Surface waters are a source of polychlorinated biphenyls to the coastal atmosphere of the North-Western Mediterranean Sea.

Atmospheric (gaseous and particulate) and seawater (dissolved and particulate in the surface microlayer and underlying waters) samples were collected in 2001 and 2002 in two North-Western Mediterranean contrasting coastal environments, Banyuls-sur-Mer (France) and Barcelona (Spain). The total aerosol suspended particle concentrations (microg m(-3)) were higher in Barcelona (266+/-132) than in Banyuls-sur-Mer (149+/-43), even under near-gale conditions. The influence of the marine aerosol in the total suspended particles (TSP) concentration was backed by both organic carbon (OC) and elemental carbon (EC) concentrations, as they exhibited lower levels in Banyuls (3+/-2 microg OC m(-3) and 0.4+/-0.3 microg EC m(-3)) than in Barcelona (31+/-26 microg OC m(-3) and 6+/-8 microg EC m(-3)). Moreover, samples from Barcelona, both atmospheric and seawater, showed greater variability than in Banyuls (Snedecor's test (p<0.001)) possibly reflecting the influence of urban sources of pollutants. Concentrations of atmospheric PCBs (Sigma41 congeners) off-shore Barcelona ranged from 389 to 1410 pg m(-3) in the gas phase and from 71 to 78 pg m(-3) in the aerosol phase. In Banyuls, concentrations were 30.7-858 pg m(-3) in the gas phase and 12.8-41.2 pg m(-3) in the aerosol phase. Their gas-particle partitioning suggested that PCBs in the samples were close to equilibrium (deduced from the regression of the experimental logK(p) and logP(l)(0)). Moreover, a positive correlation was found between wind direction, wind speed and atmospheric PCB concentrations, which is consistent with the fact the PCB concentration of the marine waters, influenced by coastal run-off, become a secondary source for these semi-volatile compounds after volatilization to the coastal atmosphere. This is supported by the high dissolved concentrations in the coastal surface waters, and specially by the enrichment found in the surface microlayer.

Occurrence and fate of polycyclic aromatic hydrocarbons in the coastal surface microlayer.

Polycyclic aromatic hydrocarbons (PAHs) were measured in the coastal sea surface microlayer (SML), the sub-surface waters (SSW) and the overlying atmosphere in order to investigate the influence of the SML on contaminant enrichment and air-sea exchange. Samples were collected at two contrasting locations of the NW Mediterranean, one urban influenced (off Barcelona, Spain) and another comparatively clean (off Banyuls-sur-Mer, France). Statistical data analysis confirmed the accumulation of PAHs in the SML with respect to the SSW (20.3+/-9.1 vs. 13.1+/-10.0 ng L(-1) in the dissolved phase; 709+/-207 vs. 158+/-111 ng g(-1) in the particulate phase). This accumulation was higher at the contaminated location (Barcelona station) compared with the more pristine one, with PAH enrichments 1.5 and 4.5 times higher for the dissolved and particulate phases, respectively, indicating that the enrichment of PAHs in the SML is dominated by particle transport processes.