稻田土壤中砷的生物地球化学行为研究进展及污染防控策略

doi:10.16258/j.cnki.1674-5906.2025.11.013

生态环境学报 ›› 2025, Vol. 34 ›› Issue (11): 1802-1811.DOI: 10.16258/j.cnki.1674-5906.2025.11.013

稻田土壤中砷的生物地球化学行为研究进展及污染防控策略

吴小令¹(), 周琪川², 梁小佳², 周燕敏², 钟松雄²^,^*()

1.深圳市生态环境智能管控中心，广东深圳 518034
2.广东省科学院生态环境与土壤研究所，广东广州 510650

收稿日期:2025-05-20 出版日期:2025-11-18 发布日期:2025-11-05
通讯作者: *E-mail: sxzhong@soil.gd.cn
作者简介:吴小令（1973年生），女，高级工程师，主要从事生态环境管理论证与咨询、生态环境信息化管理等研究。E-mail: 1003405501@qq.com
基金资助:
国家重点研发计划项目(2022YFD1700802);国家自然科学基金项目(42577035);国家自然科学基金项目(42207052)

Research Progress on the Biogeochemical Behavior of Arsenic in Paddy Soils and Pollution Prevention and Control Strategies

WU Xiaoling¹(), ZHOU Qichuan², LIANG Xiaojia², ZHOU Yanmin², ZHONG Songxiong²^,^*()

1. Shenzhen Ecological Environment Intelligent Management and Control Center, Shenzhen 518034, P. R. China
2. Institute of Eco-Environmental and Soil Science, Guangdong Academy of Sciences, Guangzhou 510650, P. R. China

Received:2025-05-20 Online:2025-11-18 Published:2025-11-05

摘要/Abstract

摘要：

土壤砷的迁移转化过程影响水稻砷累积，进而危害人体健康。该过程由土壤砷的赋存形态决定，与土壤的理化性质及土壤微生物等因素有关。开展定向土壤砷污染防控，需明晰砷在土壤中的物理化学和生物化学行为，包括砷的氧化还原和甲基化过程及其在矿物相中的吸附特性。该文系统探讨了水分管理措施、铁矿物成分、氮循环过程及有机质（主要以腐殖质为例）对砷迁移转化过程的制约效应及其关键调控机制：间歇灌溉可有效抑制厌氧条件下砷的释放，降低稻米籽粒中的砷含量；根表铁膜作为重要的“天然屏障”，其稳定性受矿物结晶度和微生物铁还原作用影响；铵态氮氧化促进砷的活化，而硝态氮则通过驱动As(Ⅲ)的厌氧氧化并与铁氧化作用耦合，从而实现对砷的钝化；腐殖质作为电子供体或电子穿梭体，可刺激微生物铁还原和砷还原过程，增加土壤溶液中活性砷的浓度，从而存在潜在风险。为有效降低砷积累、保障农产品的安全生产，提出应从单一因子提升至多因子作用影响研究，构建“土壤环境化学-微生物学-植物生理学”的多学科交叉研究链条，精准识别砷转化的物理化学机制及微生物分子机制，优化绿色调控技术，实现区域尺度砷污染风险预测与智慧管控。

关键词: 砷, 水稻土, 铁矿物, 有机质, 硝态氮

Abstract:

The migration and transformation processes of arsenic (As) in soil affect As accumulation in rice, which posing a threat to human health. These processes are determined by As speciation in the soil and are related to soil physicochemical properties and soil microorganisms. To effectively control As pollution in soil, it is necessary to understand the physicochemical and biochemical behaviors of As in soil, including its redox reactions, methylation processes, and adsorption characteristics on mineral surfaces. This study systematically discusses the effects and key regulatory mechanisms of water management practices, iron mineral composition, nitrogen cycling, and organic matter (primarily humic substances) on As migration and transformation. Intermittent irrigation can effectively inhibit As release under anaerobic conditions, thereby reducing the As content in rice grains. The iron layer on root surfaces acts as an important “natural barrier,” and its stability is affected by mineral crystallinity and microbial iron reduction. Ammonium nitrogen oxidation promotes As activation, whereas nitrate nitrogen, through anaerobic oxidation of As(Ⅲ) coupled with iron oxidation, can inactivate arsenic. Humic substances, as electron donors or shuttles, can stimulate microbial iron and As reduction processes, increasing the concentration of active As in soil solution, thus posing potential risks. To effectively reduce As accumulation and ensure the safety of agricultural products, research should shift from single-factor studies to multi-factor interactions, establishing a multidisciplinary research framework encompassing soil environmental chemistry, microbiology, and plant physiology. This approach will allow for the precise identification of the physicochemical and microbial mechanisms of As transformation, optimization of green remediation technologies, and ultimately, regional-scale As pollution risk prediction and intelligent management of As-contaminated environments.

Key words: arsenic, paddy soil, iron minerals, organic matter, NO₃^--N

中图分类号:

X142
X53

吴小令, 周琪川, 梁小佳, 周燕敏, 钟松雄. 稻田土壤中砷的生物地球化学行为研究进展及污染防控策略[J]. 生态环境学报, 2025, 34(11): 1802-1811.

WU Xiaoling, ZHOU Qichuan, LIANG Xiaojia, ZHOU Yanmin, ZHONG Songxiong. Research Progress on the Biogeochemical Behavior of Arsenic in Paddy Soils and Pollution Prevention and Control Strategies[J]. Ecology and Environmental Sciences, 2025, 34(11): 1802-1811.

图/表 3

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不同铁矿物	物理化学性质	与砷的结合方式	与砷的氧化还原
水铁矿	比表面积达到248 m²∙g⁻¹；非晶态，短程有序纳米颗粒	与表面OH−和OH₂发生配位体交换，形成内圈螯合物；三价砷吸附，双齿单核配位吸附，形成内圈螯合物或外圈螯合物	氧化：表面的Fe(Ⅲ)可通过配位氧空位或羟基自由基缓慢氧化三价砷；还原：五价砷被Fe²⁺或微生物代谢产物还原（Liu et al.，2022）
针铁矿	比表面积10－132 m²∙g⁻¹；自然条件下稳定性强；表面结构存在两层吸附水与两种终止羟基（Huhmann et al.，2017）	表面羟基用于配体交换；砷在针铁矿覆盖率较高时主要以双齿双核螯合方式；覆盖率较低时为单齿螯合；五价砷在针铁矿表面形成单齿螯合物而非双齿双核螯合物	氧化：表面Fe(Ⅲ)对三价砷的氧化需依赖共存的氧化剂；还原：针铁矿的Fe(Ⅲ)被还原，矿物部分溶解并释放吸附的砷
赤铁矿	比表面积为9.33 m²∙g⁻¹；水铁矿或针铁矿脱水脱羟基时转换成赤铁矿	氢键与静电力稳定化表面的五价砷；通过单齿螯合、角落共享和边缘共享式双齿双核螯合，形成内圈和外圈螯合物；内部水结构稳定化五价砷，如五价砷可持续在赤铁矿上形成外圈螯合物（Catalano et al.，2007）	氧化：在光照下产生活性氧物种，显著促进三价砷氧化；还原：强还原条件下可被部分还原为磁铁矿，释放结合态砷
纤铁矿	斜方晶系，层状结构，比表面积50－150 m²∙g⁻¹；碱性或有机质存在的环境中易转化为针铁矿	五价砷通过双齿双核表面复合物与纤铁矿结合；三价砷在酸性条件（pH<6）下通过单齿单核配位吸附	氧化：通过表面吸附的Fe²⁺催化反应间接氧化三价砷；还原：还原条件下（如微生物作用）溶解，释放砷
磁铁矿	反尖晶石结构，具磁性，比表面积20－90 m²∙g⁻¹	五价砷通过配体交换吸附在磁铁矿表面；三价砷在酸性条件（pH 4－6）下通过单齿单核配位吸附	氧化：在氧化条件下部分转化为赤铁矿；还原：表面的Fe²⁺可直接还原五价砷为三价砷（Gubler et al.，2021）
绿锈	层状双氢氧化物，比表面积50－200 m²∙g⁻¹	五价砷通过配体交换吸附在表面层间；三价砷在表面形成单齿单核复合物	氧化：暴露于氧气时分解为针铁矿/赤铁矿；还原：层间的Fe²⁺快速还原五价砷

不同铁矿物	物理化学性质	与砷的结合方式	与砷的氧化还原
水铁矿	比表面积达到248 m²∙g⁻¹；非晶态，短程有序纳米颗粒	与表面OH−和OH₂发生配位体交换，形成内圈螯合物；三价砷吸附，双齿单核配位吸附，形成内圈螯合物或外圈螯合物	氧化：表面的Fe(Ⅲ)可通过配位氧空位或羟基自由基缓慢氧化三价砷；还原：五价砷被Fe²⁺或微生物代谢产物还原（Liu et al.，2022）
针铁矿	比表面积10－132 m²∙g⁻¹；自然条件下稳定性强；表面结构存在两层吸附水与两种终止羟基（Huhmann et al.，2017）	表面羟基用于配体交换；砷在针铁矿覆盖率较高时主要以双齿双核螯合方式；覆盖率较低时为单齿螯合；五价砷在针铁矿表面形成单齿螯合物而非双齿双核螯合物	氧化：表面Fe(Ⅲ)对三价砷的氧化需依赖共存的氧化剂；还原：针铁矿的Fe(Ⅲ)被还原，矿物部分溶解并释放吸附的砷
赤铁矿	比表面积为9.33 m²∙g⁻¹；水铁矿或针铁矿脱水脱羟基时转换成赤铁矿	氢键与静电力稳定化表面的五价砷；通过单齿螯合、角落共享和边缘共享式双齿双核螯合，形成内圈和外圈螯合物；内部水结构稳定化五价砷，如五价砷可持续在赤铁矿上形成外圈螯合物（Catalano et al.，2007）	氧化：在光照下产生活性氧物种，显著促进三价砷氧化；还原：强还原条件下可被部分还原为磁铁矿，释放结合态砷
纤铁矿	斜方晶系，层状结构，比表面积50－150 m²∙g⁻¹；碱性或有机质存在的环境中易转化为针铁矿	五价砷通过双齿双核表面复合物与纤铁矿结合；三价砷在酸性条件（pH<6）下通过单齿单核配位吸附	氧化：通过表面吸附的Fe²⁺催化反应间接氧化三价砷；还原：还原条件下（如微生物作用）溶解，释放砷
磁铁矿	反尖晶石结构，具磁性，比表面积20－90 m²∙g⁻¹	五价砷通过配体交换吸附在磁铁矿表面；三价砷在酸性条件（pH 4－6）下通过单齿单核配位吸附	氧化：在氧化条件下部分转化为赤铁矿；还原：表面的Fe²⁺可直接还原五价砷为三价砷（Gubler et al.，2021）
绿锈	层状双氢氧化物，比表面积50－200 m²∙g⁻¹	五价砷通过配体交换吸附在表面层间；三价砷在表面形成单齿单核复合物	氧化：暴露于氧气时分解为针铁矿/赤铁矿；还原：层间的Fe²⁺快速还原五价砷

不同水管理措施	氧化还原电位（Eh）和pH	水稻产量	砷的累积效果	土壤-溶液界面砷的环境化学行为和微生物
长期淹水	低Eh，高pH	淹水管理水稻产量均较高（Arao et al.，2009；Mukherjee et al.，2017；Carrijo er al.，2018）	籽粒对砷的累积量最高	水稻根际土地杆菌属和厌氧粘细菌属具有较高的相对丰度（Das et al.，2016）
间歇式淹水	低Eh和高Eh交替；高pH和低pH交替	比长期淹水和长期干旱处理高（Xu et al.，2008；Honma et al.，2016；Islam et al.，2017）	显著降低水稻对砷的吸收累积	水稻根际土地杆菌属和厌氧粘细菌属相对丰度较低（Das et al.，2016）
点喷式水灌溉管理	高Eh，低pH	与长期淹水管理的水稻产量没有显著差异	极大程度地降低籽粒砷累积	根部周边存在砷氧化基因（aioA）、砷还原基因（arsC）和砷甲基化基因（arsM）；证实了砷存在五价砷的形式，以及相应地水稻籽粒无机砷和有机砷的存在（Jia et al.，2014）
缺水式（有氧过程）灌溉管理	高Eh，低pH	四种处理中产量最低	籽粒中砷的累积最低（Wang et al.，2023）	稻根际土铁氧化菌相对丰度较高，促进了铁的氧化过程

不同水管理措施	氧化还原电位（Eh）和pH	水稻产量	砷的累积效果	土壤-溶液界面砷的环境化学行为和微生物
长期淹水	低Eh，高pH	淹水管理水稻产量均较高（Arao et al.，2009；Mukherjee et al.，2017；Carrijo er al.，2018）	籽粒对砷的累积量最高	水稻根际土地杆菌属和厌氧粘细菌属具有较高的相对丰度（Das et al.，2016）
间歇式淹水	低Eh和高Eh交替；高pH和低pH交替	比长期淹水和长期干旱处理高（Xu et al.，2008；Honma et al.，2016；Islam et al.，2017）	显著降低水稻对砷的吸收累积	水稻根际土地杆菌属和厌氧粘细菌属相对丰度较低（Das et al.，2016）
点喷式水灌溉管理	高Eh，低pH	与长期淹水管理的水稻产量没有显著差异	极大程度地降低籽粒砷累积	根部周边存在砷氧化基因（aioA）、砷还原基因（arsC）和砷甲基化基因（arsM）；证实了砷存在五价砷的形式，以及相应地水稻籽粒无机砷和有机砷的存在（Jia et al.，2014）
缺水式（有氧过程）灌溉管理	高Eh，低pH	四种处理中产量最低	籽粒中砷的累积最低（Wang et al.，2023）	稻根际土铁氧化菌相对丰度较高，促进了铁的氧化过程

稻田土壤中砷的生物地球化学行为研究进展及污染防控策略

Research Progress on the Biogeochemical Behavior of Arsenic in Paddy Soils and Pollution Prevention and Control Strategies

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