鲁北平原浅层地下水锰空间演化及成因机制

doi:10.13745/j.esf.sf.2025.10.23

地学前缘 ›› 2026, Vol. 33 ›› Issue (1): 107-120.DOI: 10.13745/j.esf.sf.2025.10.23

鲁北平原浅层地下水锰空间演化及成因机制

郭记菊¹^,²(), 曹文庚¹^,²^,^*(), 鲁重生¹^,², 王哲³, 朱静思⁴^,^*(), 王妍妍¹^,², 李祥志¹^,², 马翠艳¹^,²

1.中国地质科学院水文地质环境地质研究所, 河北石家庄 050061
2.河北省/中国地质调查局地下水污染机理与修复重点实验室, 河北石家庄 050061
3.水利部海河水利委员会, 天津 300170
4.水利部海河水利委员会水文局, 天津 300170

收稿日期:2025-07-05 修回日期:2025-10-26 出版日期:2026-01-25 发布日期:2025-11-10
通信作者: *曹文庚(1985—),男,研究员,主要从事水文地质和水文地球化学方面的研究工作。 E-mail: 281084632@qq.com; 朱静思(1988—),女,高级工程师,主要从事水文水资源方面的工作。 E-mail: 735077092@qq.com
作者简介:郭记菊(2002—),女,博士研究生,主要研究方向为水文地球化学。E-mail: g_jmiao@163.com
基金资助:
国家自然科学基金地质联合基金项目(U2444218);中央引导地方科技发展资金项目(246Z3601G);中国地质科学院基本科研业务费项目(YK202301);中国地质科学院基本科研业务费项目(SK202416)

Spatial evolution and genetic mechanisms of manganese in shallow groundwater of the North Shandong Plain

GUO Jiju¹^,²(), CAO Wengeng¹^,²^,^*(), LU Chongsheng¹^,², WANG Zhe³, ZHU Jingsi⁴^,^*(), WANG Yanyan¹^,², LI Xiangzhi¹^,², MA Cuiyan¹^,²

1. The Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geosciences, Shijiazhuang 050061, China
2. Key Laboratory of Groundwater Contamination and Remediation, Hebei Province & China Geological Survey, Shijiazhuang 050061, China
3. Haihe River Water Conservancy Commission, Ministry of Water Resources of China, Tianjin 300170, China
4. Hydrology Bureau of Haihe River Water Conservancy Commission, Ministry of Water Resources of China, Tianjin 300170, China

Received:2025-07-05 Revised:2025-10-26 Online:2026-01-25 Published:2025-11-10

摘要/Abstract

摘要： 锰(Mn)作为地下水中广泛存在的神经毒性金属元素,其超标(> 0.1 mg·L^-1)不仅导致饮用水感官恶化,更可能引发帕金森样神经病变。尽管前期研究揭示了黄河下游冲积平原浅层地下水Mn存在高度空间异质性及大面积异常,但对冲积沉积体系下不同地貌单元Mn富集的水文地球化学机制仍缺乏系统性认知。本研究从区域上尺度上,查明鲁北平原浅层地下水Mn的分布特征和影响因素,同时结合典型水文地质剖面精细刻画,揭示了高Mn地下水的水文地球化学过程及其形成机制。结果表明:区域上地下水中Mn含量从未检出至12.0 mg·L^-1,平均值为0.65 mg·L^-1,超标率为96.6%;沿典型剖面方向,古河道高地地段地下水Mn的平均质量浓度(0.27 mg·L^-1)显著低于泛滥平原段(0.83 mg·L^-1),在滨海平原再显著升高(2.53 mg·L^-1),水化学类型逐渐由HCO₃-Na·Mg和HCO₃·Cl-Na·Mg转变为以Cl·HCO₃-Na·Mg型为主,最终演变为Cl-Na型水。鲁北平原浅层地下水中Mn最可能的来源是沉积物中的锰氢氧化物和菱锰矿,地下水在漫长的循环过程中,影响该地区地下水Mn含量分布的因素主要有硅酸盐风化、蒸发盐矿物溶解、蒸发浓缩作用、阳离子交替吸附作用、酸碱反应、氧化还原作用等一系列水岩交互作用过程。鲁北平原不同水文地球化学分区的污染源贡献率呈现显著空间分异,与Mn含量的空间演化规律相似。综合研究发现:研究区浅层地下水Mn的空间分异主要受pH驱动的溶解和吸附过程、盐度驱动的离子交替吸附以及原生沉积背景下Mn的释放共同影响。

关键词: 鲁北平原, 地下水, 锰, 冲积平原, 水文地球化学

Abstract:

Manganese (Mn), a widespread neurotoxic metallic element in groundwater, poses significant health risks when its concentration exceeds the permissible limit (> 0.1 mg·L^-1), potentially inducing Parkinsonian-like neurological disorders. Although previous studies have revealed pronounced spatial heterogeneity of Mn in the shallow groundwater of the lower Yellow River alluvial plain, a systematic understanding of the hydrogeochemical mechanisms controlling its enrichment across different geomorphic units is still lacking. To address this gap, this study investigates the regional distribution of Mn and its controlling factors, complemented by a detailed characterization of representative hydrogeological cross-sections to elucidate the key processes governing high-Mn groundwater. The results indicate that the regional groundwater Mn concentration ranges from below the detection limit to 12.0 mg·L^-1, with a mean of 0.65 mg·L^-1 and an exceedance rate of 96.6%. Along a representative transect, the average Mn concentration increases significantly from the paleochannel highland (0.27 mg·L^-1) to the fluvial plain (0.83 mg·L^-1) and reaches its peak in the coastal plain (2.53 mg·L^-1). This spatial pattern is accompanied by a gradual evolution of hydrochemical facies, from HCO₃-Na-Mg and HCO₃-Cl-Na-Mg types to predominantly Cl-HCO₃-Na-Mg, and finally to the Cl-Na type. The primary sources of Mn are identified as manganese hydroxides and rhodochrosite within the sediments. The regional distribution of Mn is primarily influenced by a series of water-rock interactions, including silicate weathering, dissolution of evaporite minerals, cation exchange, and redox processes. The contributions of these natural sources exhibit significant spatial variations across different hydrogeochemical zones, mirroring the evolution of Mn concentrations. Integrated analysis reveals that the spatial heterogeneity of shallow groundwater Mn is collectively controlled by pH-driven dissolution and adsorption, salinity-driven ion exchange, and the release of Mn from primary sediments under the prevailing depositional background.

Key words: North Shandong Plain, groundwater, manganese (Mn), alluvial plain, hydrogeochemistry

中图分类号:

P641

郭记菊, 曹文庚, 鲁重生, 王哲, 朱静思, 王妍妍, 李祥志, 马翠艳. 鲁北平原浅层地下水锰空间演化及成因机制[J]. 地学前缘, 2026, 33(1): 107-120.

GUO Jiju, CAO Wengeng, LU Chongsheng, WANG Zhe, ZHU Jingsi, WANG Yanyan, LI Xiangzhi, MA Cuiyan. Spatial evolution and genetic mechanisms of manganese in shallow groundwater of the North Shandong Plain[J]. Earth Science Frontiers, 2026, 33(1): 107-120.

图/表 14

图1 研究区概况 (地貌分区据文献[22])

Fig.1 Study area overview. Geomorphic divisions adapted from[22].

表1 鲁北平原浅层地下水采样点主要理化参数的统计特征(n=1 083)

Table 1 Statistical characteristics of the main physicochemical parameters of shallow groundwater sampling points in the typical profile of the study area (n=1 083)

图2 鲁北平原浅层地下水Mn含量分布图

Fig.2 Distribution map of Mn concentration in shallow groundwater within the North Shandong Plain

表2 超过25%毫克当量的离子统计结果

Table 2 Statistical results for ions exceeding 25% of the total milliequivalents

超过25%毫克当量的离子	HCO₃	HCO₃·SO₄	HCO₃·SO₄·Cl	HCO₃·Cl	SO₄	SO₄·Cl	Cl
Ca	4	0	0	0	0	0	0
Ca·Mg	24	8	0	1	0	8	0
Mg	3	2	0	0	0	0	0
Na·Ca	58	31	9	2	0	9	2
Na·Ca·Mg	118	83	58	0	0	48	2
Na·Mg	84	87	120	14	1	79	43
Na	24	22	24	1	0	19	95

图3 Piper三线图显示了鲁北平原典型剖面浅层地下水中的主要阳离子和阴离子浓度(单位为% meq·L-1)

Fig.3 The Piper diagram shows the concentrations of major cations and anions in shallow groundwater of the typical profile in the study area (expressed in units of % meq·L-1)

表3 鲁北平原浅层地下水锰含量与各水化学参数的Spearman相关系数

Table 3 Spearman correlation coefficients between Mn concentration and various hydrochemical parameters in shallow groundwater of the study area

水化学参数	相关系数	水化学参数	相关系数
pH	-0.304^**	${\mathrm{NO}}_{3}^{-}$	0.139^**
Eh	0.196^**	${\mathrm{NO}}_{2}^{-}$	0.133^**
TDS	0.441^**	${\mathrm{NH}}_{4}^{+}$	-0.066^*
Ca²⁺	0.542^**	Fe³⁺	0.128^**
Mg²⁺	0.497^**	Fe²⁺	0.006
K⁺	0.071^*	F^-	-0.211^**
Na⁺	0.322^**	耗氧量	0.213^**
Cl^-	0.494^**	偏硅酸	-0.338^**
${\mathrm{SO}}_{4}^{2-}$	0.426^**	As	-0.176^**
${\mathrm{HCO}}_{3}^{-}$	0.043

图4 鲁北平原典型剖面浅层地下水中锰含量(a)及相关理化因子((b) Eh、(c) pH、(d)TDS)的剖面变化特征

Fig.4 Variation characteristics of Mn(a) and related physicochemical factors ((b) Eh、(c) pH、(d)TDS) in shallow groundwater along a representative study area profile

图5 鲁北平原典型剖面浅层地下水 (a) Mg2+/Na+以及(b) ${\mathrm{HCO}}_{3}^{-}$/Na+与Ca2+/Na+的归一化摩尔比关系图

Fig.5 Normalized molar ratio relationships of (a) Mg2+/Na+ and (b) ${\mathrm{HCO}}_{3}^{-}$/Na+ with Ca2+/Na+ in shallow groundwater of the typical profile in the study area

图6 研究区地下水含锰矿物饱和指数分布图

Fig.6 Distribution map of the SI of Mn-bearing minerals in the groundwater of the study area

图7 鲁北平原典型剖面浅层地下水Gibbs图

Fig.7 Gibbs diagram of shallow groundwater of the typical profile in the study area

图8 鲁北平原典型剖面浅层地下水${{\mathrm{Ca}}^{2+}}^{}$+ ${{\mathrm{Mg}}^{2+}}^{}$- ${\mathrm{HCO}}_{3}^{-}$ -${\mathrm{SO}}_{4}^{2-}$与 ${{\mathrm{Na}}^{+}}^{}$+ ${{\mathrm{K}}^{+}}^{}$-Cl-比值和氯碱指数比

Fig.8 Ratios of major ions in shallow groundwater of the typical profile in the study area: ${{\mathrm{Ca}}^{2+}}^{}$+ Mg2+ -${{\mathrm{HCO}}_{3}^{-}}^{}$-${\mathrm{SO}}_{4}^{2-}$ to ${{\mathrm{Na}}^{+}}^{}$+ ${{\mathrm{K}}^{+}}^{}$-Cl- ratio; Chloro-alkali index

图9 研究区地下水锰的(a)Eh-pH图及(b)Eh-Mn和(c)pH-Mn的统计关系。图例同图5和7。

Fig.9 Relationships related to Mn in the groundwater of the study area: (a) Eh-pH diagram; (b) statistical relationship between Eh and Mn; (c) statistical relationship between pH and Mn

图10 基于PMF模型的地下水化学主控因子贡献率解析

Fig.10 Analysis of the contribution rates of the main controlling factors of groundwater chemistry based on the PMF model

图11 鲁北平原浅层高锰地下水成因机制示意图

Fig.11 Schematic diagram of the genetic mechanisms for shallow high-Mn groundwater in the North Shandong Plain

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鲁北平原浅层地下水锰空间演化及成因机制

Spatial evolution and genetic mechanisms of manganese in shallow groundwater of the North Shandong Plain

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