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.

No abstract

The Southern Ocean is one of the most pristine environments in the world, but is nonetheless affected by inputs of persistent organic pollutants (POPs). In the present work, we report the concentrations of hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), and 26 polychlorinated biphenyl (PCBs) congeners in seawater and phytoplankton from samples obtained during three Antarctic cruises in 2005, 2008, and 2009. The levels of PCBs, HCHs, and HCB are low in comparison to the few previous reports for this region and studies from other oceans. The long-term decline of POP concentrations in the Southern Ocean seawater since early 1980 is consistent with half-lives of 3.4 and 5.7 years for HCHs and PCBs, respectively. There is a large variability of PCBs, HCHs, and HCB concentrations in water and phytoplankton within the Bransfield Strait, South Scotia, Weddell, and Bellingshausen Seas that masks the differences between the studied Seas. However, the variability of PCBs concentrations in phytoplankton is significantly correlated with phytoplankton biomass, with lower concentrations in the most productive waters. This trend is more apparent for the more hydrophobic congeners, consistent with the role of settling fluxes of organic matter decreasing the concentrations of hydrophobic POPs in productive waters. The present work reports the most extensive data set on concentrations in seawater and phytoplankton for the Southern Ocean, and points to the important biogeochemical drivers, such as settling and degradation, influencing the occurrence of POPs in the ocean.

Atmospheric transport and deposition of polycyclic aromatic hydrocarbons (PAHs) over tropical oceans has not yet been studied even though tropical oceans account for 35% of the global oceans. Here we show the results from measurements of gas- and aerosol-phase PAHs and dry deposition samples in the NE tropical Atlantic Ocean atmosphere, a region between 26 degrees and 21 degrees N, off shore of the Saharan desert. The results show that PAHs concentrations are high at the coastal ocean (15-20 ng m(-3) for sum of 27 gas-phase individual PAHs) and decrease by a factor of 2-3 at open ocean (26 degrees W). The spatial variability observed is consistent with dilution, reaction, and deposition during transport. Atmospheric dry deposition velocities ranged between 0.1 and 0.3 cm s(-1) with higher deposition velocities for the more volatile PAHs. Outbreaks of Saharan Dust significantly increase the deposition rates of PAHs. The occurrence and deposition of PAHs in tropical regions is complex and results from the interplay of a number of processes, such as wind speed, aerosol loads, important sources from West Africa, processes controlling the diurnal variability, and sequestration driven by high primary productivity regions. The measured average atmospheric residence times of gas- and aerosol-phase PAHs are 3.7 and 3.5 days, respectively.

Phytoplankton and bacteria play an important role on the biogeochemical cycles of persistent organic pollutants (POPs). However, experimental data and quantitative knowledge of the kinetics of uptake and depuration of most POPs by bacteria and phytoplankton are scarce. In the present paper, a procedure to predict the sorption kinetics to bacteria and phytoplankton is developed. The prediction method is the combination of a mechanistic model for sorption and quantitative structure-activity relationships relating bioconcentration factors and membrane permeability to the chemical physical-chemical properties. The model consists of two compartments where the first compartment is the cellular surface and the second compartment is the cell biomass or matrix. Equations for estimating uptake and depuration rate constants into the matrix and adsorption and desorption rate constants onto the surface are obtained. These expressions depend on the physical-chemical properties of the chemical, the environmental temperature, the microorganism size, and species-specific quality of organic matter. While microorganism shape has a secondary influence on uptake dynamics, microorganism size and chemical hydrophobicity arise as the key factors controlling the kinetics of POP incorporation into bacteria and plankton. Uptake, depuration, adsorption, and desorption rate constants are reported for POPs such as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dioxins and furans (PCDD/Fs), and POPs of emerging concern, such as polybrominated diphenyl ethers (PBDEs). Finally, implications of uptake and depuration dynamics on the biogeochemical cycling of POPs are discussed.