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Multi-phase PAH transport across the land-sea continuum: Mechanistic drivers of source-sink dynamics and
Yang Ye1, Huijun Liu1, Jiajie Hu1
1Zhejiang Key Laboratory of Solid Waste Pollution Control and Resource Utilization, Zhejiang Gongshang University, Hangzhou, 310018, PR China; School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou, 310018, PR China.
Abstract:
Estuarine systems, where intensified biogeochemical processes enhance polycyclic aromatic hydrocarbons (PAHs) accumulation and water-air exchange critically governs contaminant transport, require deeper understanding of land-use and anthropogenic drivers. This study quantifies PAH dynamics in a representative semi-enclosed watershed-estuary system, revealing dissolved concentrations from 2.0 to 49.2 ng/L (normal season), 2.3-37.4 ng/L (flood season), and 2.7-34.8 ng/L (dry season), while atmospheric levels peaking in winter (8.9-250.4 ng/m3). Dissolved PAHs exhibited about 1.5- to 1.9-fold estuarine enrichment during normal/flood seasons but reversed to inland dominance in dry periods, while gaseous PAHs showed consistent estuarine enrichment. Net deposition fluxes (-0.02 to -0.64 ng/m2/day) peaked in winter due to elevated gaseous concentrations and lower temperatures. Land-use conflicts dictated source-sink balances, with construction zones (0.5 km radius) as emission hotspots and waters/wetlands (2 km radius) as primary sinks. Positive Matrix Factorization identified traffic emissions, petrogenic, and coal/biomass combustion sources. PCA-K-means clustering resolved distinct spatiotemporal patterns, including dry-season biomass clusters (48.2%) near construction areas, petrogenic-dominated areas (56.9%) mobilizing during floods, and traffic-intensive residential zones requiring emission controls. Spearman correlation analysis and redundancy analysis (RDA) demonstrated a notable decoupling trend: improved energy structures were significantly associated with decreased high-molecular-weight PAH emissions, whereas the increase in vehicle numbers presented a dual challenge, mitigating gaseous low-molecular-weight PAHs but aggravating aquatic middle-molecular-weight PAHs via road runoff. These findings establish a regional conceptual model illustrating how hydrological forcing, energy structure transitions, and transportation dynamics collectively modulate coastal PAH transport, offering mechanistic insights for pollution mitigation in similar urbanized estuaries.
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