Dissolved polycyclic aromatic hydrocarbons from the Northwestern Pacific to the Southern Ocean: Surface seawater distribution, source apportionment, and air-seawater exchange

Polycyclic aromatic hydrocarbons (PAHs) as a group of toxic and carcinogenic compounds are large scale globally emitted anthropogenic pollutants mainly emitted into the atmosphere. However, atmospheric transport cannot fully explain the spatial variability of PAHs in the marine atmosphere and seawater. It is hypothesized that PAHs accumulated in seawater and ocean circulation can also influence PAHs observed in air above the ocean. In order to investigate PAHs in seawater as a potential secondary source to air, we collected paired air and seawater samples during a research cruise from China to the Antarctic in 2018-2019, covering the Pacific Ocean, the Indian Ocean, and the Southern Ocean. Summed concentrations of 28 analyzed PAHs in seawater were highest in the Pacific Ocean (4000 +/- 1400 pg/L), followed by the Indian Ocean (2700 +/- 1000 pg/L), and the Southern Ocean (2300 +/- 520 pg/L). Three-ringed PAHs dominated the composition profile. We found that PAH levels in the Pacific and Indian Oceans were strong inversely correlated with salinity and distance to the coastline. This suggests that riverine inputs and continental discharges are important sources of PAHs to the marine environment. Derived air-seawater fugacity ratios suggest that net fluxes of PAHs were from seawater to the air in the Pacific and Indian Oceans at 9.0-8100 (median: 1600) ng/m2/d and 290-2000 (median: 1300) ng/ m2/d, respectively. In the Southern Ocean, the net flow of PAHs was from air to seawater with a flux of -1000-450 (median: -82) ng/m2/d. Source apportionment from two different models suggested that the largest contribution to total PAHs was from petrogenic sources (44-57%), followed by coal/wood combustion (30-31%), fossil fuel combustion (15%), and engine combustion emissions (2.8-9.5%). Higher contributions from petrogenic sources were found at sites close to coastal regions. Both coal/wood combustion and petrogenic sources are responsible for the PAH concentrations detected in the Indian and Southern Oceans.