The oceanic production and release of volatile halocarbons (VHCs) to the atmosphere play a vital role in regulating the global climate. In this study, seasonal and spatial variations in VHCs, including trichlorofluoromethane (CFC-11), methyl iodide (CH₃I), dibromomethane (CH₂Br₂), and bromoform (CHBr₃), and environmental parameters affecting their concentrations were characterized in the atmosphere and seawater of the Yangtze River Estuary and its adjacent marine area during two cruises from October 17 to October 26, 2019 and from May 12 to May 25, 2020. Significant seasonal variations were observed in the atmosphere and seawater because of seasonal differences in the prevalent monsoon, water mass (Yangtze River Diluted Water), and biogenic production. VHCs concentrations were positively correlated with Chl-a concentrations in the surface water during autumn. The average sea-to-air fluxes of CH₃I, CH₂Br₂, and CHBr₃ in autumn were 19.7, 4.0, and 7.6 nmol m⁻² d⁻¹, respectively, while those in spring were 6.3, 6.4, and −3.6 nmol m⁻² d⁻¹. In the ship-based incubation experiments, ocean acidification and dust deposition had no significant effects on VHCs concentrations. The concentrations of CH₂Br₂ and CHBr₃ were significantly positively correlated with phytoplankton biomass under lower pH condition (M3: pH 7.9). This result indicated that CH₂Br₂ and CHBr₃ concentrations were mainly related to the biological release.

Volatile brominated compounds are important trace gases for stratospheric ozone chemistry. In this study, the spatial variations of dibromomethane (CH₂Br₂), bromodichloromethane (CHBrCl₂), dibromochloromethane (CHBr₂Cl) and bromoform (CHBr₃) in the seawater and overlying atmosphere were measured in the Yellow Sea (YS) and the East China Sea (ECS) in winter. The air-sea fluxes of CH₂Br₂, CHBrCl₂, CHBr₂Cl and CHBr₃ ranged from −11.46 to 25.33, −4.68 to 7.91, −8.60 to 4.08 and −88.57 to 8.84 nmol m⁻²·d⁻¹, respectively. In order to understand the mechanism of halocarbons production, we measured bromoperoxidase (BrPO) activity (39.18–186.74 μU·L⁻¹) in the YS and ECS for the first time using an aminophenyl fluorescein (APF) method and performed in-situ incubation experiments in BrPO-treated seawater. The production rates of CH₂Br₂, CHBrCl₂, CHBr₂Cl and CHBr₃ ranged from 14.21 to 94.74, 0.00 to 19.74, 0.00 to 30.62 and 6.18–72.75 pmol L⁻¹·h⁻¹, respectively, in BrPO-treated seawater. There were significantly higher production rates in coastal waters compared with the open sea (P = 0.016) because of higher DOC levels near the coast. Moreover, the production rates of halocarbons increased with BrPO activity and H₂O₂ concentration. The results showed that enzyme-mediated reaction was an important source for the production of halocarbons in seawater. The present research is of great significance for understanding the production mechanisms of halocarbons in seawater and global oceanic halocarbons emissions.