Naiara Berrojalbiz

Polycyclic aromatic hydrocarbons (PAHs) in the Mediterranean Sea: Atmospheric occurrence, deposition and decoupling with settling fluxes in the water column

∑(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.

Persistent Organic Pollutants in Mediterranean Seawater and Processes Affecting their Accumulation in Plankton

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.

The oceanic biological pump modulates the atmospheric transport of persistent organic pollutants to the Arctic.

Semivolatile persistent organic pollutants have the potential to reach remote environments, such as the Arctic Ocean, through atmospheric transport and deposition. Here we show that this transport of polychlorinated biphenyls to the Arctic Ocean is strongly retarded by the oceanic biological pump. A simultaneous sampling of atmospheric, seawater and plankton samples was performed in July 2007 in the Greenland Current and Atlantic sector of the Arctic Ocean. The atmospheric concentrations declined during atmospheric transport over the Greenland Current with estimated half-lives of 1-4 days. These short half-lives can be explained by the high air-to-water net diffusive flux, which is similar in magnitude to the estimated settling fluxes in the water column. Therefore, the decrease of atmospheric concentrations is due to sequestration of atmospheric polychlorinated biphenyls by enhanced air-water diffusive fluxes driven by phytoplankton uptake and organic carbon settling fluxes (biological pump).

Occurrence of aerosol-bound fullerenes in the Mediterranean Sea atmosphere.

This work describes the assessment of a selection of fullerenes including C(60) and C(70) fullerene, N-methylfulleropyrrolidine, C(60) pyrrolidine tris-acid ethyl ester, [6,6]-Phenyl-C(61) butyric acid butyl ester and [6,6]-Thienyl C(61) butyric acid methyl ester, in airborne particulate from the Mediterranean Sea collected during two sampling campaigns from Barcelona to Istanbul and Alexandria, respectively. The analysis of the samples was carried out using a new method based on liquid chromatography coupled to mass spectrometry (LC-MS) presenting sensitivities between 5.4 and 20.9 pg/m(3). A total number of 43 samples covering the different basins of Mediterranean Sea were analyzed. Fullerenes were detected in all analyzed samples and quantifiable concentrations were found in 28 of the analyzed samples. The median of C(60) and C(70) fullerenes aerosol phase concentrations were 0.06 ng/m(3) and 0.48 ng/m(3) respectively for the Mediterranean Sea atmosphere. C(70) fullerene was the most frequently detected compound and also it was found in the higher concentrations for most samples, reaching 233.8 ng/m(3). The modeled back-trajectories disclose that those samples with higher concentrations of fullerenes were related to air masses which had been circulating over regions with an intense industrial activity, but the variability of the C(70)/C(60) ratio suggests multiple different sources. These results are related to the incidental emissions from urban and industrial development, underpinning the need of studying the possible risks associated to carbon nanoparticles in the environment and the need of evaluating the possible consequences of their ubiquitous occurrence.

Organophosphate Ester (OPE) Flame Retardants and Plasticizers in the Open Mediterranean and Black Seas Atmosphere

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.

Decrease in the abundance and viability of oceanic phytoplankton due to trace levels of complex mixtures of organic pollutants.

Long range atmospheric transport and deposition is a significant introduction pathway of organic pollutants to remote oceanic regions, leading to their subsequent accumulation in marine organisms. Persistent organic pollutants (POPs) bioconcentrate in planktonic food webs and these exert a biogeochemical control on the regional and global cycling of POPs. Therefore, an important issue is to determine whether the anthropogenic chemical perturbation of the biosphere introduced by the myriad of organic pollutants present in seawater influences phytoplankton abundance and productivity. The results reported here from five sets of experiments performed in the NE Atlantic Ocean show that there is a toxic effect induced by trace levels of complex mixtures of organic pollutants on phytoplankton oceanic communities. The levels of single pollutant, such as phenanthrene and pyrene, at which lethality of phytoplankton is observed are high in comparison to field levels. Complex mixtures of organic pollutants, however, have an important toxic effect on phytoplankton abundances, viability and concentrations of Chlorophyll a at pollutant concentrations 20-40 folds those found in the open ocean. The toxicity of these complex mixtures of organic pollutants exceeds by 10(3) times the toxicity expected for a single pollutant. Therefore, our results point out the need for a systematic investigation of the influence of complex mixtures of organic hydrophobic pollutants to oceanic phytoplankton communities, a perturbation not accounted for on previous assessments of anthropogenic pressures in the marine environment.

Polychlorinated Biphenyls, Hexachlorocyclohexanes and Hexachlorobenzene in Seawater and Phytoplankton from the Southern Ocean (Weddell, South Scotia, and Bellingshausen Seas)

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 Occurrence and Deposition of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans (PCDD/Fs) in the Open Mediterranean Sea

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.

The "degradative" and "biological" pumps controls on the atmospheric deposition and sequestration of hexachlorocyclohexanes and hexachlorobenzene in the North Atlantic and Arctic Oceans

The cycling of hexachlorobenzene (HCB) and hexachlorocyclohexanes (HCHs) has been studied in the North Atlantic and Arctic Ocean. Concentrations of HCHs and HCB were measured simultaneously in the atmosphere (gas and aerosol phases), seawater (dissolved and particulate phases), and phytoplankton. The atmospheric concentrations of HCHs decrease during transport over the Greenland Current with estimated e-folding times of 1.6 days, a trend not observed for HCB. This strong decrease in atmospheric concentrations of HCH is consistent with the estimated atmospheric depositional fluxes driven by the air-water disequilibrium. The removal of HCHs from the surface ocean by the degradative pump due to hydrolysis and microbial degradation and by the biological pump due to settling of particle-associated HCHs are estimated; the removal fluxes are within a factor of 2 of the atmospheric inputs for most sampling events, suggesting an important role of the degradative pump in the overall oceanic sink of HCHs. Conversely, the lack of degradation of HCB in surface waters and its relatively low hydrophobicity imply a lack of effective removal processes, consistent with the observed air and water concentrations close to equilibrium. This work is the first that estimates the relative importance of the biological and degradative pumps on the atmospheric deposition of the less persistent organic pollutants and points out the need for further research for quantifying the magnitude of degradative processes in the environment.

Integrated modelling of Polycyclic Aromatic Hydrocarbons in the marine environment: Coupling of hydrodynamic, fate and transport, bioaccumulation and planktonic food-web models

Spatio-temporal variability of pollutants in the environment is a complex phenomenon that requires a combined approach for its analysis. Whereas data on measured levels of contaminants in various environmental compartments is essential, it is not always possible to monitor at the necessary frequency and with the adequate spatial sampling distribution to capture this variability. Therefore a modelling approach able to complement experimental data and close the gaps in the monitoring programs is useful for assessing the contaminant dynamics occurring at different time scales. In this work a 1D water column fate model has been developed and tested for Polycyclic Aromatic Hydrocarbons (PAHs). The model has been coupled with a simple ecological model that includes a bioaccumulation module. Afterwards, the model has been used to study the temporal variability of contaminant concentrations as well as the fluxes between compartments. The results evidence the complex coupling between spatio-temporal scales and its influence on environmental concentration levels.