No abstract

[1] The Mediterranean and Black Seas are unique marine environments subject to important anthropogenic pressures due to atmospheric and riverine inputs of organic pollutants. They include regions of different physical and trophic characteristics, which allow the studying of the controls on pollutant occurrence and fate under different conditions in terms of particles, plankton biomass, interactions with the atmosphere, biodegradation, and their dependence on the pollutant physical chemical properties. Polycyclic Aromatic Hydrocarbons (PAHs) have been measured in samples of seawater (dissolved and particulate phases) and plankton during two east-west sampling cruises in June 2006 and May 2007. The concentrations of dissolved PAHs were higher in the south-western Black Sea and Eastern Mediterranean than in the Western Mediterranean, reflecting different pollutant loads, trophic conditions and cycling. Particle and plankton phase PAH concentrations were higher when lower concentrations of suspended particles and biomass occurred, with apparent differences due to the PAH physical chemical properties. The surface PAH particle phase concentrations decreased when the total suspended particles (TSP) increased for the higher molecular weight (MW) compounds, consistent with controls due to particle settling depletion of water column compounds and dilution. Conversely, PAH concentrations in plankton decreased at higher biomass only for the low MW PAHs, suggesting that biodegradative processes in the water column are a major driver of their occurrence in the photic zone. The results presented here are the most extensive data set available for the Mediterranean Sea and provide clear evidence of the important physical and biological controls on PAH occurrence and cycling in oceanic regions.

The overall objective of this work is to provide the first evaluation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurrence and deposition to Mediterranean open seawater. sigma2,3,7,8-PCDD/F air (gas+aerosol) concentrations over the Mediterranean Sea ranged from 60 to 1040 fg m(-3). The highest value (1555 fg m(-3)) was measured in a reference sample taken in the SW Black Sea. No consistent trend regarding the diel cycle of PCDD/Fs was observed. PCDD/Fs transported to the open sea waters from continental areas and across the Atlantic as well as ship emissions may be significant sources to the open Mediterranean. Seawater concentrations in the Mediterranean ranged from 42 to 64 fg L(-1). The sigma2,3,7,8-PCDD/F dry deposition fluxes in the Marmara and Black Seas (210 kg year(-1)) are from 2 to 55 times higher than dry fluxes in the Mediterranean Sea (4-156 kg year(-1)). Analysis of estimated diffusive air-water fluxes and air/water fugacity ratios show that a net volatilization of some PCDD congeners is feasible. However, evidence of a net absorption flux for the rest of PCDD/F is found. When both atmospheric deposition processes are considered together the open Mediterranean Sea is a net sink of PCDD/F, due to the importance of dry deposition fluxes of aerosol-bound PCDDFs.