Mechanisms of cycling and burying of iron-bound phosphorus (Fe-P) in marine sediments: A review
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摘要:
海洋沉积物中铁结合态磷（Fe-P）的循环机制是调控磷长期封存与再活化的关键环节，深刻影响着海洋初级生产力及全球碳-磷-铁耦合循环。传统理论将Fe-P视为易释放的“临时储存库”，但近年研究发现其内部赋存形态（尤其是蓝铁矿）在特定氧化还原条件下可实现稳定埋藏，成为被低估的重要磷汇。本文系统解析了Fe-P形态转化的前沿进展：揭示铁氧化物驱动的甲烷厌氧氧化通过生成Fe2+直接驱动蓝铁矿沉淀，指出冰期低海平面时期陆源铁输入的增加可促进非渗漏区蓝铁矿形成；阐明海平面波动、硫化物竞争及全球变暖驱动的缺氧扩张如何通过改变沉积物氧化还原梯度和铁供给通量，调控Fe-P的活化-再固定平衡。指出深化Fe-P形态的精准识别、微生物-矿物的相互作用及全球变化级联效应的研究是构建更完善的海洋磷循环模型的核心挑战，对预测近海富营养化趋势及地质历史时期磷-气候反馈机制具有重要科学意义。
Abstract:The cycling mechanisms of iron-bound phosphorus (Fe-P) in marine sediments are pivotal in regulating the long-term sequestration and remobilization of phosphorus, profoundly influencing marine primary productivity and global carbon-phosphorus-iron coupled cycles. Traditional paradigms regard Fe-P as an easily remobilized "temporary reservoir"; however, recent studies reveal that specific occurrence forms within Fe-P—particularly vivianite—can achieve stable burial under certain redox conditions, representing an underestimated yet significant phosphorus sink. This review systematically summarizes the cutting-edge advances in Fe-P transformation mechanisms, unveils how iron oxide-driven anaerobic oxidation of methane (Fe-AOM) directly promotes vivianite precipitation by generating Fe2+, and indicated that enhanced terrigenous iron input during glacial lowstand periods could facilitate vivianite formation in non-seep areas. Furthermore, this paper elucidates how sea-level fluctuation, sulfide competition, and global warming-induced expansion of hypoxia modulate the activation-reimmobilization equilibrium of Fe-P by altering sedimentary redox gradients and iron supply fluxes. In this review, we identified key challenges—including precise identification of Fe-P speciation, microbe-mineral interactions, and cascading effects of global change—that are critical for constructing more robust marine phosphorus cycle models. These advances shall have significant scientific implications for predicting coastal eutrophication trends and phosphorus-climate feedback mechanisms throughout Earth’s history.
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表 1 不同海洋环境下铁还原、硫循环、有机质降解作用对磷循环的影响
Table 1. Effects of iron reduction, sulfur cycling, and organic matter degradation on phosphorus cycling in different marine environments
环境条件 铁结合态磷（Fe-P）
的形态铁还原过程 硫循环过程 有机质（OM）降解作用 磷形态转化的
关键路径高氧 + 低盐度
（如河口）主要为 Fe (Ⅲ) 氧化物
结合磷（Fe/P≈10）铁还原过程受到抑制，以 Fe (Ⅲ) 氧化物
稳定存在硫化物生成少，
Fe2+不易被固定有氧呼吸主导，OM 降解缓慢，释放 PO43−有限 Fe (Ⅲ) 氧化物吸附 PO43−形成 Fe-P，少部分随颗粒沉降埋藏 低氧 + 中低盐度
（如波罗的海）蓝铁矿
（Fe (II)3(PO4)2·8H2O，Fe/P≈1.5）Fe-AOM（铁介导的
甲烷厌氧氧化）活跃，Fe3+→Fe2+硫化物浓度低
（＜100 μmol/L），Fe2+过量厌氧降解主导，OM
分解释放大量 PO43−Fe2+与 PO43−结合形成蓝铁矿，富集于硫酸盐 - 甲烷过渡带（SMTZ）下方 缺氧 + 高盐度（如切萨皮克湾高盐区） Fe (Ⅲ) 氧化物结合磷向 FeSx转化，Fe-P 占比低 铁还原受硫化物抑制（Fe2+→FeSx） 硫化物浓度高
（＞500 μmol/L），Fe2+被完全固定硫酸盐还原耦合 OM 降解，PO43−释放后难以与 Fe 结合 Fe-P 因 Fe2+被硫化物消耗而溶解，PO43−转向形成钙结合磷（CFA） 开阔大洋
（低 OM 通量）以 Fe (Ⅲ) 氧化物
结合磷为主铁还原微弱，Fe (Ⅲ)
氧化物稳定性高硫循环不活跃，
硫化物浓度极低OM 降解缓慢，
PO43−释放少Fe-P 主要通过颗粒沉降埋藏，少部分在沉积物表层因受氧化还原波动发生溶解再吸附 
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