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The sources, biogeochemical controls and sinks of perfluoroalkyl substances, such as perfluoroalkyl acids (PFAAs), in polar coastal regions are largely unknown. These were evaluated by measuring a large multi-compartment dataset of PFAAs concentrations at coastal Livingston and Deception Islands (maritime Antarctica) during three austral summers. PFAAs were abundant in atmospheric-derived samples (aerosols, rain, snow), consistent with the importance of atmospheric deposition as an input of PFAAs to Antarctica. Such PFAAs deposition was unequivocally demonstrated by the occurrence of PFAAs in small Antarctic lakes. Several lines of evidence supported the relevant amplification of PFAAs concentrations in surface waters driven by snow scavenging of sea-spray aerosol-bound PFAAs followed by snow-melting. For example, vertical profiles showed higher PFAAs concentrations at lower-salinity surface seawaters, and PFAAs concentrations in snow were significantly higher than in seawater. The higher levels of PFAAs at Deception Island than at Livingston Island are consistent with the semi-enclosed nature of the bay. Concentrations of PFOS decreased from 2014 to 2018, consistent with observations in other oceans. The sink of PFAAs due to the biological pump, transfer to the food web, and losses due to sea-spray aerosols alone are unlikely to have driven the decrease in PFOS concentrations. An exploratory assessment of the potential sinks of PFAAs suggests that microbial degradation of perfluoroalkyl sulfonates should be a research priority for the evaluation of PFAAs persistence in the coming decade., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Jordi Dachs reports financial support and administrative support were provided by Spanish Scientific Research Council. Jordi Dachs reports financial support was provided by Spanish agency for research., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Semivolatile organic pollutants have potential for long range atmospheric transport and can thus reach pristine remote lakes by atmospheric deposition. Polycyclic aromatic hydrocarbons (PAHs) are among the most abundant and toxic semivolatile pollutants affecting lakes, however, the main factors controlling their fate are still poorly known. Here we show two contrasting lines of evidence for the importance of microbial degradation on the environmental fate of PAHs in a high altitude deep lake. The first evidence is given by an assessment of the metagenomes from surface and deep waters from Lake Redon (Pyrenees Mountains), which shows the occurrence of the initial ring hydroxylating dioxygenases as well as other PAH degrading genes from the complete metabolic route of PAH degradation. The second line of evidence is by the application of an environmental fate model for PAHs to Lake Redon under two contrasting scenarios considering the inclusion or not of degradation. When degradation is included in the model, PAH concentrations in the sediment are predicted within a factor of two of those measured in Lake Redon. Finally, the extent of the degradation sink is quantified and compared to other cycling PAH fluxes in the lake., (Copyright © 2022. Published by Elsevier Ltd.)

In this study, the occurrence and diffusive air-water exchange of POPs in Panguipulli Lake (39°42'S-72°13'W), an oligotrophic lake located in northern Patagonia (Chile), were determined. Air and water samples were collected between March and August 2017 (autumn-winter) and analyzed for concentrations of OCPs (α-HCH, β-HCH, γ-HCH and HCB) and PCBs (PCB-28,-52,-101,-118,-153,-158,-180) using gas chromatography coupled with an electron capture detector. The direction of air-water exchange direction was evaluated using a fugacity approach (ƒ w ƒ a -1 ), and net diffusive exchange fluxes (F AW , ng m -2 d -1 ) were also estimated. Total ∑ 4 OCP levels in air ranged from 0.31 to 37 pg m -3 , with a maximum for β-HCH, while Σ 7 PCB levels ranged from 3.05 to 43 pg m -3 . The most abundant congener was PCB-153, accounting for 60% of the total PCBs in air. Surface water ∑ 4 OCPs measured in this study ranged from 1.01 to 3.9 pg L -1 , with γ-HCH predominating, while surface water Σ 7 PCB levels ranged from 0.32 to 24 pg L -1 , with PCB-101, PCB-118, and PCB-153 presenting the highest levels. Diffusive air-water exchanges of HCB, α-HCH, γ-HCH and PCBs in the form of volatilization from the lake to air predominated; in contrast, for β-HCH net deposition dominated during the sampling period. Estimates suggested faster microbial degradation in the dissolved phase compared to atmospheric degradation for all analyzed POPs. Overall, these results could indicate that the oligotrophic lakes of northern Patagonia act as a secondary source of atmospheric POPs, mainly PCBs and some OCPs. This study is a first attempt to understand the occurrence of POPs in air and water, as well as their dynamics in oligotrophic lakes in the southern hemisphere., (Copyright © 2021. Published by Elsevier Inc.)

The ubiquitous occurrence of perfluoroalkyl substances (PFAS) in the open ocean has been previously documented, but their vertical transport and oceanic sinks have not been comprehensively characterized and quantified at the oceanic scale. During the Malaspina 2010 circumnavigation expedition, 21 PFAS were measured at the surface and at the deep chlorophyll maximum (DCM) in the Atlantic, Indian and Pacific oceans. In this work, we report an extended data set of PFAS dissolved phase concentrations at the DCM. ∑PFAS at the DCM varied from 130 to 11 000 pg L -1 , with a global average value of 500 pg L -1 . Perfluorooctanesulfonate (PFOS) abundance contributed 39% of ∑PFAS, followed by perfluorodecanoate (PFDA, 17%), and perfluorohexanoate (PFHxA, 12%). The relative contribution of the remaining compounds was below 10%, with perfluorooctanoate (PFOA) contributing only 5% to PFAS measured at the DCM. Estimates of vertical diffusivity, derived from microstructure turbulence observations in the upper (<300 m) water column, allowed the derivation of PFAS eddy diffusive fluxes from concurrent field measurements of eddy diffusivity and PFAS concentrations. The PFAS concentrations at the DCM predicted from an eddy diffusivity model were lower than field-measured concentrations, suggesting a relevant role of other vertical transport mechanisms. Settling fluxes of organic matter bound PFAS (biological pump), oceanic circulation and potential, yet un-reported, biological transformations are discussed.

Organic pollutants are continuously being introduced in seawater with uncharacterized impacts on the engines of the marine biogeochemical cycles, the microorganisms. The effects on marine microbial communities were assessed for perfluoroalkyl substances, organophosphate esters flame retardants and plasticizers, polycyclic aromatic hydrocarbons, and n-alkanes. Dose-response experiments were performed at three stations and at three depths in the NW Mediterranean with contrasted nutrient and pollutant concentrations. In these experiments, the microbial growth rates, the abundances of the main bacterial groups, measured by Catalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD-FISH), and extracellular enzymatic activities, were quantified. Increasing concentrations of organic pollutants (OPs) promoted different responses in the communities that were compound, organism and nutrient availability (trophic status). The largest differences between OP treatments and controls in the growth rates of both heterotrophic and phototrophic microbial groups were observed in seawater from the deep chlorophyll maxima. Furthermore, there was a compound specific stimulation of different extracellular enzymatic activities after the exposure to OPs. Our results revealed that marine microbial communities reacted not only to hydrocarbons, known to be used as a carbon source, but also to low concentrations of organic pollutants of emerging concern in a complex manner, reflecting the variability of various environmental variables. Multiple linear regressions suggested that organic pollutants modulated the bacterial growth and extracellular enzymatic activities, but this modulation was of lower magnitude than the observed pronounced response of the microbial community to nutrient availability., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The anthropogenic perturbation of the phosphorus (P) marine biogeochemical cycle due to synthetic organophosphorus compounds remains unexplored. The objective of this work was to investigate the microbial degradation of organophosphate triesters (OPEs), widely used as plasticizers and flame retardants, in seawater and their effects on the physiology and composition of microbial communities. Experiments were performed in July 2014 using surface seawater from the Blanes Bay Microbial Observatory (NW Mediterranean) to which OPEs were added at environmentally relevant concentrations. The concentrations of OPEs in the dissolved-phase generally decreased after 24 hours of incubation at in situ conditions. The fitted first order reaction constants were significantly different than zero for the trihaloalkyl phosphate, tris(2-chloroethyl) phosphate and trialyl phosphate tricresyl phosphate. In general, OPEs triggered an increase of the percentage of actively respiring bacteria, total bacterial activity, and the number of low-nucleic acid bacteria, and a decrease in the percentage of membrane-compromised bacteria. Members of some bacterial groups, in particular Flavobacteria, increased their specific activity, indicating that seawater contains bacteria with the potential to degrade OPEs. In aged seawater that was presumably depleted of labile dissolved organic carbon and inorganic P, alkaline phosphatase activities significantly decreased when OPEs were added, indicating a relief on P stress, consistent with the role of OPEs as potential P sources.

Persistent organic pollutants (POPs) reach Antarctica through atmospheric transport, oceanic currents, and to minor extent, by migratory animals. The Southern Ocean is a net sink for many POPs, with a key contribution of the settling fluxes of POPs bound to organic matter (biological pump). However, little is known about POP transfer through the food web in the Southern Ocean and Antarctic waters, where krill is an important ecological node. In this study, we assessed the occurrence of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs) in Antarctic krill (Euphausia superba) from the Bellingshausen, South Scotia and Weddell Seas around the Antarctic Peninsula. The concentrations of PCDD/Fs, PBDEs and PCBs in krill showed a large variability and the average were higher (generally within a factor 3) than those previously reported for eastern Antarctica. This result highlights regional differences related to atmospheric transport and deposition, and also probable regional sources due to human activities. Bioaccumulation and biomagnification factors for PCBs in krill were estimated using previously reported phytoplankton and seawater concentrations for this region. These suggested a near water-krill equilibrium for PCBs, which was not observed for water-phytoplankton partitioning. The estimated removal settling fluxes of PCBs due to the biological pump were several orders of magnitude higher than the estimated fluxes of PCBs transferred from phytoplankton to krill., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The impact of organic pollutants on oceanic ecosystem functioning is largely unknown. Prochlorococcus, the most abundant known photosynthetic organism on Earth, has been suggested to be especially sensible to exposure to organic pollutants, but the sub-lethal effects of organic pollutants on its photosynthetic function at environmentally relevant concentrations and mixtures remain unexplored. Here we show the modulation of the expression of two photosynthetic genes, rbcL (RuBisCO large subunit) and psbA (PSII D1 protein), of oceanic populations of Prochlorococcus from the Atlantic, Indian and Pacific Oceans when exposed to mixtures of organic pollutants consisting of the non-polar fraction of a seawater extract. This mixture included most persistent organic pollutants, semivolatile aromatic-like compounds, and the unresolved complex mixture of hydrocarbons. Prochlorococcus populations in the controls showed the expected diel cycle variations in expression of photosynthetic genes. However, exposure to a complex mixture at concentrations only 2-fold above the environmental levels resulted in a decrease of expression of both genes, suggesting an effect on the photosynthetic function. While organic pollutant effects on marine phytoplankton have been already demonstrated at the cellular level, this is the first field study showing alterations at the molecular level of the photosynthetic function due to organic pollutants.

The bioaccumulation of perfluoroalkylated substances (PFASs) in plankton has previously been evaluated only in freshwater and regional seas, but not for the large oligotrophic global oceans. Plankton samples from the tropical and subtropical Pacific, Atlantic and Indian Oceans were collected during the Malaspina 2010 circumnavigation expedition, and analyzed for 14 ionizable PFASs, including perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS) and their respective linear and branched isomers. PFOA and PFOS concentrations in plankton ranged from 0.1 to 43 ng g dw -1 and from 0.5 to 6.7 ng g dw -1 , respectively. The relative abundance of branched PFOA in the northern hemisphere was correlated with distance to North America, consistent with the historical production and coherent with previously reported patterns in seawater. The plankton samples showing the highest PFOS concentrations also presented the largest relative abundances of branched PFOS, suggesting a selective cycling/fractionation of branched PFOS in the surface ocean mediated by plankton. Bioaccumulation factors (BAFs) for plankton were calculated for six PFASs, including short chain PFASs. PFASs Log BAFs (wet weight) ranged from 2.6 ± 0.8 for perfluorohexanesulfonic acid (PFHxS), to 4.4 ± 0.6 for perfluoroheptanoic acid (PFHpA). The vertical transport of PFASs due to the settling of organic matter bound PFAS (biological pump) was estimated from an organic matter settling fluxes climatology and the PFAS concentrations in plankton. The global average sinking fluxes were 0.8 ± 1.3 ng m -2 d -1 for PFOA, and 1.1 ± 2.1 ng m -2 d -1 for PFOS. The residence times of PFAS in the surface ocean, assuming the biological pump as the unique sink, showed a wide range of variability, from few years to millennia, depending on the sampling site and individual compound. Further process-based studies are needed to constrain the oceanic sink of PFAS.

Semivolatile and persistent organic pollutants (POPs) undergo atmospheric transport before being deposited to the oceans, where they partition to phytoplankton organic matter. The goal of this study was to determine the toxicity of naturally occurring complex mixtures of organic pollutants to temperate and polar phytoplankton communities from the Mediterranean Sea, the North East (NE) Atlantic, and Southern Oceans. The cell abundance of the different phytoplankton groups, chlorophyll a concentrations, viability of the cells, and growth and decay constants were monitored in response to addition of a range of concentrations of mixtures of organic pollutants obtained from seawater extracts. Almost all of the phytoplankton groups were significantly affected by the complex mixtures of non-polar and polar organic pollutants, with toxicity being greater for these mixtures than for single POPs or simple POP mixtures. Cocktails' toxicity arose at concentrations as low as tenfold the field oceanic levels, probably due to a higher chemical activity of the mixture than of simple POPs mixtures. Overall, smaller cells were the most affected, although Mediterranean picophytoplankton was significantly more tolerant to non-polar POPs than picophytoplankton from the Atlantic Ocean or the Bellingshausen Sea microphytoplankton., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Atmospheric deposition of particulate matter (PM) is recognized as a relevant input vector for toxic compounds, such as polycyclic aromatic hydrocarbons (PAHs), into the marine environment. In this work we aimed to analyse the biological activity and potential adverse effects of PM constituents to aquatic organisms. Organic extracts of atmospheric PM samples from different sub-basins of the Mediterranean and Black Seas were screened using different toxicological tests. A yeast-based assay (AhR-RYA) revealed that dioxin-like activity correlated with the concentration of total PAHs in the PM samples, as well as with their predicted toxic equivalent values (TEQs). Although the zebrafish embryotoxicity test (the ZET assay) showed no major phenotypical adverse effects, up-regulation of mRNA expression of cyp1a, fos and development-related genes (previously described as related to PM toxicity) was observed in exposed embryos when compared to controls. Results showed that mRNA patterns of the studied genes followed a similar geographic distribution to both PAH content and dioxin-like activity of the corresponding extracts. The analysis also showed a distinct geographical pattern of activation of pancreatic markers previously related to airborne pollution, probably indicating a different subset of uncharacterized particle-bound toxicants. We propose the combination of the bioassays tested in the present study to be applied to future research with autochthonous species to assess exposure and potential toxic effects of ambient PM. The present study emphasizes the need for more in-depth studies into the toxic burden of atmospheric PM on aquatic ecosystems, in order to improve future regulatory guidelines., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in plankton samples from the Atlantic, Pacific, and Indian Oceans collected during the Malaspina circumnavigation cruise. The concentrations of PCDD/Fs and dl-PCBs in plankton averaged 14 and 240 pg gdw(-1), respectively, but concentrations were highly variable. The global distribution of PCDD/Fs and dl-PCBs was not driven by proximity to continents but significantly correlated with plankton biomass, with higher plankton phase PCDD/F and dl-PCB concentrations at lower biomass. These trends are consistent with the interactions between atmospheric deposition, biomass dilution, and settling fluxes of organic matter in the water column (biological pump), as key processes driving POPs plankton phase concentrations in the global oceans. The application of a model of the air-water-plankton diffusive exchange reproduces in part the influence of biomass on plankton phase concentrations and suggests future modeling priorities. The estimated oceanic sink (Atlantic, Pacific, and Indian Oceans) due to settling fluxes of organic matter bound PCDD/Fs and dl-PCBs is of 400 and 10,500 kg y(-1), respectively. The atmospheric inputs due to gross diffusive absorption and dry deposition are nearly 3 and 10 times larger for PCDD/Fs and dl-PCBs, respectively, than the oceanic sink. These observations suggest that the coupling of atmospheric deposition with water column cycling supports and drives the accumulation of dl-PCBs and PCDD/Fs in plankton from the global oligotrophic oceans.

Here we estimate the importance of vertical eddy diffusion in removing perfluorooctanoic acid (PFOA) from the surface Ocean and assess its importance as a global sink. Measured water column profiles of PFOA were reproduced by assuming that vertical eddy diffusion in a 3-layer ocean model is the sole cause for the transport of PFOA to depth. The global oceanic sink due to eddy diffusion for PFOA is high, with accumulated removal fluxes over the last 40 years of 660 t, with the Atlantic Ocean accounting for 70% of the global oceanic sink. The global oceans have removed 13% of all PFOA produced to a depth greater than 100 m via vertical eddy diffusion; an additional 4% has been removed via deep water formation. The top 100 m of the surface oceans store another 21% of all PFOA produced (∼1100 t)., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

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.

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.

Hydroxyl radical (OH), the main atmospheric oxidant at the global scale, is believed to play an important role in the dynamics of dissolved organic matter in the sea. Herein, we provide evidence, on the basis of seven experiments performed in contrasting ecosystems (subtropical NE Atlantic and Antarctic waters), of high fluxes of atmospheric OH into the surface oceanic layer, particularly during afternoon events. The experiments demonstrated a tight negative relationship between phytoplankton abundance and the concentration of OH in surface seawater, with acute cell death during afternoon atmospheric OH influx events. The effect of OH radical was higher for picophytoplankton organisms, with Prochlorococcus showing the highest decay rate and the shortest half-life among the phytoplankton populations habiting the ocean surface layers. Our results provide evidence for a high toxicity of atmospheric-derived OH radical to phytoplankton of the surface layer of the ocean., (© 2012 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2012 The American Society of Photobiology.)

∑(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., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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).

The goal of this study was to experimentally assess the coupling between primary producer biomass dynamics and the distribution and fate of persistent organic pollutants (POPs) in a lake pelagic ecosystem. This was done by following the short-term evolution of polychlorinated biphenyl (PCB) concentrations in water and biota (phytoplankton and zooplankton) and the variability of bioconcentration (BCF), biomagnification (BMF), and bioaccumulation (BAF) factors during the development of a typical spring ecological progression in which the phytoplankton bloom is followed by a peak in the zooplankton abundance. The bulk of compounds with log K(OW) > 6.5 in the lake epilimnion was mainly associated with primary producer biomass. The phytoplankton biological pump was a major driver of POP export from the epilimnion, causing the decline of dissolved-phase concentrations. The BCF of phytoplankton for the more hydrophobic PCBs showed minima during the period of biomass climax. The concentration in the zooplankton of all selected PCBs sharply declined from March to May, with BAFs having minima in the post algal bloom phase. Biomagnification occurred during the pre algal bloom and algal bloom phases but appeared to be absent during the post algal bloom. This study highlights the occurrence of a prompt and complex response in the fate and distribution of POPs to dynamic biogeochemical control. Within the frame of the ecological succession, phytoplankton and zooplankton biomass dynamics produced bioaccumulation metrics varying over 1-2 orders of magnitude in the time frame of a few weeks and resulted in reduced trophic web exposure.

Partitioning behavior of hydrophobic and semivolatile chemicals (such as many POPs and PAHs) in water is key in controlling their environmental distribution and fate. A new equilibrium method is presented here which allows determination of the equilibrium partition coefficient of hexachlorobenzene with suspended particle (K(SPM)≈ 337 L gOC(-1)) in a complex bulk water sample by correcting for a number of sampling artifacts and for the presence of dissolved matter. The method provides simultaneous experimental determination of the fraction of chemical truly dissolved in water (representing in this case about 54% of the bulk water concentration) and that associated to DM (21%). The Henry's law constant was also experimentally determined during the K(SPM) measurements, providing information on the occurrence of partitioning equilibrium in the system for each single observation. Results showed that the high level of quality control and accuracy provided confidence intervals for the K(SPM) estimates within 1 order of magnitude.

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.

Polycyclic Aromatic Hydrocarbons' (PAHs) toxicity is enhanced by the presence of ultraviolet radiation (UVR), which levels have arisen due to the thinning of the ozone layer. In this study, PAHs' phototoxicity for natural marine phytoplankton was tested. Different concentrations of a mixture of 16 PAHs were added to natural phytoplankton communities from the Mediterranean Sea, Atlantic, Arctic and Southern Oceans and exposed to natural sunlight received in situ, including treatments where the UVR bands were removed. PAHs' toxicity was observed for all the phytoplankton groups studied in all the waters and treatments tested, but only for the pico-sized group a synergetic effect of the mixture and UVR was observed (p=0.009). When comparing phototoxicity in phytoplankton from oligotrophic and eutrophic waters, synergy was only observed at the oligotrophic communities (p=0.02) where pico-sized phytoplankton dominated. The degree of sensitivity was related to the trophic degree, decreasing as Chlorophyll a concentration increased., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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., ((c) 2010 Elsevier Ltd. All rights reserved.)

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.

A dynamic flux model for lakes taking into account the interactions between atmospheric depositional and biogeochemical processes (BIODEP model) was used to assess the importance of internal cycling and biogeochemical processes with respect to accumulation of four different polychlorinated biphenyls (PCBs) (congeners 28, 52, 101 and 153) in Lake Redo, a high-altitude lake in the Spanish Pyrenees. To investigate the effect of temperature on sediment accumulation, the model was run at different temperatures and corresponding sediment inventories were plotted vs. reciprocal temperature. In line with measurements from a previous study looking at sediment inventories of 19 European high-altitude lakes (MOLAR study), we found a stronger temperature dependence of lake sediment concentrations for the less volatile/less soluble PCBs. Seasonal and annual mass balances were investigated and highlighted the importance of internal lake processes controlling the differences in sediment accumulation for the different PCB congeners. For example, the higher temperature dependence of sediment inventories for the high chlorinated congeners is due to the fast dynamics of water-to-sediment transport in comparison to atmospheric deposition processes.

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.

Polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and surface seawater between 49 degrees N and 25 degrees S in the open Atlantic Ocean. Elevated concentrations of PAHs (sigma10 PAHs approximately 1.4-2.5 ng m(-3) air, and 0.7-1 ng L(-1) seawater) occurred in the Biscay Bay and off the northwest coast of Africa. The unexpectedly high concentrations off NW Africa were discussed assessing the possible contribution of the emerging oil industry along the African shore, the role of biomass burning and natural sources of PAHs. In the southern Atlantic, concentrations of PAHs were close to detection limits (sigma10 PAHs approximately 0.02-0.5 ng m(-3) air, and 0.06-0.5 ng L(-1) seawater) and showed decreasing trends with increasing latitudes. Correlations of PAHs' partial pressures versus inverse temperature were not significant in contrast to results for polychlorinated biphenyls from the same transect. This could have been due to the importance of ongoing primary sources and the shorter atmospheric life-times of PAHs. Air-water fugacity ratios (fa/fw) were calculated for selected compounds. They were close to 1 for fluoranthene and pyrene in remote open ocean areas suggesting air-water partitioning near equilibrium. Ratios for anthracene and phenanthrene were < 0.3 in the remote tropical Atlantic, suggesting net volatilization.

Air and seawater samples were collected on board the RV Polarstern during a cruise from Bremerhaven, Germany to Cape Town, South Africa from October-November 2005. Broad latitudinal trends were observed with the lowest sigma27PCB air concentration (approximately 10 pg m(-3)) in the South Atlantic and the highest (approximately 1000 pg m(-3)) off the west coast of Africa. Sigma(ICES)PCBs ranged from 3.7 to 220 pg m(-3) in air samples and from 0.071 to 1.7 pg L(-1) in the dissolved phase seawater samples. Comparison with other data from cruises in the Atlantic Ocean since 1990 indicate little change in air concentrations over the remote open ocean. The relationship of gas-phase partial pressure with temperature was examined using the Clausius-Clapeyron equation; significant temperature dependencies were found for all PCBs over the South Atlantic, indicative of close air-water coupling. There was no temperature dependence for atmospheric PCBs overthe North Atlantic, where concentrations were controlled by advection of contaminated air masses. Due to large uncertainties in the Henry's Law Constant (HLC), fugacity fractions and air-water exchange fluxes were estimated using different HLCs reported in the literature. These suggest that conditions are close to air-water equilibrium for most of the ocean, but net deposition is dominating over volatilization in parts of the transect. Generally, the tri- and tetrachlorinated homologues dominated the total flux (> 70%). Total PCB fluxes (28, 52, 118, 138, and 153) ranged from -7 to 0.02 ng m(-2) day(-1).

The effect of vertical turbulent mixing on the dynamics of persistent organic pollutants has long been overlooked and its role is still hardly understood. Here we present the first comprehensive analysis of the role of turbulent diffusion on the distribution of those contaminants and its interplay with sinking fluxes. To this end, a 1D dynamic coupled hydrodynamic-contaminant model has been developed and applied to a Mediterranean continental shelf environment. The hydrodynamic sub-model is adapted from COHERENS, the contaminant sub-model is an improvement from the BIODEP model and considers the contaminant in 3 phases: dissolved-colloidal-particulate. The simulation highlights the role of turbulence in determining the POP distribution and variability in the water column. In short, turbulent flux of contaminants strengthens the upward diffusion of sediment entrained contaminants and determines the extent to which inputs from the atmosphere mix into the water column. It acts in parallel with degradation and sinking fluxes, the combined effect yielding a surface enriched - depth depleted - benthic layer enriched region distribution, which presents similarities to reported experimental measures.

Wet deposition fluxes of polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and furans to the Atlantic Ocean have been estimated by combining meteorological satellite data and measured atmospheric field concentrations. They are then compared to other atmospheric depositional mechanisms on a global scale. Additional features not treated in traditional studies are addressed such as contaminant adsorption onto raindrops and enhancement of dry gaseous diffusive fluxes due to rain-induced turbulence. Wet deposition estimates show a high spatial and seasonal variability, with maxima located in the Intertropical Convergence Zone (ITCZ) and in low-temperature regions. Seasonal variability reflects the northward shift of ITCZ in July. Average wet deposition fluxes estimated for the Atlantic Ocean in this study are 110 and 45 ng m(-2) yr(-1) for sigmaPCB and sigmaPCDD/Fs, respectively. Furthermore, the total wet deposition to the Atlantic results in 4100 kg yr(-1) (sigmaPCB) and 2500 kg yr(-1) (sigmaPCDD/Fs). Model validation shows good agreement with available coastal data measurements of wet deposition fluxes. When compared to other atmospheric depositional mechanisms and during precipitation events, wet deposition is found to be dominant. However, when raining events and non-raining time periods are integrated, air-water diffusive exchange fluxes acquire an important role, which can be dominant in some regions and for some POPs.

The first estimates of atmospheric deposition fluxes of polychlorinated biphenyls (PCBs) to the Hudson River Estuary are presented. Concentrations of PCBs were measured in air, aerosol, and precipitation at nine sites representing a variety of land-use regimes at regular intervals from October 1997 through May 2001. Highest concentrations in the gas phase were observed at urban sites such as Camden and Jersey City (sigmaPCB concentrations averaged 3250 and 1260 pg m(-3), respectively). In great portions of the state encompassing forested, coastal, and suburban environments, gas-phase sigmaPCB concentrations were essentially the same (averaging 150-220 pg m(-3)). This spatial trend suggests that atmospheric PCBs arise from highly localized, urban sources which influence atmospheric concentrations and deposition fluxes over a distance of a few tens of kilometers. Atmospheric sigmaPCB deposition fluxes (gas absorption + dry particle deposition + wet deposition) ranged from 7.3 to 340 microg m(-2) yr(-1) and increased with proximity to urban areas. While the magnitude of the fluxes increased with urbanization,the relative proportions of wet, dry, and gaseous deposition remained largely constant. Because the Hudson River Estuary is adjacent to urban areas such as Jersey City, it is subject to higher depositional fluxes of PCBs. These depositional fluxes are at least 2-10 times those estimated for the Chesapeake Bay and Lake Michigan. Inputs of PCBs to the Hudson River Estuary from the upper Hudson River and from wastewater treatment plants are 8-18 times atmospheric inputs, and volatilization of PCBs from the estuary exceeds atmospheric deposition of low molecular weight PCBs.

The oceans play an important role as a global reservoir and ultimate sink of persistent organic pollutants (POPs) such as polychlorinated biphenyls congeners (PCBs). However, the physical and biogeochemical variables that affect the oceanic capacity to retain PCBs show an important spatial and temporal variability which have not been studied in detail, so far. The objective of this paper is to assess the seasonal and spatial variability of the ocean's maximum capacity to act as a reservoir of atmospherically transported and deposited PCBs. A level I fugacity model is used which incorporates the environmental variables of temperature, phytoplankton biomass, and mixed layer depth, as determined from remote sensing and from climatological datasets. It is shown that temperature, phytoplankton biomass and mixed layer depth influence the potential PCB reservoir of the oceans, being phytoplankton biomass specially important in the oceanic productive regions. The ocean's maximum capacities to hold PCBs are estimated. They are compared to a budget of PCBs in the surface oceans derived using a level III model that assumes steady state and which incorporates water column settling fluxes as a loss process. Results suggest that settling fluxes will keep the surface oceanic reservoir of PCBs well below its maximum capacity, especially for the more hydrophobic compounds. The strong seasonal and latitudinal variability of the surface ocean's storage capacity needs further research, because it plays an important role in the global biogeochemical cycles controlling the ultimate sink of PCBs. Because this modeling exercise incorporates variations in downward fluxes driven by phytoplankton and the extent of the water column mixing, it predicts more complex latitudinal variations in PCBs concentrations than those previously suggested.

Understanding and quantifying the global dynamics and sinks of persistent organic pollutants (POPs) is important to assess their environmental impact and fate. Air-surface exchange processes, where temperature plays a central role in controlling volatilization and deposition, are of key importance in controlling global POP dynamics. The present study is an assessment of the role of oceanic biogeochemical processes, notably phytoplankton uptake and vertical fluxes of particles, on the global dynamics of POPs. Field measurements of atmospheric polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDDs), and furans (PCDFs) are combined with remote sensing estimations of oceanic temperature, wind speed, and chlorophyll, to model the interactions between air-water exchange, phytoplankton uptake, and export of organic matter and POPs out of the mixed surface ocean layer. Deposition is enhanced in the mid-high latitudes and is driven by sinking marine particulate matter, rather than by a cold condensation effect. However, the relative contribution of the biological pump is a function of the physical-chemical properties of POPs. It is concluded that oceanic biogeochemical processes play a critical role in controlling the global dynamics and the ultimate sink of POPs.

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.

Polycyclic aromatic hydrocarbons (PAHs, n = 36) were measured in the gas and particle phases in the atmosphere and the dissolved and particle phases in the waters of the New York-New Jersey Harbor Estuary, USA, during a weeklong intensive field campaign in July 1998. Mean total (gas + particulate) phenanthrene and pyrene concentrations were 3.3 and 0.33 ng/m3, respectively, over Raritan Bay, and 14 and 1.1 ng/ml, respectively, over New York Harbor. Similar PAH profiles (p values < 0.01) in the atmospheric gas phase and the dissolved phase in water demonstrate the close coupling of the air and water compartments. Air-water exchange fluxes of PAHs estimated using shore-based air data lead to erroneous flux estimates when compared to those derived using over-water air samples. The gross absorptive air-water flux dominates atmospheric loadings (wet, dry particle, gas absorption) to the estuary for PAHs of molecular weight < 234 g/mol. Dry particle deposition is increasingly more important for the higher-molecular-weight, particle-bound PAH species. Gross volatilization dominates gross absorption for the majority of PAHs in the New York-New Jersey Harbor Estuary.