Coastal observation of halocarbons in the Yellow Sea and East China Sea during winter: Spatial distribution and influence of different factors on the enzyme-mediated reactions

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 mu U.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 enzymemediated 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.