•Variation and composition in atmospheric PCBs were closely related to the continental outflow.•Aerosol phase PCBs were well predicted by the adsorption and absorption model.•Soot carbon acted as transport medium for the aerosol phase PCBs.•Transport mass of particulate PCBs into the NWP totaled 2333 kg in the spring.Ship-board air samples were collected during March to May 2015 from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) to explore the atmospheric occurrence and gas–particle partitioning of polychlorinated biphenyls (PCBs) when the westerly East Asian Monsoon prevailed. Total PCB concentrations in the atmosphere ranged from 56.8 to 261 pg m−3. Higher PCB levels were observed off the coast and minor temperature-induced changes showed that continuous emissions from East Asia remain as an important source to the regional atmosphere. A significant relationship between Koa (octanol–air partition coefficient) and KP (gas–particle partition coefficient) for PCBs was observed under continental air masses, suggesting that land-derived organic aerosols affected the PCB gas–particle partitioning after long-range transport, while an absence of this correlation was identified in marine air masses. The PCB partitioning cannot be fully explained by the absorptive mechanism as the predicted KP were found to be 2–3 orders of magnitude lower than the measured Kp, while the prediction was closely matched when soot adsorption was considered. The results suggested the importance of soot carbon as a transport medium for PCBs during their long-range transport and considerable impacts of continental outflows on PCBs across the downwind area. The estimated transport mass of particulate PCBs into the ECS and NWP totals 2333 kg during the spring, constituting ca. 17% of annual emission inventories of unintentionally produced PCB in China.Download high-res image (269KB)Download full-size image

•PAHs were observed in air and water from the East China Sea to the northwestern Pacific Ocean.•Air–sea exchange fluxes of gaseous PAHs were indicative of variations of land-based PAH inputs.•Soot carbon acted as transport medium for the aerosol phase PAHs over the northwestern Pacific Ocean.We measured 15 parent polycyclic aromatic hydrocarbons (PAHs) in atmosphere and water during a research cruise from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) in the spring of 2015 to investigate the occurrence, air–sea gas exchange, and gas–particle partitioning of PAHs with a particular focus on the influence of East Asian continental outflow. The gaseous PAH composition and identification of sources were consistent with PAHs from the upwind area, indicating that the gaseous PAHs (three-to five-ring PAHs) were influenced by upwind land pollution. In addition, air–sea exchange fluxes of gaseous PAHs were estimated to be −54.2–107.4 ng m−2 d−1, and was indicative of variations of land-based PAH inputs. The logarithmic gas–particle partition coefficient (logKp) of PAHs regressed linearly against the logarithmic subcooled liquid vapor pressure (logPL0), with a slope of −0.25. This was significantly larger than the theoretical value (−1), implying disequilibrium between the gaseous and particulate PAHs over the NWP. The non-equilibrium of PAH gas–particle partitioning was shielded from the volatilization of three-ring gaseous PAHs from seawater and lower soot concentrations in particular when the oceanic air masses prevailed. Modeling PAH absorption into organic matter and adsorption onto soot carbon revealed that the status of PAH gas–particle partitioning deviated more from the modeling Kp for oceanic air masses than those for continental air masses, which coincided with higher volatilization of three-ring PAHs and confirmed the influence of air–sea exchange. Meanwhile, significant linear regressions between logKp and logKoa (logKsa) for PAHs were observed for continental air masses, suggesting the dominant effect of East Asian continental outflow on atmospheric PAHs over the NWP during the sampling campaign.Download high-res image (372KB)Download full-size image

The concentrations of halogenated flame retardants (HFRs) in PM2.5 were monitored for one year at 10 urban sites in China during 2013–2014. This study investigated four classes of HFRs: nine polybrominated diphenyl ethers (PBDEs), six nonbromodiphenyl ether (BDE) brominated flame retardants, two dechlorane plus (DP) flame retardants, and three chlorinated organophosphate flame retardants (OPFRs). Extremely high concentrations of BDE-209 and DBDPE were observed in only one city (Guangzhou), which was a consequence of the intensive e-waste recycling and disposal operations in the Pearl River Delta. This result differed from the tris(monochloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) distributions, which showed high concentrations in most cities, suggesting wide usage and large emissions in China in recent years. The highest TCPP and TCEP concentrations were observed in the summer, indicating that emission from local sources was an important factor controlling the levels in the air. This was not the case for BDE-209 and DBDPE, for which higher concentrations were found in winter. When bound to particulate matter due to low vapor pressure, these compounds may be more persistent in air, and temperature-dependent gas-particle partitioning was a key factor. Moreover, regional pollution and long-range transport had a significant influence on the seasonal distributions of BDE-209 and DBDPE, especially in cities (Guangzhou and Shanghai) close to electrical/electronic waste recycling sites. Residents in urban areas were exposed to higher levels of chlorinated OPFRs. This raises considerable concern, and an appropriate risk assessment is required.

Gaseous exchange fluxes of organochlorine pesticides (OCPs) across the air–water interface of the coastal East China Sea were determined in order to assess whether the contaminated plume of the Yangtze River could be an important regional source of OCPs to the atmosphere. Hexachlorocyclohexanes (HCHs), chlordane compounds (CHLs), and dichlorodiphenyltrichloroethanes (DDTs) were the most frequently detected OCPs in air and water. Air–water exchange was mainly characterized by net volatilization for all measured OCPs. The net gaseous exchange flux ranged 10–240 ng/(m2·day) for γ-HCH, 60–370 ng/(m2·day) for trans-CHL, 97–410 ng/(m2·day) for cis-CHL, and ∼0 (e.g., equilibrium) to 490 ng/(m2·day) for p,p′-DDE. We found that the plume of the large contaminated river can serve as a significant regional secondary atmospheric source of legacy contaminants released in the catchment. In particular, the sediment plume represented the relevant source of DDT compounds (especially p,p′-DDE) sustaining net degassing when clean air masses from the open ocean reached the plume area. In contrast, a mass balance showed that, for HCHs, contaminated river discharge (water and sediment) plumes were capable of sustaining volatilization throughout the year. These results demonstrate the inconsistencies in the fate of HCHs and DDTs in this large estuarine system with declining primary sources.

•The concentrations are close to the lowest values recorded in the global marine environment.•Different spatial variations between PBDEs and PCBs were observed.•The role of biological pump determined the accumulation of low chlorinated PCBs.•The large riverine sediment discharge was an important source of BDE-209.•The degradation of BDE-209 was an important source of the low brominated PBDEs.Ten surface sediments were collected from the open Indian Ocean at depths below 4000 m in 2011, for the analysis of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). The concentrations of Σ32 PCBs, Σ7 PBDEs, and BDE-209 were 120–514, 49–152, and 7–133 pg/g, respectively. These concentrations are close to the lowest values recorded in the global marine environment. The PCBs had a relatively uniform composition, and were dominated by low chlorinated congeners. The concentrations of di-, tri-, and tetra-PCBs were strongly correlated with the total organic carbon (TOC), suggesting the dissolved PCBs were derived from the atmosphere via diffusive air–water exchange, and absorbed by phytoplankton. A high proportion of BDE209 was only detected in the sediment of the low fan of the Ganga River. There were weak correlations between low brominated BDEs and TOC, implying the degradation of BDE209 is a possible source of lower-brominated BDEs in deep-sea sediments.