Ecology and Environmental Sciences ›› 2025, Vol. 34 ›› Issue (11): 1802-1811.DOI: 10.16258/j.cnki.1674-5906.2025.11.013
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WU Xiaoling1(
), ZHOU Qichuan2, LIANG Xiaojia2, ZHOU Yanmin2, ZHONG Songxiong2,*(
)
Received:2025-05-20
Online:2025-11-18
Published:2025-11-05
吴小令1(
), 周琪川2, 梁小佳2, 周燕敏2, 钟松雄2,*(
)
通讯作者:
E-mail: 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:CLC Number:
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.
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.
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URL: https://www.jeesci.com/EN/10.16258/j.cnki.1674-5906.2025.11.013
| 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., |
| 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., | 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., | 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., |
| 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 |
Table 1 The effect of different iron mineral on arsenic’s geochemical behavior on paddy soil and rice accumulation efficiency
| 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., |
| 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., | 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., | 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., |
| 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., | 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., |
| 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., | 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., |
| 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., |
| 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., | 稻根际土铁氧化菌相对丰度较高,促进了铁的氧化过程 |
Table 2 The effect of different water management on arsenic’s geochemical behavior on paddy soil and rice accumulation efficiency
| 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., | 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., |
| 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., | 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., |
| 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., |
| 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., | 稻根际土铁氧化菌相对丰度较高,促进了铁的氧化过程 |
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