趵突泉泉域岩溶水化学特征及成因研究

王楠; 胥芹; 孙小艳; 武显仓; 李常锁; 高帅

doi:10.11932/karst20240203

趵突泉泉域岩溶水化学特征及成因研究

doi: 10.11932/karst20240203

王楠^{1, 2,},
胥芹³,
孙小艳⁴,
武显仓^5, ,,
李常锁^{1, 2},
高帅^{1, 2}

1.
山东省地矿工程勘察院(山东省地质矿产勘查开发局八〇一水文地质工程地质大队), 山东济南 250014
2.
山东省地下水环境保护与修复工程技术研究中心(筹), 山东济南 250014
3.
山东金利地质勘察有限公司,山东济南 250014
4.
山东地矿新能源有限公司, 山东济南 250013
5.
济南大学, 山东济南 250022

基金项目: 国家自然科学基金项目（42202294）；山东省自然科学基金项目（ZR2021QD084）

详细信息

作者简介:
王楠（1981－），女，硕士，高级工程师，主要从事水工环方面研究工作。E-mail：878870341@qq.com。

通讯作者:
李常锁（1976－），男，博士，研究员，主要从事岩溶水水文地球化学方向的研究。E-mail：lics120@163.com。

中图分类号: P641
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- 被引次数: 0
出版历程
- 收稿日期: 2023-08-04
- 录用日期: 2023-11-14
- 修回日期: 2023-11-13
- 网络出版日期: 2024-07-10
- 刊出日期: 2024-04-30

Hydrochemical characteristics and formation mechanism of karst water in Baotu Spring watershed

WANG Nan^{1, 2
,},
XU Qin³,
SUN Xiaoyan⁴,
WU Xiancang^{5
, ,},
LI Changsuo^{1, 2},
GAO Shuai^{1, 2}

1.
Shandong Provincial Geo-mineral Engineering Exploration Institute (No. 801 Hydrogeological and Engineering Geology Brigade of Shandong Provincial Bureau of Geology and Mineral Resources), Jinan, Shandong 250014, China
2.
Shandong Engineering Research Center for Environmental Protection and Remediation on Groundwater (under preparation), Jinan, Shandong 250014, China
3.
Shandong Jinli Geological Survey Co., Ltd., Jinan, Shandong 250014, China
4.
Shandong Geo-Mineral New Energy Co., Ltd., Jinan, Shandong 250013, China
5.
University of Jinan, Jinan, Shandong 250022, China

摘要

摘要: 趵突泉泉域是中国北方岩溶的典型分布区，近年来面临着水质恶化问题。为系统研究趵突泉泉域岩溶水水化学形成机制，采集60组趵突泉泉域地表水、地下水样品，利用Piper三线图、离子比值、相关性分析、因子分析和聚类分析等多元统计方法，并结合ArcGIS地理统计功能，对趵突泉泉域岩溶水水化学形成机制及空间差异性进行研究。结果表明，研究区地表水水化学类型主要为HCO₃·SO₄-Ca，地下水以HCO₃-Ca、HCO₃·SO₄-Ca、HCO₃-Ca·Mg型水为主，${\rm{SO}}_4^{2-}$占比有升高趋势。研究区地下水水化学组成主要受到碳酸盐、硫酸盐、岩盐等矿物溶解的影响。人类活动的污染导致地下水中Cl⁻、${\rm{NO}}_3^{-}$含量增加，并对地下水中天然水岩相互作用机制造成了影响。研究区地下水总体受污染程度不大，水化学组成主要受到水岩相互作用的影响，而受到Cl⁻、${\rm{NO}}_3^{-}$污染的地下水则主要分布在研究区的中部岩溶强渗漏带区域。
- 趵突泉泉域 /
- 地下水水化学 /
- 多元统计 /
- 空间分布
Abstract: Karst groundwater is an important water source for human production and livelihood, but it faces the risk of pollution. The study of the hydrochemical formation mechanism of karst groundwater is an important research topic. However, due to the evident control of factors such as local hydrogeological conditions and the intensity and manner of human activities on karst groundwater, it is challenging for us to explore the hydrochemical formation mechanism of karst groundwater. The Baotu Spring watershed is a typical distribution area of karst in Northern China, which has faced water quality deterioration in recent years. However, there is a lack of comprehensive case studies that combine multiple mathematical and statistical methods with hydrochemical analysis in the study of spatial differences in the hydrochemical formation mechanism of groundwater in Baotu Spring watershed. This study collected three surface water samples, six pore water samples, 47 karst groundwater samples, and four fracture water samples from the Baotu Spring watershed. Hydrochemical and multivariate statistical methods, such as Piper diagram, ion ratio, correlation analysis, factor analysis, and cluster analysis, were used. Additionally, ArcGIS geostatistical functionality was applied to investigate the hydrochemical formation mechanism and spatial differences of karst groundwater in the Baotu Spring watershed. The results indicate that the contents of Total Dissolved Solid (TDSs) in surface water samples ranged from 268.65 to 317.86 mg·L⁻¹, with small spatial variations in different chemical parameters. The hydrochemical type was primarily HCO₃·SO₄-Ca, indicating good connectivity of surface water. The TDS contents in groundwater samples ranged from 191.65 to 948.69 mg·L⁻¹, with large variations in all chemical parameters except for K⁺, indicating significant influences from local hydrogeological conditions or human activities on karst groundwater. The hydrochemical types of karst groundwater were mainly HCO₃-Ca, HCO₃·SO₄-Ca and HCO₃-Ca·Mg, with an increasing proportion of ${\rm{SO}}_4^{2-}$. The dominant cations in karst groundwater were Ca²⁺ and Mg²⁺. For anion, in the indirect recharge zone and discharge zone, karst groundwater was mainly dominated by ${\rm{HCO}}_3^{-}$ and ${\rm{SO}}_4^{2-}$, while in the direct recharge zone, the proportions of ${\rm{SO}}_4^{2-}$ and Cl⁻ in karst groundwater significantly increased. Correlation analysis and ion ratio analysis reveal that the hydrochemical composition of karst groundwater in the study area is mainly influenced by the dissolution/precipitation of minerals such as carbonate, sulfate, and halite. With an increase in the flow path, the interaction between water and rock became more thorough, leading to an increase in ion content in groundwater. Pollution caused by human activities increased the concentration of ${\rm{NO}}_3^{-}$ in groundwater, and the nitration process reduced the release of carbonates resulting from carbonate mineral dissolution. Therefore, human activities can directly pollute groundwate and affect the natural water–rock interaction mechanisms in groundwater. Overall, the degree of pollution in groundwater in the study area is not significant, with the hydrochemical composition being mainly influenced by water–rock interactions. However, human activities have also led to the contamination of Cl⁻ and ${\rm{NO}}_3^{-}$ in groundwater, with the polluted groundwater primarily distributed in the central karst zone with strong leakage in the study area. The karst groundwater in the northwest area was polluted in a lower degree, mainly because the thickness of the Quaternary system may reduce the direct pollution of karst groundwater by human activities. This study explores the hydrochemical formation mechanisms of the Baotu Spring watershed and provides preliminary analysis of the spatial differences in the hydrochemical formation mechanism, which can support the protection of local groundwater environment.
- Baotu Spring watershed /
- groundwater hydrochemistry /
- multivariate statistics /
- spatial distribution

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图 1 研究区水文地质简图及采样点分布情况

Figure 1. Hydrogeological map of the study area and locations of water samples

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图 2 研究区地质剖面图

Figure 2. Geological profile of the study area

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图 3 研究区水样Piper三线图

Figure 3. Piper diagram of water samples in the study area

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图 4 岩溶水中主要离子比值图

Figure 4. Ratios of main ions in karst water

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图 5 研究区岩溶水水化学指标各因子得分空间分布图

Figure 5. Spatial distribution of hydrochemical indexes of karst water in the study area

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图 6 研究区地下水中K⁺浓度空间分布图

Figure 6. Spatial distribution of K⁺ concentration in the study area

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图 7 研究区地下水水化学样品聚类树状图

Figure 7. Cluster dendrogram of hydrochemical samples of groundwater in the study area

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图 8 研究区地下水样不同聚类分组的空间分布

Figure 8. Spatial distribution of different groundwater cluster groups in the study area

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表 1 取样点情况及水温、pH统计表

Table 1. Statistics of situations, water temperatures, and pH of sampling points

编号	深度/m	含水层	类型	水温/℃	pH	编号	深度/m	含水层	类型	水温/℃	pH
J1	170	花岗岩	裂隙水	17.2	7.54	J32	—	石灰岩	岩溶水	13.7	7.78
J2	47	闪长岩	裂隙水	15.1	7.38	J33	0.5	—	地表水	17.4	7.42
J3	75	花岗岩	裂隙水	17.1	6.88	J34	215	石灰岩	岩溶水	17.4	7.14
J4	120	石灰岩	岩溶水	16.2	7.23	J35	58	白云岩	岩溶水	15.9	7.91
J5	86	白云岩	岩溶水	17.0	7.22	J36	0.5	—	地表水	17.1	7.56
J6	130	白云岩	岩溶水	18.3	7.83	J37	2 300	石灰岩	岩溶水	16.4	7.26
J7	127	石灰岩	岩溶水	16.8	7.39	J38	100	白云岩	岩溶水	14.5	7.17
J8	148	石灰岩	岩溶水	16.9	7.51	J39	352	白云岩	岩溶水	14.9	7.70
J9	152	石灰岩	岩溶水	16.6	7.69	J40	250	石灰岩	岩溶水		7.91
J10	26	粉砂	孔隙水	17.4	7.46	J41	4	白云岩	岩溶水	14.2	7.82
J11	100	石灰岩	岩溶水	17.6	7.43	J42	50	石灰岩	岩溶水	14.6	7.34
J12	183	石灰岩	岩溶水	18.6	7.58	J43	31	石灰岩	岩溶水	17.6	7.84
J13	130	白云岩	岩溶水	16.2	7.07	J44	200	白云岩	岩溶水	17.7	7.65
J14	137	白云岩	岩溶水	19.1	7.52	J45	300	石灰岩	岩溶水	19.0	7.85
J15	87	石灰岩	岩溶水	15.9	7.38	J46	20	石灰岩	岩溶水	16.2	7.56
J16	60	石灰岩	岩溶水	16.8	7.21	J47	23	石灰岩	岩溶水	16.6	7.49
J17	213	石灰岩	岩溶水	16.0	7.35	J48	36	白云岩	岩溶水	19.2	7.49
J18	158	石灰岩	岩溶水	16.5	7.13	J49	3	石灰岩	岩溶水	17.7	7.72
J19	0.5	—	地表水	15.3	8.02	J50	180	石灰岩	岩溶水	17.3	7.47
J20	186	石灰岩	岩溶水	17.0	7.49	J51	220	石灰岩	岩溶水	17.2	7.54
J21	125	石灰岩	岩溶水	17.2	7.05	J52	350	石灰岩	岩溶水	18.5	7.25
J22	22	砂质黏土	孔隙水	16.8	7.48	J53	260	石灰岩	岩溶水	18.6	7.34
J23	93	石灰岩	岩溶水	18.1	7.51	J54	280	石灰岩	岩溶水	19.7	7.44
J24	146	石灰岩	岩溶水	14.9	8.05	J55	40	砂质黏土	孔隙水	16.5	7.28
J25	33	石灰岩	岩溶水		7.61	J56	183	石灰岩	岩溶水	18.2	7.57
J26	—	—	岩溶泉	18.0	7.36	J57	15	粉砂	孔隙水	16.4	7.10
J27	—	白云岩	岩溶水		7.28	J59	5	砂质黏土	孔隙水	16.8	7.80
J29	—	石灰岩	岩溶水	14.1	7.58	J60	30	砂质黏土	孔隙水	17.6	7.54
J30	245	闪长岩	裂隙水	14.5	7.55	J61	—	白云岩	岩溶水	16.9	7.27
J31	50	白云岩	岩溶水	16.1	7.40	J62	—	—	岩溶泉	17.6	8.06

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表 2 水化学指标数学统计表

Table 2. Statistics of hydrochemical parameters

水样类型	数学指标	Na⁺ mg·L⁻¹	K⁺ mg·L⁻¹	Mg²⁺ mg·L⁻¹	Ca²⁺ mg·L⁻¹	Cl⁻ mg·L⁻¹	${\rm{NO}}_3^{-}$ mg·L⁻¹	${\rm{SO}}_4^{2-}$ mg·L⁻¹	${\rm{HCO}}_3^{-}$ mg·L⁻¹	TDS mg·L⁻¹
地表水	最大值	31.16	3.71	17.41	77.05	32.67	10.96	114.38	180.42	379.75
	最小值	10.06	1.76	12.04	64.62	12.07	7.81	67.99	174.69	268.65
	平均值	18.91	2.61	14.82	68.93	21.93	9.44	90.61	178.51	317.86
	变异系数	0.47	0.31	0.15	0.08	0.38	0.14	0.21	0.02	0.15
孔隙水	最大值	70.75	2.59	49.96	234.58	105.47	93.72	159.12	549.86	948.69
	最小值	12.08	0.61	15.98	75.02	23.91	4.35	10.47	226.24	283.85
	平均值	32.73	1.47	29.45	142.14	54.77	41.77	82.42	336.98	554.27
	变异系数	0.58	0.56	0.44	0.36	0.60	0.85	0.68	0.31	0.37
岩溶水	最大值	98.78	8.91	42.10	216.20	95.05	148.44	187.12	549.86	822.35
	最小值	3.98	0.38	7.43	10.12	1.82	1.71	23.62	80.19	191.65
	平均值	23.76	1.57	19.73	112.12	40.92	39.51	92.80	276.27	475.44
	变异系数	0.69	0.84	0.31	0.36	0.57	0.87	0.40	0.26	0.30
裂隙水	最大值	23.56	4.00	26.26	106.07	37.04	69.50	74.00	340.80	454.51
	最小值	10.12	1.32	7.23	41.96	7.85	1.99	30.49	111.69	160.27
	平均值	18.23	2.13	14.00	63.82	17.98	31.67	46.05	207.63	298.47
	变异系数	0.30	0.51	0.54	0.39	0.65	0.93	0.36	0.45	0.36

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表 3 水化学指标Spearman相关系数矩阵

Table 3. Spearman correlation matrices of hydrochemical parameters

	Na⁺	K⁺	Mg²⁺	Ca²⁺	Cl⁻	${\rm{NO}}_3^{-}$	${\rm{SO}}_4^{2-}$	${\rm{HCO}}_3^{-}$	TDS
Na⁺	1.000
K⁺	0.134	1.000
Mg²⁺	0.468**	−0.021	1.000
Ca²⁺	0.401**	−0.344**	0.309*	1.000
Cl⁻	0.658**	−0.214	0.451**	0.567**	1.000
${\rm{NO}}_3^{-}$	0.150	−0.371**	0.193	0.675**	0.535**	1.000
${\rm{SO}}_4^{2-}$	0.606**	−0.044	0.200	0.651**	0.553**	0.467**	1.000
${\rm{HCO}}_3^{-}$	0.227	−0.337*	0.462**	0.600**	0.384**	0.441**	0.205	1.000
TDS	0.686**	−0.234	0.456**	0.850**	0.741**	0.668**	0.815**	0.585**	1.000
*. 相关性在 0.01 层上显著（双尾）；. 相关性在 0.05 层上显著（双尾）。 ** The correlation is significant at the level of 0.01 (double-tail). * The correlation is significant at the level of 0.05 (double-tail).

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表 4 旋转因子载荷矩阵

Table 4. Loading matrix of rotated factor

	F1	F2	F3
Na⁺	0.203	0.787	−0.238
K⁺	−0.138	0.123	−0.824
Mg²⁺	0.000	0.845	0.251
Ca²⁺	0.785	0.155	0.486
Cl⁻	0.669	0.479	0.086
${\rm{NO}}_3^{-}$	0.838	−0.019	0.265
${\rm{SO}}_4^{2-}$	0.808	0.297	−0.125
${\rm{HCO}}_3^{-}$	0.403	0.352	0.743
TDS	0.845	0.425	0.302
pH	−0.463	0.129	−0.185
贡献率(%)	35.712	20.122	18.059
累积贡献率(%)	35.712	55.834	73.893

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