黄河下游冲积扇地下水中DOM来源及其对砷富集的影响

李浩林; 魏玉龙; 苏春利; 江嘉琪; 蒋格; 王春晖; 刘海风

doi:10.19509/j.cnki.dzkq.tb20250110

黄河下游冲积扇地下水中DOM来源及其对砷富集的影响

doi: 10.19509/j.cnki.dzkq.tb20250110

李浩林^1,,
魏玉龙^{2, 3},
苏春利^1, ,,
江嘉琪¹,
蒋格¹,
王春晖^{2, 3},
刘海风^{2, 3}

1.
中国地质大学（武汉）环境学院，武汉 430078
2.
河南省第五地质勘查院有限公司，郑州 450001
3.
河南自然资源科技创新中心（生态环境评价与修复技术研究），郑州 450001

基金项目: 国家自然科学基金项目（42177078）；河南省自然资源科研项目（豫自然资函[2023]610号-5）

详细信息

作者简介:
李浩林：E-mail：18538985753@163.com

通讯作者:
E-mail：chl.su@cug.edu.cn

计量
- 文章访问数: 33
- PDF下载量: 2
- 被引次数: 0
出版历程
- 收稿日期: 2025-03-10
- 录用日期: 2025-06-17
- 修回日期: 2025-06-16
- 网络出版日期: 2025-06-17

Dissolved organic matter sources in groundwater in alluvial fan of lower reaches of Yellow River and their influence on arsenic enrichment

LI Haolin^1
,,
WEI Yulong^{2, 3},
SU Chunli^{1
, ,},
JIANG Jiaqi¹,
JIANG Ge¹,
WANG Chunhui^{2, 3},
LIU Haifeng^{2, 3}

1.
School of Environmental Studies, China University of Geosciences (Wuhan), Wuhan 430078, China
2.
Henan Fifth Geological Exploration Institute Co., Ltd., Zhengzhou 450001, China
3.
Henan Provincial Natural Resources Science and Technology Innovation Center (Research on Ecological Environment Assessment and Restoration Technology), Zhengzhou 450001, China

More Information

Author Bio:
E-mail：18538985753@163.com

Corresponding author: E-mail：chl.su@cug.edu.cn

摘要

摘要:
豫东平原为黄河下游典型农灌区，区内广泛分布高砷地下水，对居民饮水安全构成严重威胁。揭示冲积平原地下水砷迁移转化的生物地球化学机制，可为防控地方性砷中毒提供科学依据。从黄河冲积平原、决口扇、河间洼地3类地貌单元采集 200 组地下水样品，综合运用水文地球化学分析、三维荧光光谱（3D-EEM）及平行因子分析（PARAFAC），阐明高砷地下水空间分异规律及溶解性有机质（DOM）介导的砷活化机制。研究表明，高砷地下水（ρ（As）>10 μg/L）主要赋存于 20～50 m 浅层含水层，空间分布受黄河现代河道与故道沉积体系控制，在决口扇前缘与河间洼地形成富集区。DOM 表征显示，高砷水 DOM 具高芳香性与强腐殖化特征，以小分子量腐殖质组分（C1，相对荧光强度占比54%）和类黄腐酸组分（C3，相对荧光强度占比29%）为主，揭示陆源−微生物源协同输入机制。相关性分析表明，地下水砷含量与 Fe（Ⅱ），NH₄⁺-N 及 DOM 组分 C1（最大荧光强度F_max）、C3（F_max）呈显著正相关。弱还原−还原沉积环境中，有机质驱动微生物介导铁（氢）氧化物还原性溶解、腐殖质−铁−砷三元络合物解吸共同构成砷活化双途径；类色氨酸组分（C2）厌氧降解可提升微生物代谢活性，加速沉积物中砷二次释放。研究结果可为黄河下游冲积扇高砷地下水风险管控与安全供水提供理论支撑。
- 砷 /
- 地下水 /
- 溶解性有机质(DOM) /
- 砷富集 /
- 黄河下游冲积扇 /
- 豫东平原
Abstract:
Objective
The East Henan Plain is a typical agricultural irrigation area in the lower reaches of the Yellow River, where high-arsenic groundwater is widely distributed, posing a severe threat to drinking water safety. Revealing the biogeochemical mechanisms of arsenic migration and transformation in groundwater in alluvial plain aquifers can provide a scientific basis for prevention and control of endemic arsenic contamination.
Methods
In this study, 200 groundwater samples were collected from three geomorphic units, including Yellow River alluvial plain, crevasse splays, and interriver depressions, to identify the distribution of high-arsenic groundwater. Hydrogeochemical analysis, three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, and parallel factor analysis (PARAFAC) were applied to clarify its spatial differentiation pattern and the arsenic activation mechanism mediated by dissolved organic matter (DOM).
Results
High-arsenic groundwater (ρ(As)>10 μg/L) was mainly distributed in shallow aquifers at depths of 20-50 m. Its spatial distribution was controlled by sedimentary systems of modern Yellow River channel and paleochannels, forming enrichment zones at the fronts of crevasse splays and interriver depressions. DOM in high-arsenic groundwater was characterized by high aromaticity and strong humification, dominated by low-molecular-weight humic-like (C1, 54%) and fulvic-like (C3, 29%) components, revealing a synergistic input mechanism of terrestrial and microbial sources. Correlation analysis indicated that arsenic concentration in groundwater was significantly positively correlated with Fe (Ⅱ), NH₄⁺-N, and DOM components C1 (maximum fluorescence intensity, F_max) and C3 (F_max).
Conclusion
In weakly reducing to reducing sedimentary environments, arsenic activation is jointly controlled by two pathways: Microbially mediated reductive dissolution of Fe (hydr)oxides driven by organic matter, and desorption of humic-Fe-As complexes. Anaerobic degradation of tryptophan-like component (C2) enhances microbial metabolic activity and accelerates secondary release of arsenic from sediments. The results provide theoretical support for risk management and safe utilization of high-arsenic groundwater in the alluvial fan in the lower reaches of the Yellow River.
- arsenic /
- groundwater /
- dissolved organic matter (DOM) /
- arsenic enrichment /
- alluvial fan in lower reaches of Yellow River /
- Yudong Plain

HTML全文

图 1 研究区地貌、地下水水位和地下水砷含量的分布

Figure 1. Distribution of geomorphology, groundwater level, and arsenic concentration in groundwater of study area

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图 2 地下水砷质量浓度与井深(a)和地下水氧化还原电位(b)的关系及不同沉积环境氧化还原条件(c)

Figure 2. Relationships of arsenic concentration in groundwater with well depth (a) and redox potential (b), and redox conditions under different sedimentary environments (c)

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图 3 不同地貌单元地下水中砷含量与Fe(Ⅱ) (a)、Mn (b)、NH₄⁺-N (c)的关系（r. 相关系数；p. 显著性水平；下同）

Figure 3. Relationships of arsenic concentration with Fe(Ⅱ) (a), Mn (b), and NH₄⁺-N (c) in groundwater of different geomorphic units

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图 4 地下水中ρ(Cl⁻)/ρ(Br⁻)与地下水中ρ(Cl⁻) (a)和ρ(As) (b)的关系

Figure 4. Relationships of ρ(Cl⁻)/ρ(Br⁻) (mass ratio) and ρ(Cl⁻) in groundwater (a) with ρ(As) (b)

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图 5 地下水DOM三维荧光光谱

Figure 5. Three-dimensional excitation-emission matrix fluorescence spectra of dissolved organic matter (DOM) in groundwater

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图 6 地下水中不同DOM组分的相对含量（IQR. 四分位距）

Figure 6. Relative contents of different dissolved organic matter (DOM) components in groundwater

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图 7 DOM各组分（C1，C2，C3）相对荧光强度占比(a～c)、最大荧光强度F_max(b)与砷质量浓度的关系

Figure 7. Relationships of relative contents (a-c) and maximum fluorescence (F_max) (b-f) intensity of dissolved organic matter (DOM) components (C1, C2, C3) with arsenic concentration

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图 8 生物指数BIX与腐殖化指数HIX的关系(a)及各光学特征指标（荧光指数FI、HIX、BIX）与砷质量浓度的关系(b～d)

Figure 8. Relationships between HIX and BIX (a), between optical indices (FI, HIX, BIX) and arsenic concentration (b-d)

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表 1 研究区中3个荧光组分特征及与先前研究的对比

Table 1. Characteristics of three fluorescence components in study area and comparison with previous studies

荧光组分	研究区 (Ex/Em)/nm	描述	前人研究(Ex/Em)/nm
C1	<250/430	陆源腐殖质，小分子量	(237～260)/(400～500)^[37]； 250(325)/416^[38]
C2	300(<250)/350	微生物源类蛋白，类似游离态和蛋白结合态氨基酸色氨酸，内源输入	(225～237)/(340～381)^[37]； 240/338^[39]
C3	<250/500	类腐殖质，黄腐酸样成分，高分子量	(237～260)/(400～500)^[37]； 255(345)/472^[40]
注：Ex. 激发波长；Em. 发射波长；下同

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