淮河流域煤粮复合区溶解性有机质组分特征及转化机制

刘彦君; 高良敏; 武慧君; 宋涵; 开晓莉; 栾磊磊; 陈晓晴; 许婧; 庞振东

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中国环境科学 ›› 2025, Vol. 45 ›› Issue (12) : 6869-6880.

环境生态

淮河流域煤粮复合区溶解性有机质组分特征及转化机制

刘彦君¹, 高良敏¹, 武慧君¹, 宋涵¹, 开晓莉¹, 栾磊磊¹, 陈晓晴¹, 许婧¹, 庞振东²

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Characteristics and transformation mechanism of dissolved organic matter components in the coal-grain overlapping areas of the Huaihe River Basin

LIU Yan-jun¹, GAO Liang-min¹, WU Hui-jun¹, SONG Han¹, KAI Xiao-li¹, LUAN Lei-lei¹, CHEN Xiao-qing¹, XU Jing¹, PANG Zhen-dong²

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摘要

本文以淮河流域煤粮复合区为研究对象,系统采集了煤粮复合区31个水体样品,通过耦合三维荧光光谱-平行因子分析(EEMs-PARAFAC)和傅里叶变换离子回旋共振质谱(FT-ICR MS)技术,揭示了高强度人为扰动下DOM的组成特征,重点解析了淮南段DOM的分子转化路径.结果表明: (1)PARAFAC模型识别出3种荧光组分(C1:UV类腐殖质; C2:陆源胡敏酸; C3:类色氨酸),其强度分布(C1>C3>C2)及荧光参数(FI=(1.77±0.12),HIX=(0.73±0.07)),表明水体DOM来源呈现陆源输入与微生物活动共同作用的特征,印证农业支流陆源输入与城市干流微生物降解的协同作用; (2)FT-ICR MS揭示DOM分子组成呈现“上游农业-下游工业”空间梯度,上游农业区以高占比CHO和CHON为特征,下游城市化区域CHOS占比提升,且PAHs氧化开环与硫醚向磺酸基转化主导分子转化过程; (3)煤粮复合区DOM具有“富硫氮、多源耦合”的特征,农业支流CHON占比(33%~37%)对应化肥输入衍生的脱氨反应,而干流下游“煤-硫”污染物通过光-金属协同催化(Fe²⁺/H₂O₂)驱动自由基断键,形成高芳香性、低氧化态的稳定产物.研究结果揭示了煤粮复合区DOM“自然-人为”双重调控机制,为流域有机污染溯源与面源治理提供了分子层面的理论依据.

Abstract

This study focused on the coal-grain overlapping areas of the Huaihe River Basin, analyzing 31 water samples through integrated EEMs-PARAFAC and FT-ICR MS techniques to unravel DOM molecular signatures and transformation pathways under intense anthropogenic disturbances. Key findings include: (1) PARAFAC identified three fluorescent components (C1: UV humic-like; C2: terrestrial humic acid; C3: tryptophan-like), where intensity distribution (C1 > C3 > C2) and spectral indices (FI = (1.77 ± 0.12); HIX = (0.73 ± 0.07)) revealed dual DOM origins from terrestrial inputs (agricultural tributaries) and microbial degradation (urbanized mainstream), highlighting their synergistic interactions. (2) FT-ICR MS unveiled a distinct "upstream agriculture-downstream industry" spatial gradient: CHO and CHON molecules dominated agricultural headwaters, while CHOS compounds increased downstream, governed by PAHs oxidative ring-opening and thioether-to-sulfonic-group conversion. (3) DOM in coal-grain overlapping areas exhibited "sulfur/nitrogen-enriched, multi-source coupling" characteristics. Elevated CHON proportions (33%~37%) in tributaries correlated with fertilizer-derived deamination processes, whereas downstream photochemical-metal co-catalysis (Fe²⁺/H₂O₂) triggered radical cleavage of "coal-sulfur" pollutants, generating highly aromatic, low-oxidation-state stable products. These findings elucidate the dual natural-anthropogenic regulatory mechanisms of DOM, providing molecular-level insights for organic pollutant source tracing and non-point source management in the basin.

导出引用

刘彦君, 高良敏, 武慧君, 宋涵, 开晓莉, 栾磊磊, 陈晓晴, 许婧, 庞振东. 淮河流域煤粮复合区溶解性有机质组分特征及转化机制[J]. 中国环境科学. 2025, 45(12): 6869-6880

LIU Yan-jun, GAO Liang-min, WU Hui-jun, SONG Han, KAI Xiao-li, LUAN Lei-lei, CHEN Xiao-qing, XU Jing, PANG Zhen-dong. Characteristics and transformation mechanism of dissolved organic matter components in the coal-grain overlapping areas of the Huaihe River Basin[J]. China Environmental Science. 2025, 45(12): 6869-6880

中图分类号： X131

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