧化。地表水和地下水中Cl⁻、${\rm{NO}}_3^{-}$主要是来源于生活污水和农业活动。本研究阐明了湘西南典型煤矿区地表水和地下水水化学演化特征及其驱动机制。多指标综合分析矿井水对区域地表水和地下水水化学演变规律提供了较为系统的方法，可为类似区域研究提供借鉴。
- 湘西南煤矿区 /
- 地表水和地下水 /
- 矿井水 /
- 水化学特征 /
- 水岩作用 /
- 控制因素.
Abstract: The southwestern Hunan region is a significant coal resource accumulation zone in China. Within its coal mining areas, carbonate rocks and coal-bearing clastic rock strata are distributed in an interbedded manner, resulting in complex geological structures. Hydrogeochemical processes are jointly influenced by mining activities and karstification. This study focuses on a typical small watershed in southwestern Hunan, with a total area of approximately 20.51 km². The landform is predominantly characterized by dissolution-tectonic features of low mountains and wide valleys, and denudation-tectonic features of clastic rock hills and valleys. The regional strata are primarily composed of the Quaternary System of the Cenozoic Erathem and the Carboniferous System of the Upper Paleozoic Erathem. Groundwater types mainly include pore water in loose rocks, fissure-karst water in carbonate rocks, and pore-fissure water in clastic rocks. To systematically reveal the hydrochemical characteristics and dominant controlling factors of surface water and groundwater in this typical coal mining area of southwestern Hunan, 16 surface water and 13 groundwater samples (including 4 mine water samples) were collected. A comprehensive multi-indicator analysis was conducted using mathematical statistical analysis, Piper trilinear diagrams, Gibbs diagrams, and ion ratio methods to investigate the hydrochemical composition, spatial distribution patterns, and formation mechanisms of various water bodies in the region.The results indicate that both surface water and groundwater in the study area are generally weakly alkaline, with pH values ranging from 7.06 to 8.33 and TDS values between 236 and 884 mg·L⁻¹. Groundwater is minimally affected by mine water, with its hydrochemical types predominantly being HCO₃·SO₄-Ca, followed by HCO₃-Ca. For surface water, the major hydrochemical indicators (${\rm{SO}}_4^{2-}$, Ca²⁺, Mn, TDS, and toxic metals) exhibited the spatial distribution pattern: Shiqiao Creek (North Branch) > Shiyan Creek (Downstream) > Shijing Creek (South Branch). In contrast, the trends for pH and ${\rm{HCO}}_3^{-}$ concentration were the opposite. The North Branch (Shiqiao Creek), influenced by mine water input, has a SO₄-Ca hydrochemical type. The South Branch (Shijing Creek), less affected by mining activities, is primarily of the HCO₃·SO₄-Ca type. After their confluence, the main stream of Shiyan Creek generally exhibits a SO₄-Ca hydrochemical type.Gibbs diagrams show that most samples from the study area plot within the rock weathering dominance field, indicating that the chemical composition of the water bodies is primarily controlled by mineral dissolution within the aquifers, with relatively weaker influences from evaporation concentration and atmospheric precipitation. However, most mine water samples deviate from the model's distribution range, and their spatial heterogeneity may originate from geochemical disturbances caused by historical coal mining activities. The end-member diagram illustrating the relative contributions of rock weathering and dissolution shows that regional water samples are concentrated towards the carbonate rock end-member, with some samples trending towards the silicate rock end-member. Ion ratio analysis indicates that Ca²⁺, Mg²⁺, and ${\rm{HCO}}_3^{-}$ are mainly derived from the dissolution of carbonate minerals. ${\rm{SO}}_4^{2-}$ primarily originates from the dissolution of gypsum interbeds within the Zimenqiao Formation limestone and the oxidation of pyrite in the coal-bearing strata. Cl⁻ and ${\rm{NO}}_3^{-}$ are mainly attributed to inputs from human activities such as domestic sewage and agricultural fertilization. Mine water samples exhibit significantly higher concentrations of Fe and Mn and are locally acidic, indicating that historical mining disturbances have enhanced sulfide oxidation, creating an acidic environment that promotes the dissolution and migration of metallic elements. In surface water, the concentrations of ions like ${\rm{SO}}_4^{2-}$, Ca²⁺, and TDS show a positive correlation with the intensity of mine water input, reflecting the significant impact of mining activities on surface water chemistry.Principal Component Analysis results reveal that groundwater chemical composition is primarily controlled by three factors: PC1, with a variance contribution of 39.65%, reflects the dominant role of carbonate rock dissolution on regional groundwater chemistry; PC2, with a variance contribution of 36.08%, represents the influence of Cl⁻ and Na⁺ inputs from human activities; PC3, with a variance contribution of 11.35%, signifies the effect of gypsum dissolution. Surface water chemistry is mainly governed by three factors: PC1, with a variance contribution of 54.28%, characterizes the dual influence of gypsum dissolution and coal seam sulfide oxidation on surface water chemistry; PC2, with a variance contribution of 24.69%, embodies the coupled effects of silicate weathering from the Carboniferous Ceshui Formation and anthropogenic NaCl input; PC3, with a variance contribution of 11.80%, reflects ${\rm{NO}}_3^{-}$ input from agricultural fertilization.Integrating the multi-indicator analysis results, rock weathering/dissolution and human activities are identified as the two main factors controlling the hydrochemical evolution in the study area. Specifically, carbonate rock dissolution governs the variations of Ca²⁺, Mg²⁺, and ${\rm{HCO}}_3^{-}$; sulfide oxidation and gypsum dissolution control ${\rm{SO}}_4^{2-}$ enrichment; and human activities primarily influence the distribution of Cl⁻ and ${\rm{NO}}_3^{-}$. This study systematically reveals the hydrochemical characteristics and formation mechanisms of surface water and groundwater in a typical coal mining area of southwestern Hunan, clarifying the hydrochemical relationships and spatial distribution patterns within the "surface water-groundwater-mine water" ternary system. The results demonstrate that the coupled effects of carbonate rock weathering/dissolution and sulfide oxidation from coal-bearing strata jointly determine the chemical evolution of regional water bodies, while human activities have intensified ion migration in localized areas. The comprehensive multi-indicator analytical methodology proposed in this study can provide a scientific basis and methodological reference for identifying hydrochemical characteristics, preventing and controlling pollution, and protecting regional water resources in karst coal mining areas.
- Southwestern Hunan coal mining area /
- surface water and groundwater /
- mine water /
- hydrochemical characteristics /
- water-rock interaction /
- controlling factors

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图 1 区域地表水和地下水采样点分布图

Figure 1. Distribution map of regional surface water and groundwater sampling points

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图 2 研究区水文地质剖面图

Figure 2. Hydrogeological profile of the study area

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图 3 研究区水体主要离子箱体图

Figure 3. Boxplot of regional hydrochemical components

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图 4 地表水水化学参数空间变化图

Figure 4. Spatial variations in hydrochemical parameters for surface water

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图 5 区域水样piper三线图

Figure 5. Piper trilinear diagram of regional water samples

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图 6 研究区不同水体Gibbs图

Figure 6. Gibbs diagram of different water bodies in the study area

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图 7 研究区岩石风化溶解相对贡献端元图

Figure 7. End element diagram showing the relative contribution of rock weathering and dissolution in the study area

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图 8 区域水体主要离子比值关系

Figure 8. Geochemical controls on major ion ratios in regional water bodies

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图 9 人类活动对水体水化学组分影响

Figure 9. Impacts of anthropogenic activities on hydrochemical composition of water bodies

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表 1 区域不同水体水化学特征统计

Table 1. Statistical analysis of hydrochemical characteristics in regional water bodies

类型		项目	pH	TDS	K⁺	Na⁺	Ca²⁺	Mg²⁺	Cl⁻	${\rm{SO}}_4^{2-}$	${\rm{HCO}}_3^{-}$	${\rm{NO}}_3^{-}$	Fe	Mn	有害金属
地下水	地下水 (n=9)	最小值	7.06	256.00	0.17	1.21	66.90	7.07	1.61	14.90	12.10	0.21	0.01	0.01	2.85
		最大值	8.07	884.00	29.30	25.10	212.20	29.20	27.90	317.40	289.80	27.20	0.20	0.38	17.71
		平均值	7.78	466.33	8.10	9.58	143.32	19.66	10.44	80.03	203.68	12.95	0.04	0.10	7.09
		标准偏差	0.31	213.62	9.64	8.79	55.68	8.11	7.81	94.48	91.68	8.98	0.07	0.13	5.07
		变异系数	4.05	45.81	119.02	91.72	38.85	41.23	74.79	118.06	45.01	69.36	159.49	124.63	71.57
	矿井水 (n=4)	最小值	2.42	938.00	1.13	1.67	205.30	44.40	1.21	551.50	2.50	0.00	0.12	2.41	22.32
		最大值	7.14	3536.00	15.90	74.80	463.80	105.30	9.14	1138.00	66.50	4.05	267.50	40.32	1894.60
		平均值	4.85	1994.50	6.78	20.39	296.65	71.70	4.06	727.85	20.19	1.39	75.87	12.53	559.89
		标准偏差	2.09	1098.21	6.50	36.28	114.38	25.61	3.48	278.83	31.04	1.91	128.83	18.55	897.73
		变异系数	43.09	55.06	95.98	177.94	38.56	35.72	85.81	38.31	153.78	137.71	169.81	147.97	160.34
地表水	北支石桥溪(n=6)	最小值	7.58	571.00	4.71	2.48	130.50	25.30	5.83	335.70	11.90	1.27	0.03	1.00	20.38
		最大值	7.95	863.00	5.40	4.49	206.60	29.90	7.08	578.70	141.60	2.87	0.44	3.62	137.89
		平均值	7.85	712.00	5.01	3.86	170.55	27.22	6.37	446.67	105.33	2.23	0.14	1.75	47.30
		标准偏差	0.13	96.40	0.30	0.72	25.06	1.79	0.54	78.64	46.83	0.57	0.15	0.94	44.62
		变异系数	1.71	13.54	6.03	18.70	14.69	6.56	8.47	17.61	44.46	25.60	105.03	53.87	94.34
	南支石井溪(n=7)	最小值	8.13	236.00	0.80	0.96	76.80	5.91	2.26	68.70	138.10	0.02	0.01	0.02	3.71
		最大值	8.33	392.00	5.34	5.34	103.90	22.50	8.64	121.20	233.00	3.40	0.10	0.32	24.98
		平均值	8.27	350.40	3.73	3.14	95.34	16.60	5.97	104.52	187.90	1.59	0.06	0.11	9.05
		标准偏差	0.08	64.68	2.21	1.98	10.76	6.27	2.89	21.07	36.68	1.24	0.03	0.12	9.06
		变异系数	0.99	18.46	59.16	63.16	11.28	37.74	48.43	20.16	19.52	78.10	60.83	107.15	100.11
	汇合石燕溪(n=3)	最小值	7.96	602.00	5.17	5.10	148.60	23.50	7.64	341.50	128.50	1.93	0.03	0.85	26.65
		最大值	8.02	634.50	5.28	6.12	157.30	24.00	8.09	374.40	140.50	1.99	0.09	1.16	41.94
		平均值	7.99	618.25	5.23	5.61	152.95	23.75	7.87	357.95	134.50	1.96	0.06	1.00	34.29
		标准偏差	0.04	22.98	0.08	0.72	6.15	0.35	0.32	23.26	8.49	0.04	0.04	0.22	10.81
		变异系数	0.53	3.72	1.49	12.86	4.02	1.49	4.05	6.50	6.31	2.16	75.59	22.27	31.53
注：变异系数和pH无量纲；最小值、最大值、平均值、标准偏差单位mg∙L⁻¹；有害金属为Cd、Co、Ni，单位为μg∙L⁻¹。

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表 2 矿井水水化学特征

Table 2. Hydrochemical characteristics of mine water

矿井水	pH	TDS	K⁺	Na⁺	Ca²⁺	Mg²⁺	Cl⁻	${\rm{SO}}_4^{2-}$	${\rm{HCO}}_3^{-}$	${\rm{NO}}_3^{-}$	Fe	Mn	有害金属
M1	7.14	938.00	3.35	2.36	205.30	44.40	2.95	668.30	66.50	0.00	0.35	2.40	22.31
M2	2.42	1816.00	6.72	2.72	265.50	62.50	2.94	553.60	2.50	4.05	35.50	2.83	282.52
M3	5.89	3536.00	15.90	74.80	463.80	105.30	9.14	1138.00	9.24	0.00	267.50	4.58	40.04
M4	3.93	1688.00	1.13	1.67	252.00	74.60	1.21	551.50	2.50	1.50	0.12	40.32	1894.66
注：pH无量纲；有害金属为Cd、Co、Ni，单位为μg∙L⁻¹；其余单位mg∙L⁻¹。

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表 3 研究区不同水体主成分分析

Table 3. PCA of water bodies in the study area

指标	主成分
	地表水n=16			地下水n=9
	PC1	PC2	PC3	PC1	PC2	PC3
${\rm{HCO}}_3^{-}$	−0.881	−0.027	0.033	0.932	−0.306	0.091
Cl⁻	−0.091	0.984	0.000	0.464	0.833	0.081
${\rm{SO}}_4^{2-}$	0.832	0.168	0.495	0.258	−0.037	0.939
${\rm{NO}}_3^{-}$	0.019	−0.043	0.962	−0.212	0.678	0.586
K⁺	0.208	0.902	0.197	−0.43	0.869	0.104
Na⁺	0.093	0.942	0.032	0.005	0.973	−0.05
Ca²⁺	0.754	0.207	0.581	0.808	0.046	0.109
Mg²⁺	0.542	0.271	0.751	0.862	0.061	0.302
TDS	0.761	0.212	0.594	0.675	0.302	0.632
pH	−0.878	0.061	−0.073	0.614	−0.49	−0.242
特征值	5.428	2.469	1.180	3.965	3.609	1.135
贡献率	54.279	24.691	11.802	39.652	36.087	11.351
累计贡献率	54.279	78.970	90.773	39.652	75.739	87.090

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