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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.
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| 科 Family | 属数 Number of genus | 种数 Number of species | 占总种数比例 Percentage of total species (%) | 属 Genus | 种数 Number of species | 占总种数比例 Percentage of total species (%) |
|---|---|---|---|---|---|---|
| 鹅膏菌科Amanitaceae | 2 | 11 | 5.26 | 鹅膏菌属 Amanita | 10 | 4.78 |
| 小菇科 Mycenaceae | 2 | 12 | 5.74 | 丝盖伞属 Inocybe | 5 | 2.39 |
| 多孔菌科 Polyporaceae | 8 | 14 | 6.70 | 蜡蘑属 Laccaria | 5 | 2.39 |
| 红菇科 Russulaceae | 3 | 23 | 11.00 | 小皮伞属 Marasmius | 6 | 2.87 |
| 小菇属 Mycena | 11 | 5.26 | ||||
| 光柄菇属 Pluteus | 5 | 2.39 | ||||
| 红菇属 Russula | 17 | 8.13 | ||||
| 栓菌属 Trametes | 5 | 2.39 |
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