巫山官渡河流域黑色岩系中镉元素在地下水系统中的迁移特征研究

刘永旺; 朱宗林; 李海; 柯青青; 罗波; 刘进; 邓鑫钱; 张永文

doi:10.11932/karst20250203

巫山官渡河流域黑色岩系中镉元素在地下水系统中的迁移特征研究

doi: 10.11932/karst20250203

1.
重庆市地质矿产勘查开发局川东南地质大队, 重庆 400038
2.
重庆市地质矿产勘查开发局 107 地质队, 重庆 401120

基金项目: 重庆市规划和自然资源局地质矿产勘查类项目（ZC-2021109、21C01719-06）

详细信息

作者简介:
刘永旺（1985-），男，高级工程师，主要从事水文地质调查、区域地质调查。E-mail：364995909@qq.com

中图分类号: P641.3
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出版历程
- 收稿日期: 2024-08-30
- 录用日期: 2025-02-14
- 修回日期: 2025-01-21
- 刊出日期: 2025-04-20

Study on the migration characteristics of cadmium element in the black shales of the groundwater system in the Guandu River Basin of Wushan area

1.
Southeast Sichuan Geological Team, Chongqing Bureau of Geology and Minerals Exploration, Chongqing 400038, China
2.
Geological Team 107 of Chongqing Bureau of Geology and Minerals Exploration and Development, Chongqing 401120, China

摘要

摘要: 巫山地区二叠系黑色岩系有害元素Cd高背景值突出，表层土壤已受到污染，对地下水的影响尚不清楚。本次工作以巫山官渡河流域为研究区，通过野外调查、资料收集、数据分析、水样测试等方法，分析研究区二叠系黑色岩系有害元素Cd对地下水的影响，以期揭示Cd在岩石—土壤—水中的运移特征。结果表明：（1）研究区含Cd地下水样均来自该流域发源于二叠系黑色岩系的岩溶地下水系统，水样具有典型的碳酸盐岩岩溶的化学特征，含Cd水样与不含Cd水样最显著的差别是含Cd水样${\rm{SO}}_4^{2-}$平均含量是不含Cd水样的3倍。（2）研究区内二叠系黑色岩性中的Cd含量较高，以二叠系孤峰组为最高，岩石风化成土壤后Cd依旧富集，但含量大幅降低；Cd通过溶滤作用进入地下水系统，是研究区含地下水中Cd的主要来源，Cd与${\rm{SO}}_4^{2-}$具有极显著正相关。（3）煤矿开采改变了地下水的运动路径，强化了溶滤作用，Cd在坑道涌水中富集作用加强，煤矿坑道涌水中Cd含量迅速增高，相应TDS也增高，水质变差，具有潜在风险，不宜作为引用水源。研究区三叠系岩溶地下水系统水量丰富，稀释了二叠系岩溶地下水中Cd的浓度，降低了Cd污染的风险。（4）Cd在岩石中赋存状态以碳酸盐矿物为主，风化后Cd多数溶解或转化其它可迁移形态，土壤的酸化使得Cd容易迁入水体，增加环境风险。通过饱和指数分析Cd地下水在迁移过程中尚未达到饱和。
- 官渡河流域 /
- 黑色岩系 /
- 地下水系统 /
- 镉污染 /
- 镉迁移
Abstract: The Permian black shale in the Wushan area is characterized by high background values of harmful trace elements, among which cadmium (Cd) is particularly prominent. These elements can easily enter groundwater systems through rock weathering, soil erosion, and human activities such as coal mining, thus posing potential threats to regional ecosystems and public health. However, previous studies have predominantly focused on Cd accumulation in soil and crops, while paying less attention to the migration characteristics and pollution mechanisms of Cd in groundwater systems. This study employs a multidisciplinary approach, integrating techniques from geology, hydrology, geochemistry, and environmental science, to systematically investigate the migration characteristics of Cd in the Guandu River Basin. The primary research methods include field surveys, water sampling and testing, data analysis, and geochemical modeling. By examining the pathways and mechanisms of Cd migration from black shale to groundwater, this study reveals the transport patterns of Cd within the rock–soil–groundwater system, clarifies its pollution mechanisms, and provides a scientific basis for environmental protection and resource utilization.Analysis of 40 groundwater samples revealed that eight samples contained detectable levels of Cd, ranging from 0.0001 mg·L⁻¹ to 0.0036 mg·L⁻¹, while Cd was undetectable in the other 32 samples. The pH values of Cd-containing samples ranged from 7.16 to 8.26, indicating neutral conditions. The average sulfate (SO$_4^{2-} $) concentration in Cd-containing samples was 67.84 mg·L⁻¹, three times higher than that in Cd-free samples (22.81 mg·L⁻¹), highlighting a strong correlation between SO$_4^{2-} $ and Cd migration. Additionally, the Total Dissolved Solids (TDS) values in Cd-containing samples ranged from 215 mg·L⁻¹ to 365 mg·L⁻¹, with an average of 268.56 mg·L⁻¹, indicating moderately hard to hard water. Research findings show that Cd-containing groundwater in the Guandu River Basin primarily originates from the karst groundwater system of the Permian black shale. The Gufeng Formation within the Permian System exhibited the highest Cd content. Although Cd remained enriched in soils derived from weathered rocks, its concentration significantly decreased. Cd entered the groundwater system through leaching, which is the main source of Cd in the groundwater of the study area. Coal mining activities have significantly altered the groundwater flow paths and intensified leaching effects, leading to Cd enrichment in mine gushing water. The highest Cd concentration detected was 0.0036 mg·L⁻¹ in gushing water (Sample S131) in an abandoned coal mine, indicating that coal mining activities are a significant anthropogenic factor contributing to Cd contamination. Additionally, TDS values in mine gushing water increased sharply, resulting in water quality deterioration and posing potential environmental risks. The Triassic karst groundwater system can effectively dilute Cd concentrations. This system is characterized by abundant water resources and demonstrates significant dilution effects on Cd concentrations in Permian karst water. For example, Cd was detected in the Longdong Underground River (Sample S039) during both the dry season and wet season, but its concentration was only 0.0003 mg·L⁻¹, which is far lower than that in mine gushing water. This dilution effect effectively reduces the risk of Cd contamination. Geochemical modeling revealed that calcite and dolomite in groundwater are close to saturation, while cadmium sulfate and cadmium carbonate have not yet reached saturation. This indicates that Cd has the potential for further enrichment in groundwater. Cd in rocks mainly exists in carbonate minerals (19%−66%). Analysis of Cd speciation in soil shows that Cd primarily exists in the forms of iron-manganese oxide-bound (25.03%) and residual (24.22%) fractions, with the smallest proportion in the water-soluble fraction (0.63%), indicating that soluble Cd in soils is mostly leached into groundwater through weathering, and soil acidification further enhances the dissolution and migration of Cd.This study elucidates the migration mechanisms and contamination risks of Cd within the black shale–soil–groundwater system, offering essential theoretical support for controlling Cd contamination in similar regions. The findings regarding Cd enrichment in coal mine gushing water provide scientific evidence for groundwater protection and pollution management in mining areas. By clarifying the impact of soil acidification on Cd migration, this study underscores the significance of controlling soil acidification for regional ecological restoration and environmental protection. Additionally, this study also highlights the dilution effect of Triassic karst groundwater on Cd pollution, offering guidance for the sustainable development and utilization of groundwater in the region. The results of this study can serve as a reference for ecological conservation in the Wushan area and other regions characterized by black shale.
- the Guandu River Basin in Wushan area /
- black shale /
- groundwater system /
- cadmium contamination /
- cadmium migration

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图 1 研究区位置及概况

Figure 1. Location and general situation of the study area

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图 2 研究区水文地质图及采样点位

Figure 2. Hydrogeological map and sampling sites of the study area

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图 3 地下水水样Durov图

Figure 3. Durov diagram of the groundwater samples

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图 4 研究区地下水Cd分布与表层土壤Cd含量关系

Figure 4. Relationship between Cd distribution in groundwater and Cd content in surface soil in the study area

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图 5 地下水运动特征图

Figure 5. Characteristics of groundwater movement

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图 6 含Cd水样矿物饱和指数箱形图

Figure 6. SI box-plot of the Cd-containing groundwater samples

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表 1 含镉水样主要化学指标

Table 1. Main chemical indicators of Cd-containing water samples

编号	pH	Na⁺	K⁺	Ca²⁺	Mg²⁺	${\rm{HCO}}_3^{-}$	${\rm{SO}}_4^{2-}$	Cl⁻	${\rm{NO}}_3^{-}$	TDS	镉
S040	7.19	1.37	0.41	57.43	6.08	149.62	39.33	1.46	0.67	281.81	0.0001
S224	8.08	1.65	0.66	72.94	16.4	183.47	89.94	2.61	1.15	291.50	0.0002
S2251	7.51	1.16	0.47	51.96	2.76	131.67	24.04	1.46	0.67	238.84	0.0002
S227	8.26	1.15	0.32	69.67	0.99	145.25	55.07	1.3	0.66	215.00	0.0002
S0391	7.25	1.77	0.3	51.51	4.15	131.67	30.59	1.46	1.2	257.34	0.0003
S0391-1	7.98	4.19	0.51	73.84	6.27	163.43	70.80	3.48	1.25	257.00	0.0003
S226	7.70	1.55	0.25	69.67	9.94	191.11	47.72	1.74	1.28	242.00	0.001
S131	7.16	2.72	0.59	67.21	29.32	126.14	185.22	2.17	1.08	365.00	0.0036
均值	7.64	1.95	0.44	64.28	9.49	152.80	67.84	1.96	1.00	268.56	0.00074
标准差	0.43	1.03	0.15	9.22	9.33	24.47	52.05	0.76	0.28	45.86	0.00119
变异系数	0.06	0.53	0.34	0.14	0.98	0.16	0.77	0.39	0.28	0.17	1.61
最大值	8.26	4.19	0.66	73.84	29.32	191.11	185.22	3.48	1.28	365.00	0.0036
最小值	7.16	1.15	0.25	51.51	0.99	126.14	24.04	1.30	0.66	215.00	0.0001
注：指标含量单位为mg·L⁻¹，pH无量纲。下表同上。

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表 2 研究区各地质单元表层土壤及岩石中Cd元素分布特征表

Table 2. Distribution characteristics of Cd in surface soils and rocks from different geological units in the study area

	元素/指标	统计参数	P₂l	P₂q	P₂m	P₂g	P₃w	P₃d	T₁d	T₁j	T₂b	T₃xj	Q
土壤	样品件数		−	68	50	10	129	63	367	479	946	14	83
	Cd	X	−	1.945	2.332	6.671	1.697	1.582	0.461	0.327	0.223	0.162	0.3
	Cd	CV	−	1.14	0.92	0.77	2.00	1.26	1.04	0.45	0.50	0.36	0.59
	pH	X	−	6.044	5.973	6.728	5.63	6.511	6.62	7.224	7.319	5.176	7.845
	pH	CV	−	0.17	0.18	0.17	0.17	0.18	0.14	0.14	0.14	0.07	0.07
岩石	样品件数		1	1	37	21	59	9	22	−	−	−	−
岩石	Cd	X	0.42	0.28	1.03	24.41	1.16	0.19	0.06	−	−	−	−
注：X为平均值，CV为变异系数，括号内为样品数，Cd含量单位为mg/kg，pH无量纲。

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表 3 含Cd水样水化学参数相关系数矩阵（样品数8）

Table 3. Correlation coefficient matrix of hydrochemical parameters in Cd-containing water samples (eight samples)

	pH	Na⁺	K⁺	Ca²⁺	Mg²⁺	${\rm{HCO}}_3^{-}$	${\rm{SO}}_4^{2-}$	Cl⁻	${\rm{NO}}_3^{-}$	TDS	Cd
pH	1
Na⁺	0.336	1
K⁺	0.557	0.634^*	1
Ca²⁺	0.931^**	0.514	0.663^*	1
Mg²⁺	0.069	0.588^*	0.667^*	0.296	1
${\rm{HCO}}_3^{-}$	0.898^**	0.430	0.580^*	0.929^**	0.231	1
${\rm{SO}}_4^{2-}$	0.168	0.685^*	0.702^*	0.397	0.957^**	0.254	1
Cl⁻	0.519	0.917^**	0.798^**	0.696^*	0.571	0.655^*	0.637^*	1
${\rm{NO}}_3^{-}$N	0.657^*	0.671^*	0.555	0.762^**	0.460	0.784^**	0.450	0.759^**	1
TDS	0.790^**	0.575	0.809^**	0.819^**	0.602^*	0.754^**	0.641^*	0.665^*	0.724^**	1
Cd	−0.038	0.564	0.438	0.150	0.914^**	0.054	0.917^**	0.410	0.315	0.478	1
*. 在0.01 水平（双侧）上显著相关。. 在 0.05 水平（双侧）上显著相关。

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表 4 土壤Cd元素地球化学形态组成

Table 4. Geochemical speciation composition of Cd element in soil

元素形态	全量	水溶态	离子交换态	碳酸盐结合态	腐殖酸结合态	铁锰氧化物结合态	强有机结合态	残渣态
最小值	0.123	0.001	0.019	0.012	0.014	0.016	0.007	0.022
平均值	1.598	0.010	0.249	0.163	0.249	0.400	0.081	0.387
最大值	8.737	0.061	1.158	0.845	1.857	2.339	0.399	1.781
标准离差	2.044	0.014	0.275	0.206	0.437	0.556	0.096	0.502
变异系数	1.279	1.400	1.104	1.264	1.755	1.390	1.185	1.297
占比（%）	100.00	0.63	15.58	10.20	15.58	25.03	5.07	24.22
注：含量单位mg·kg⁻¹，样品数n=16。

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