长江中游故道区地下水中有机质对钙富集的指示

王蓉; 杨逸君; 田书航; 董辰灏; 王祺翔; 邓娅敏

doi:10.19509/j.cnki.dzkq.tb20240491

长江中游故道区地下水中有机质对钙富集的指示

doi: 10.19509/j.cnki.dzkq.tb20240491

中国地质大学（武汉）环境学院，武汉 430078

基金项目: 国家自然科学基金项目（42107219）；湖北省博士后创新研究岗位项目（279863）；中央高校基本科研业务费专项资金资助项目（CUG2106124）

详细信息

作者简介:
王蓉：E-mail：rong.wang@cug.edu.cn

通讯作者:
E-mail：yijun.yang@cug.edu.cn

中图分类号: P641.12；X523
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出版历程
- 收稿日期: 2024-08-28
- 录用日期: 2024-12-16
- 修回日期: 2024-12-13
- 网络出版日期: 2026-01-29

Organic matter as an indicator of groundwater calcium enrichment in paleo-channel area along middle reaches of Yangtze River

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

More Information

Author Bio:
E-mail：rong.wang@cug.edu.cn

Corresponding author: E-mail：yijun.yang@cug.edu.cn

摘要

摘要:
地下水作为饮用水的重要来源，水中钙含量异常会危害人体生长发育，引发一系列与人体健康相关的疾病。现有研究多聚焦于大气CO₂参与的无机碳酸平衡过程对钙循环的调控，忽视了有机碳库的重要作用，且不同组分的有机质与钙相互作用的微观机理仍不清楚。以长江中游故道区为研究区，对采集的地下水样品进行了水化学、主成分分析、三维荧光光谱平行因子分析和荧光光谱区域积分，研究发现地下水中钙的浓度为111～213 mg/L，其分布呈空间异质性，集中分布于故道区的河曲和牛轭湖等处。并且，钙浓度较高的地下水中具有较高的有机质含量，两者空间分布具有相似性。研究区地下水中有机质包括类蛋白质（组分C1）、微生物源和陆源类腐殖质（组分C2和C3）3种主要组分。随着地下水中钙浓度升高，类蛋白组分含量逐渐减少，类腐殖质组分增多。长江中游故道区埋藏的丰富有机质所形成的强还原环境有利于有机质中类蛋白组分的降解，这一过程可促进含钙矿物的溶解，是地下水中钙富集的重要控制过程。研究查明了地下水中钙的空间分布特征和赋存环境，刻画了不同钙含量地下水中有机质组成差异，揭示了有机质对钙迁移富集的作用机理。
- 钙 /
- 有机质 /
- 三维荧光光谱 /
- 平行因子分析法 /
- 荧光光谱区域积分 /
- 长江中游
Abstract: Objective
As an important source of drinking water, abnormal calcium (Ca) concentrations in groundwater could endanger human growth and lead to health risks. Previous research has primarily focused on how inorganic carbonate equilibrium processes involving atmospheric CO₂ regulate groundwater Ca cycling. However, the important role of the organic carbon pool has been overlooked, and the microscopic mechanisms underlying the interactions between different components of organic matter (OM) and Ca remain elusive.
Methods
This study took the paleo-channel area along the middle reaches of the Yangtze River as the study area. Groundwater samples were analyzed using hydrochemical analysis, principal component analysis, parallel factor analysis (PARAFAC) of fluorescence excitation-emission matrix (EEM) spectroscopy, and fluorescence excitation-emission matrix regional integration.
Results
The results demonstrated that groundwater Ca concentrations exhibited significant spatial heterogeneity, ranging from 111 to 213 mg/L, mainly concentrated in the meanders and oxbow lakes of the paleo-channel region. Greater OM content was observed in the groundwater with elevated Ca concentration, and the two exhibited similar spatial distribution patterns. In the study area, the EEM-PARAFAC model identified three major components in groundwater, including protein-like components (C1), microbial and terrestrial humic components (C2 and C3).
Conclusion
With the increase of Ca concentration in groundwater, the content of protein-like components decreased while that of the humic-like components increased. Notably, the abundant organic matter buried in the paleo-channel area provides a strong reducing environment that favors the degradation of protein-like organic matter. This process promotes the dissolution of Ca-bearing minerals, which contributes to the groundwater Ca enrichment. This research investigated the heterogeneous spatial distribution and occurrence environments of Ca in groundwater, characterized differences in organic matter composition among groundwater with different Ca concentrations, and revealed the mechanisms by which organic matter influenced the migration and enrichment of Ca in groundwater.
- calcium /
- organic matter /
- fluorescence excitation-emission matrix spectroscopy /
- parallel factor analysis /
- fluorescence excitation-emission matrix regional integration /
- middle reaches of Yangtze River

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图 1 研究区采样点位置和地下水中钙浓度的空间分布

Figure 1. Sampling locations and spatial distribution of Ca concentrations in groundwater at the study area

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图 2 地下水部分水化学指标相关性图（r. 相关系数；p. 显著性水平）

Figure 2. Correlations among selected hydrochemical parameters in groundwater

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图 3 研究区地下水水化学主成分分析图

Figure 3. Principal component analysis results of groundwater hydrochemistry in study area

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图 4 平行因子法鉴别出的3个荧光组分及其荧光特征

Figure 4. Optical properties of three fluorescent components identified by EEM-PARAFAC analysis in groundwater

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图 5 不同钙浓度地下水中有机质三维荧光对比图

区域Ⅰ. 酪氨酸类蛋白质，Ex=200～250 nm；Em=280～330 nm；区域Ⅱ. 色氨酸类蛋白质，Ex=200～250 nm；Em=330～380 nm；区域Ⅲ. 类富里酸，Ex=200～250 nm；Em=380～550 nm；区域Ⅳ. 溶解性微生物代谢产物，Ex=250～340 nm；Em=280～380 nm；区域Ⅴ. 类腐殖酸，Ex=250～400 nm；Em=380～550 nm

Figure 5. Comparison of EEM fluorescence characteristics of organic matter in groundwater with different Ca concentrations

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图 6 不同钙浓度地下水中有机质荧光光谱的区域积分图

P_{i, n}为某一荧光区域i的积分标准体积占总积分标准体积的比例

Figure 6. Distribution of percent fluorescence response parameters (P_i,n) of organic matter in EEM regions for groundwater with different Ca concentrations

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表 1 研究区地下水主要水化学参数

Table 1. Major hydrochemical parameters of groundwater in the study area

参数	pH	Eh/mV	K⁺	Ca²⁺	Na⁺	Mg²⁺	Cl⁻	NO₃⁻	SO₄²⁻	HCO₃⁻	NH₄⁺	Fe²⁺	DOC
参数	pH	Eh/mV	ρ_B/(mg·L⁻¹)
最小值	6.83	−143	1.28	111	7.18	17.5	2.48	2.54	1.38	306	0.03	0.01	3.16
最大值	7.39	33.0	5.85	213	41.5	53.1	29.6	38.4	50.7	942	25.0	39.8	13.1
平均值	7.15	−92.5	3.42	155	17.3	35.9	11.8	6.00	9.82	614	4.50	6.85	6.55
中位值	7.18	−97.8	3.56	153	15.3	34.9	8.84	4.84	2.88	601	2.43	3.98	5.85

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表 2 研究区地下水水化学指标的因子贡献率

Table 2. Factor contribution rates of groundwater hydrochemical parameters in study area

指标	主因子方差	主成分PC1	主成分PC2	主成分PC3
Ca²⁺	0.89	0.79	0.17	−0.48
Mg²⁺	0.95	0.88	0.37	−0.20
HCO₃⁻	0.93	0.93	0.18	−0.20
DOC	0.82	0.80	0.42	−0.09
NH₄⁺	0.92	0.51	0.26	0.77
Fe²⁺	0.60	0.50	0.07	0.59
K⁺	0.52	0.65	0.24	0.19
Na⁺	0.92	−0.28	0.91	−0.12
Cl⁻	0.70	−0.47	0.67	0.18
NO₃⁻	0.76	−0.56	0.66	−0.09
SO₄²⁻	0.77	−0.76	0.44	−0.02
贡献率/%		45.7	21.9	12.3
累计贡献率/%		45.7	67.6	79.8
注：加粗表示显著载荷

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表 3 研究区地下水中有机质的3个荧光组分特征

Table 3. Characteristics of three fluorescent components of organic matter in groundwater in study area

组分	Ex/Em/nm	本研究中DOM组分描述	以往研究中DOM组分描述
C1	220(275)/306	酪氨酸类蛋白	C3：220(280)/352^[39]
			C3：240(280)/344^[35]
			C3：220(280)/352^[40]
			B峰：270-280/300-310^[41]
C2	235(310)/426	微生物源类腐殖质	C1：240(320)/404^[39]
			C2：240(320)/400^[35]
			C3：250(320)/434^[42]
C3	255(345)/472	陆源类腐殖质	C2：290(360)/485^[42]
			C3：270(370)/470^[43]
			C1：260(340)/470^[44]

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