•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

Providing quantitative information on the sources of PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in urban regions is vital to establish effective abatement strategies for air pollution in a megacity. In this study, based on a year data set from October 2011 to August 2012, the sources of PM2.5-bound 16 USEPA priority PAHs (16 PAHs) in Shanghai, a megacity in China, were apportioned by positive matrix factorization (PMF) modeling. The average concentrations (in ng m−3) of 16 PAHs in PM2.5 in the fall, winter, spring and summer were 20.5 ± 18.2, 27.2 ± 24.0, 13.7 ± 7.7 and 6.4 ± 8.1, respectively, with an annual average of 16.9 ± 9.0. The source apportionment by PMF indicated that coal burning (30.5%) and gasoline engine emission (29.0%) were the two major sources of PAHs in the PM2.5 in Shanghai, followed by diesel engine emission (17.5%), air-surface exchange (11.9%) and biomass burning (11.1%). The highest source contributor for PAHs in the fall and winter was gasoline engine emission (36.7%) and coal burning (41.9%), respectively; while in the spring and summer, it was diesel engine emission that contributed the most (52.1% and 43.5%, respectively). It was suggested that there was a higher contribution of PAHs from engine emissions in 2011–2012 compared with those in 2002–2003. The major sources apportioned by PMF complemented well with this of using diagnostic ratios, suggesting a convincing identification of sources for the PM2.5-bound 16 PAHs in a megacity.

The Xiangjiang River (XR), the second largest tributary of the Yangtze River, is mainly located in Hunan province in south-central China. Nineteen surface sediment samples (the top 3-cm layer) collected from XR were analyzed to determine the concentrations, distribution, sources, and ecological risk of organochlorine pesticides (OCPs). The concentrations of OCPs were 3.0–29.8 ng/g (dry weight) with a mean of 12.6 ± 7.7 ng/g. The widely detected compounds included HCHs, DDTs, HCB, and dieldrin. Overall, the dominant OCPs in the sediments were mainly composed of residual and degradation products, e.g., β-HCH with a mean of 42.2 % in HCHs and p,p′-DDE with a mean of 43.5 % in DDTs, implying that OCPs in the sediments had suffered from long-term aging without fresh inputs in XR. However, there was a high proportion of p,p′-DDT to DDTs in three sites, suggesting that there was use of technical DDT from their surrounding areas at present. The ratios of α-HCH/γ-HCH and p,p′-DDD + p,p′-DDE/DDTs increase from the upper reaches to the lower reaches of XR, suggesting sediments enriched with α-HCH and metabolites DDD and DDE during sediment transport process and could be attributed to the transformation of γ-HCH to α-HCH and DDT to DDE or DDD. The assessment of the ecological risk indicates that the OCPs in the sediments of XR have a moderate adverse biological effect on organisms.

The estuarine-inner shelf region of the East China Sea (ECS) is a major sink of the Yangtze River-derived fine-grained sediments and associated organic materials. In this work, surface sediment samples from a matrix of seventy-three sites that extend from the Yangtze River estuary (YRE) to the southern inner shelf were measured for their elemental, stable isotopic and molecular indices to provide a process-oriented study on the sources, distribution and fate of sedimentary organic matter (SOM) in this region. The results indicated that the re-suspension and alongshore transport of sediments could play a key role on the accumulation of SOM in the area. In addition to the physical reworking, the low C/N ratios and the enriched δ13C values could also be likely related to the presence of microorganism-derived organic matter (OM) and soil-derived OM. The composition and principal component analyses of the n-alkanes indicated that the majority of the riverine terrigenous SOM was primarily restricted within the mud deposits along the coastal ECS. The wide occurrence and southward increasing trend of high molecular weight n-alkanes along the coastal ECS suggest an effective preferential dispersal of the terrigenous organic components. However, the local supply of the marine-derived OM potentially promotes the subsequent degradation of these terrigenous OM, which are likely responsible for the decreasing trend of the carbon preference index (CPI25–33) from the northern YRE to the southern inner shelf. This indicates that the transported SOM from the YRE could become more homogenized as it moved toward the southern inner shelf. The presence of unresolved complex mixtures (UCM), lower Pr/Ph ratios and patterns of more stable geochemical biomarkers (hopanes and steranes) in the nearshore region reveals a petroleum contamination in the coastal environment.Highlights► Process-oriented study on sources, distribution and fate of SOM in the coastal ECS. ► Hydrodynamic forces influence sediment sorting and fate of SOM in this region. ► Preferential dispersal of land-based OM is coupled with local supply of marine OM. ► Anthropogenic petroleum input is revealed by molecular compositional patterns.

Fifty-five surface sediment samples covering virtually the entire Bohai Sea (Bohai) were analyzed for organochlorine pesticides (OCPs), in order to provide the extensive information of recent occurrence levels, distribution, possible sources and potential biological risk of these compounds in this area. Concentrations of total dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) in Bohai ranged widely from 0.24 to 5.67 ng g−1 (mean 1.36 ± 0.93 ng g−1) and 0.16 to 3.17 ng g−1 (mean 0.83 ± 0.57 ng g−1), respectively. High concentrations of DDTs were observed in the coastal areas especially at the isolated sites neighboring the harbor or port regions. The recent DDT inputs could be mainly attributed to the agricultural activity (e.g. dicofol), wastewater of chemical plants and the usage of antifouling paint. The distribution pattern of HCHs was different from that of DDTs due to their different physical–chemical properties and amounts of production and usage in the past. (DDE + DDD)/DDT ratios indicated that the degradation of the parent DDT occurred significantly. The contributions of previous and current inputs of pesticides in the coastal areas were distinguished by means of principal component analysis, suggesting that the recent usage of DDT and technical chlordane could serve as important fresh input sources for OCPs. DDTs and chlordanes are the two-main species of OCPs with more ecotoxicological concern in Bohai.

•A 300 year record of PAHs in a delta wetland of Northeast China was established.•Time trend of PAHs corresponded to the regional social-economic development.•Relation of population size with LMW PAH in agricultural economy was revealed.The polycyclic aromatic hydrocarbons (PAHs) of a 210Pb-dated sediment core extracted from the Liaohe River Delta wetland were measured to reconstruct the sediment record of PAHs and its response to human activity for the past 300 years in Northeast China. The concentrations of the 16 U.S. Environmental Protection Agency priority PAHs (∑16PAHs) ranged from 46 to 1167 ng g−1 in this sediment core. The concentrations of the 16 PAHs (especially 4- and 5+6-ring PAHs) after the 1980s (surface sediments 0–6 cm) were one or two orders of magnitudes higher than those of the down-core samples. The exponential growth of 4-ring and 5+6-ring PAH concentrations after the 1980s responded well to the increased energy consumption and number of civil vehicles resulting from the rapid economic development in China. Prior to 1950, relatively low levels of the 16 PAHs and a high proportion of 2+3-ring PAHs was indicative of biomass burning as the main source of the PAHs. A significant increase in the 2 + 3 ring PAH concentration from the 1860s–1920s was observed and could be attributed to a constant influx of population migration into Northeast China. It was suggested that the link between historical trend of PAHs and population or energy use involves two different economic stages. Typically, in an agricultural economy, the greater the population size, the greater the emission of PAHs from biomass burning, while in an industrial economy, the increase in sedimentary PAH concentrations is closely related to increasing energy consumption of fossil fuels.Download high-res image (420KB)Download full-size image

•There was a sharp increase of PBDEs from 1990s in China.•There were different time trends of PBDEs between developed countries and China.•Increasing PBDE level was accompanied by the booming of manufacturing industry.•PBDE emissions from recycling centers of e-wastes were important source.•Better management of these PBDE-containing products is urgently needed in China.The East China Seas (ECSs) are the receptors of the land-based persistent organic pollutants (POPs), such as polybrominated diphenyl ethers (PBDEs) mainly from China through atmospheric deposition driven by the East Asian winter monsoon and fluvial discharge (e.g., Yangtze River and Yellow River), making the offshore sediments to be a good proxy to reconstruct history of those pollutants in China. In this work, four well-placed sediment cores were extracted from the mud areas in the ECSs, and the 210Pb-dated cores were analyzed to yield historical concentration profiles of PBDEs in the area. The results showed that there was a persistent increase from 1970s and almost no clear sign in the decline of PBDEs until recently in China. More importantly, there was a faster increase of PBDEs from 1990s in China; while this period was just shown as gradually leveling off or even declining trends in developed countries. The persistently increasing trend of PBDEs in China since 1990s could be largely due to the booming of the manufacturing industry and unexpectedly transfer of PBDE pollution from developed countries to China. Besides, the relative high concentrations and fluxes of PBDEs in the core from coastal ECS located near a well-known electrical/electronic waste (e-waste) recycling area suggests an important contribution of PBDE emissions from recycling centers of e-waste in China. Although efforts in environmental monitoring of PBDE contamination have been substantially increased over the last decade, China is still lagging behind in terms of nationwide regulation of PBDE usage and treatment of disposal PBDE-containing products.Download full-size image

Providing quantitative information on the sources of PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in urban regions is vital to establish effective abatement strategies for air pollution in a megacity. In this study, based on a year data set from October 2011 to August 2012, the sources of PM2.5-bound 16 USEPA priority PAHs (16 PAHs) in Shanghai, a megacity in China, were apportioned by positive matrix factorization (PMF) modeling. The average concentrations (in ng m−3) of 16 PAHs in PM2.5 in the fall, winter, spring and summer were 20.5 ± 18.2, 27.2 ± 24.0, 13.7 ± 7.7 and 6.4 ± 8.1, respectively, with an annual average of 16.9 ± 9.0. The source apportionment by PMF indicated that coal burning (30.5%) and gasoline engine emission (29.0%) were the two major sources of PAHs in the PM2.5 in Shanghai, followed by diesel engine emission (17.5%), air-surface exchange (11.9%) and biomass burning (11.1%). The highest source contributor for PAHs in the fall and winter was gasoline engine emission (36.7%) and coal burning (41.9%), respectively; while in the spring and summer, it was diesel engine emission that contributed the most (52.1% and 43.5%, respectively). It was suggested that there was a higher contribution of PAHs from engine emissions in 2011–2012 compared with those in 2002–2003. The major sources apportioned by PMF complemented well with this of using diagnostic ratios, suggesting a convincing identification of sources for the PM2.5-bound 16 PAHs in a megacity.