粪肥施用农田土壤中雌激素的赋存特征及生态风险
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南京农业大学土壤有机污染物控制与修复研究所

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国家自然科学基金项目(42177016,42261144738)资助


Occurrence Characteristics and Ecological Risk of Estrogens in Agricultural Soil Amended with Manure Fertilizer
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Institute of Organic Contaminant Control and Soil Remediation, Nanjing Agricultural University

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Supported by the National Natural Science Foundation of China(Nos. 42177016,42261144738)

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    摘要:

    进入土壤后,雌激素往往以有机溶剂提取态、水溶态、腐殖酸结合态、胡敏素结合态等不同形态赋存于土壤中,危害生态安全和人群健康。为探究粪肥施用土壤中雌激素的赋存特征及生态风险,本研究以黄棕壤、棕壤、黑土和红壤为供试土样,通过老化培养实验解析雌二醇(E2)、雌三醇(E3)和双酚A(BPA)的赋存形态,结合土壤基本理化参数与生态风险模型,揭示其赋存形态变化及风险差异。结果表明,土壤类型显著影响雌激素的赋存形态与降解效率。黑土因有机质含量高,老化60 d后其雌激素结合态残留量最高(总17β-E2当量浓度为11.35 μg·kg?1),具有潜在风险,但短期风险较低。红壤因有机质含量和pH低,其雌激素主要以可提取态存在,但60 d时可提取态BPA和E2的风险系数(RQ)分别达0.73和1.78,呈现中高风险。黄棕壤与棕壤中3种雌激素均以结合态为主要赋存形态,E2和E3生物降解较BPA显著,土壤中雌激素环境风险主要由E2和BPA贡献,呈现中高风险。相关性分析表明,可提取态雌激素含量与pH呈显著负相关,与有机质含量呈显著正相关。本研究旨在提出需结合赋存形态与土壤类型差异来优化风险模型,进而为农田雌激素污染的精准管控提供依据。

    Abstract:

    【Objective】 This study aimed to investigate the occurrence characteristics and ecological risks of manure-based fertilizer estrogens (estradiol [E2], estriol [E3], and bisphenol A [BPA]) in different soil types (yellow-brown soil, brown soil, black soil, and red soil) in China. The research sought to elucidate the influence of soil physicochemical properties on estrogen speciation, degradation, and bioavailability, and to establish a framework for optimizing ecological risk models. 【Method】 Four representative agricultural soils were collected, air-dried, and sieved. Cattle manure containing E2 (356.91 ± 0.27 μg·kg?1), E3 (227.58 ± 1.18 μg·kg?1), and BPA (862.21 ± 0.42 μg·kg?1) was mixed with soils at a 1:10 ratio (manure:soil) and incubated for 0–60 d under controlled conditions. Estrogen speciation (organic solvent-extractable, water-soluble, humic acid-bound, and humin-bound forms) was quantified using sequential extraction and HPLC analysis. Soil properties (pH, organic matter, cation exchange capacity, etc.) were measured via standardized methods. Ecological risks were evaluated using risk quotients (RQ) based on predicted no-effect concentrations (PNEC) and estrogen equivalency (EEQ) models. 【Result】 The result revealed that soil type significantly influenced estrogen dynamics. Black soil, with high organic matter (59.73 g·kg?1), exhibited the highest bound-state retention (humic acid-bound BPA: 33.92 μg·kg-1; bound-state total 17β-E2 equivalent: 11.35 μg·kg?1), leading to low short-term risks (E2 RQ = 0.086) but potential long-term risks due to delayed release. In contrast, red soil, with low organic content (8.25 g·kg?1) and acidic pH (5.02), showed elevated extractable state proportion, resulting in high immediate risks (E2 RQ=1.78; BPA RQ=0.73) despite faster degradation (only 6.63%, 6.36% and 1.76% extractable state of E2, E3 and BPA were transferred by day 60 respectively). In both yellow-brown soils and brown soils, the three target estrogens predominantly existed in bound states by day 60 of aging. E2 and E3 underwent significantly more biodegradation than BPA, while environmental risks were primarily contributed by E2 and BPA, presenting medium-to-high risk levels. Correlation analysis revealed extractable state estrogen content was negatively associated with pH and positively linked to organic matter (P<0.01). 【Conclusion】 This study highlights the critical role of soil-specific properties in modulating estrogen speciation and ecological risks. High-organic soils favored bound-state retention, delaying risks, while low-organic acidic soils amplified extractable state bioavailability, necessitating urgent mitigation. Current risk models, which prioritize extractable state concentrations, underestimate long-term hazards from bound-state reservoirs. The findings advocate for integrating speciation dynamics and soil heterogeneity into risk analysis to enable precision management of estrogen contamination in agricultural systems. This approach supports the transition from "total concentration control" to "speciation-targeted mitigation" for sustainable soil health and food safety.

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王俊跃,张紫康,陈 泱,凌婉婷.粪肥施用农田土壤中雌激素的赋存特征及生态风险[J].土壤学报,2026,63(1). DOI:10.11766/trxb202506230305 WANG Junyue, ZHANG Zikang, CHEN Yang, LING Wanting. Occurrence Characteristics and Ecological Risk of Estrogens in Agricultural Soil Amended with Manure Fertilizer[J]. Acta Pedologica Sinica,2026,63(1).

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  • 收稿日期:2025-06-23
  • 最后修改日期:2025-08-20
  • 录用日期:2025-09-05
  • 在线发布日期: 2025-09-17
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