The Mediterranean and Black Seas are unique marine environments subject to important anthropogenic pressures due to riverine and atmospheric inputs of organic pollutants. Here, we report the results obtained during two east-west sampling cruises in June 2006 and May 2007 from Barcelona to Istanbul and Alexandria, respectively, where water and plankton samples were collected simultaneously. Both matrixes were analyzed for hexaclorochyclohexanes (HCHs), hexachlorobenzene (HCB), and 41 polychlorinated biphenyl (PCB) congeners. The comparison of the measured HCB and HCHs concentrations with previously reported dissolved phase concentrations suggests a temporal decline in their concentrations since the 1990s. On the contrary, PCB seawater concentrations did not exhibit such a decline, but show a significant spatial variability in dissolved concentrations with lower levels in the open Western and South Eastern Mediterranean, and higher concentrations in the Black, Marmara, and Aegean Seas and Sicilian Strait. PCB and OCPs (organochlorine pesticides) concentrations in plankton were higher at lower plankton biomass, but the intensity of this trend depended on the compound hydrophobicity (K(OW)). For the more persistent PCBs and HCB, the observed dependence of POP concentrations in plankton versus biomass can be explained by interactions between air-water exchange, particle settling, and/or bioaccumulation processes, whereas degradation processes occurring in the photic zone drive the trends shown by the more labile HCHs. The results presented here provide clear evidence of the important physical and biogeochemical controls on POP occurrence in the marine environment.

There is interest in the production, use, and environmental occurrence of perfluorinated compounds (PFCs) across Asia and the Asian contributions to the burden of these compounds reaching the Arctic and other remote regions via long-range transport. A spatial survey of perfluorinated compounds was therefore undertaken across China, India, and Japan in 2009 using passive air samplers. Target analytes were fluorotelomer olefins (FTOs), acrylates (FTAs), alcohols (FTOHs), sulfonamides, and sulfonamidoethanols. Wide variations in concentrations and mixtures of compounds were apparent from the study. Generally the FTOHs were the most abundant, followed by 8:2 FTO in China and Japan and by the sulfonamides in India. There was a general decline in PFC concentration from urban, rural, to remote locations. Background stations reflected regional differences in air mass composition. A site in the west Pacific Ocean exhibited a Japanese profile in which 8:2 FTO and 8:2 FTOH were predominant. In contrast, a southern Indian profile with high 4:2 FTOH concentrations was observed at a background site in southern China.

[1] The air-sea exchange of organic carbon (OC) remains largely unexplored, except for few organic compounds comprising a small fraction of the total aerosol and gaseous OC in the atmosphere. Observations of high atmospheric concentrations and diffusive air-sea exchanges for such individual organic compounds, suggest that air-sea exchange of total OC may contribute significantly to the oceanic carbon budget. Here we quantify the atmosphere-ocean exchanges of total OC in the NE Subtropical Atlantic. Average net gaseous diffusive air-water fluxes averaged -31 and -25 mmol C m À2 d À1 for the spring and fall, respectively, exceeding measured OC inputs by dry aerosol deposition (FDD OC , À0.98 mmol C m À2 d À1) and net CO 2 exchange (F CO2 , À6.3 mmol C m À2 d À1). These fluxes are important to understand the regional carbon budget of the NE Subtropical Atlantic, and depict the atmosphere as a major dynamic vector for OC exchange with the ocean.

Polycyclic aromatic hydrocarbons (PAHs) are a geochemically relevant family of semivolatile compounds originating from fossil fuels, biomass burning, and their incomplete combustion, as well as biogenic sources. Even though PAHs are ubiquitous in the environment, there are no previous studies of their occurrence in the Southern Ocean and Antarctic atmosphere. Here we show the gas and aerosol phase PAHs concentrations obtained from three sampling cruises in the Southern Ocean (Weddell, Bellingshausen, and South Scotia Seas), and two sampling campaigns at Livingston Island (Southern Shetlands). This study shows an important variability of the atmospheric concentrations with higher concentrations in the South Scotia and northern Weddell Seas than in the Bellingshausen Sea. The assessment of the gas-particle partitioning of PAHs suggests that aerosol elemental carbon contribution is modest due to its low concentrations. Over the ocean, the atmospheric concentrations do not show a temperature dependence, which is consistent with an important role of long-range atmospheric transport of PAHs. Conversely, over land at Livingston Island, the PAHs gas phase concentrations increase when the temperature increases, consistently with the presence of local diffusive sources. The use of fugacity samplers allowed the determination of the air-soil and air-snow fugacity ratios of PAHs showing that there is a significant volatilization of lighter molecular weight PAHs from soil and snow during the austral summer. The higher volatilization, observed in correspondence of sites where the organic matter content in soil is higher, suggests that there may be a biogenic source of some PAHs. The volatilization of PAHs from soil and snow is sufficient to support the atmospheric occurrence of PAHs over land but may have a modest regional influence on the atmospheric occurrence of PAHs over the Southern Ocean.