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.

[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.

We present here the first estimates of floating macro-litter in surface waters from the Rhone River, based on monthly visual observations during 1-year period (2016-2017). Plastic represented 77% of the identified items, confirming its predominance in riverine floating litter. Fragments (2.5-50 cm) and Single Use Plastics (i.e. bags, bottles and cover/packaging) were among the most abundant items. Frequent non-plastic floating litter were paper items such as packaging material and newspapers, and metal items (mostly cans), representing 14% and 5% of total litter, respectively. A lower-end estimate resulted in ∼223,000 plastic items (∼0.7 t of plastic) transported annually by the Rhone surface waters to the Gulf of Lion (NW Mediterranean Sea). Floating macroplastics are only a fraction of the total plastic export by the Rhone. Our study highlights the current discrepancy between field observations and theoretical estimations. Improvements are needed to harmonize data collection methodologies for field studies and model validation.

∑(30)PAH gas phase concentrations (13-86 and 22-40 ng m(-3) in the Mediterranean and Black Seas, respectively) dominated the atmospheric levels due to the high contribution of phenanthrene, dibenzothiophene and their alkylated derivates. The high variability of PAH atmospheric concentrations in the different sub-basins is due to several factors (i.e. air-mass trajectory, proximity to sources and losses by deposition). The ∑(30)PAH atmospheric deposition (dominated by low MW PAH net air-water diffusive fluxes) is estimated to be ~3100 ton y(-1) (Mediterranean) and ~500 ton y(-1) (Black Sea). Net volatilization for certain PAHs was estimated. Deposition fluxes (1-2 orders of magnitude higher than reported PAH settling fluxes in the water column) confirm an important depletion/sink of water column PAH in the photic zone, especially for low MW PAHs. Degradation processes in the water column may be responsible for this decoupling. Conversely, high MW PAHs dry deposition fluxes are similar to their settling fluxes.

The presence of organophosphate ester (OPE) flame retardants and plasticizers has been confirmed for the first time in the atmosphere over the Mediterranean and Black Seas. Atmospheric aerosol samples were collected during two West-East oceanographic cruises across the Mediterranean and in the southwest Black Sea. This comprehensive assessment of baseline concentrations of aerosol phase OPEs, spatial distribution, and related deposition fluxes reveals levels ranging from 0.4 to 6.0 ng m(-3) for the ∑14OPEs and a lack of significant differences among sub-basins. Levels measured across the Mediterranean Sea and in the Black Sea are in the upper range or higher than those from previous reports for the marine atmosphere, presumably due to proximity to sources. From 13 to 260 tons of OPEs are estimated to be annually loaded to the Mediterranean Sea open waters from the atmosphere. Tris-(1-chloro-2-propyl)phosphate (TCPP) was the most abundant compound over the atmosphere of all the Mediterranean and Black Sea sub-basins, and therefore the chemical reaching surface waters at a higher extent by dry deposition. The atmospheric deposition fluxes of phosphorus due to OPE deposition is a significant fraction of known atmospheric inputs of new organic phosphorus (P), suggesting the relevant role that anthropogenic organic pollutants could play in the P cycle.

he input of solid waste from terrestrial sources to the world's oceans has become a major environmental threat, positioning marine litter and plastic pollution as priority issues in the international agenda [1][2][3][4] . If no effective measures are taken, the prospects for future growth in the production and use of plastics foresee an unsustainable increase in the amount of waste accumulated in terrestrial and aquatic ecosystems around the world 5-7 , with potential impacts on biodiversity and human health 8,9 . Jambeck et al. 10 provided a first approach to modelling mismanaged waste (MW), regarding items as waste if littered or inadequately disposed of on land. Considering the population within a 50-km distance buffer from the coast and assuming a range of conversion rates to marine debris of between 15 and 40% MW, the authors estimated a global annual input of 4.8-12.7 million tonnes (Mt) of plastic to the marine environment. This range of conversion rates of MW to marine debris (15-40%) was based on municipal water quality data gathered in the San Francisco Bay (California) watersheds. Field measurements of plastic input to the oceans are, however, essential for evaluating MW land-ocean transfer rates 6,11,12 , still leaving considerable room for improvement.Rivers act as conduits to the ocean, funnelling the waste dumped into the drainage basins and, as such, they contribute to better understanding the input of litter to the ocean from terrestrial sources. Lebreton et al. 11 and Schmidt et al. 12 estimated the export

Organophosphate esters (OPEs) are widely used as flame retardants and plasticizers and have been detected ubiquitously in the remote atmosphere. Fourteen OPEs were analyzed in 115 aerosol phase samples collected from the tropical and subtropical Atlantic, Pacific, and Indian Oceans during the MALASPINA circumnavigation campaign. OPEs were detected in all samples with concentrations ranging from 360 to 4400 pg m for the sum of compounds. No clear concentration trends were found between the Northern and Southern hemispheres. The pattern was generally dominated by tris(1-chloro-2-propyl) phosphate (TCPP), although tri-n-butyl phosphate (TnBP) had a predominant role in samples close to continents and in those influenced by air masses originating in continents. The dry deposition fluxes of aerosol phase ∑OPE ranged from 4 to 140 ng m d. An estimation of the OPE gas phase concentration and gross absorption fluxes by using three different sets of physical chemical properties suggested that the atmosphere-ocean diffusive exchange of OPEs could be 2-3 orders of magnitude larger than dry deposition. The associated organic phosphorus inputs coming from diffusive OPE fluxes were estimated to potentially trigger up to 1.0% of the reported primary production in the most oligotrophic oceanic regions. However, the uncertainty associated with these calculations is high and mostly driven by the uncertainty of the physical chemical properties of OPEs. Further constraints of the physical chemical properties and fluxes of OPEs are urgently needed, in order to estimate their environmental fate and relevance as a diffusive source of new organic phosphorus to the ocean.

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