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We studied the co-occurrence of OPEs and other constituents in atmospheric particles at the two edges of the Mediterranean Sea, under the influence of the transport of polluted air from Europe and dust from the Sahara. The highest OPE concentrations were observed during the summer period in the East Mediterranean and in spring for the NW Mediterranean. The total average atmospheric concentration of Σ 6 OPEs in the NW Mediterranean was 2103 ± 2020 pg m -3 (n = 23) with EHDPP and TCPP to be the predominant OPEs, accounting on average for 46% and 37% of the total Ʃ 6 OPEs concentrations, respectively. The average concentration of Σ 6 OPEs in East Mediterranean was 156.4 ± 170.3 pg m -3 (n = 67) with TCPP showing the highest concentration (116.1 ± 92.8 pg m -3 ), followed by TCEP (67.5 ± 55.8 pg m -3 ). In both areas, OPEs were mostly associated with fossil fuel combustion and road traffic, while the air masses from Saharan desert influenced the concentration of EHDPP, TCEP in NW Mediterranean and the TCEP concentration levels in the East Mediterranean. The total annual deposition of reported OPEs to the Mediterranean basin was estimated to be 584 tonnes, accounting for about 8.5% of the total deposited anthropogenic phosphorus., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Plastic garbage patches at the ocean surface are symptomatic of a wider pollution affecting the whole marine environment. Sinking of plastic debris increasingly appears to be an important process in the global fate of plastic in the ocean. However, there is insufficient knowledge about the processes affecting plastic distributions and degradation and how this influences the release of additives under varying environmental conditions, especially in deep-sea environments. Here we show that in abiotic conditions increasing hydrostatic pressure inhibits the leaching of the heaviest organic additives such as tris(2-ethylhexyl) phosphate and diisononyl phthalate from polyethylene and polyvinylchloride materials, whereas deep-sea and surface marine prokaryotes promote the release of all targeted additives (phthalates, bisphenols, organophosphate esters). This study provides empirical evidences for more efficient additive release at the ocean surface than in deep seawater, where the major plastic burden is supposed to transit through before reaching the sediment compartment., (© 2021. The Author(s).)

The storage capacity, trophic magnification and risk of sixty-two POPs have been evaluated in a well-characterized pelagic food web (including phytoplankton, zooplankton, six fish, and two cephalopods species) from an impacted area in NW Mediterranean Sea. Our results show the high capacity of the planktonic compartment for the storage of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), consistent with their estimated low trophic magnification factors (TMF) of 0.2-2.0 (PBDEs) and of 0.3-1.1 (PCDD/Fs). ∑PBDEs dominated in the zooplankton size-class 200-1000 μm (∼330 ng g -1 lw, median), whereas ∑PCDD/Fs accumulated preferentially in phytoplankton size-class 0.7-200 μm (875 pg g -1 lw, median). In contrast, polychlorinated biphenyls (PCBs) were preferentially bioaccumulated in the higher trophic levels (six fish species and two cephalopods) with TMFs = 0.8-3.9, reaching median concentrations of 4270 and 3140 ng g -1 lw (∑PCBs) in Atlantic bonito ( Sarda sarda ) and chub mackerel ( Scomber colias ), respectively. For these edible species, the estimated weekly intakes of dioxin-like POPs for humans based on national consumption standards overpassed the EU tolerable weekly intake. Moreover, the concentrations of nondioxin-like PCBs in S. sarda were above the EU maximum levels in foodstuffs, pointing to a risk. No risk evidence was found due to consumption of all other edible species studied, neither for PBDEs. The integrated burden of POPs in the food web reached ∼18 μg g -1 lw, representing a dynamic stock of toxic organic chemicals in the study area. We show that the characterized food web could be a useful and comprehensive "bioindicator" of the chemical pollution status of the study area, opening new perspectives for the monitoring of toxic chemicals in Mediterranean coastal waters.

Seven phthalate (PAEs) and nine organophosphate esters (OPEs) were measured in surface sediments across the Gulf of Lion (NW Mediterranean Sea) at twelve stations characterized by different anthropogenic signatures. ∑PAEs and ∑OPEs concentrations ranged from 2 to 766 ng/g DW (av. 196 ng/g DW) and from 4 to 227 ng/g DW (av. 54 ng/g DW), respectively. Our analysis of the potential sources of these organic plastic additives in sediments of the Gulf of Lion suggests that the dominant factors affecting their occurrence and environmental distribution are port-based industrial activities and urban pressures. Indeed, the highest ∑PAEs and ∑OPEs concentrations were found close to the ports of Toulon and Marseille (Estaque) and at the sites impacted by the Marseille metropolitan area (i.e. at the outlets of the waste water treatment plant at Cortiou and at the mouth of the Huveaune River). The lowest levels were generally found in protected areas (e.g. Port-Cros) and at sites relatively far from the coast. DEHP was seen to be the most abundant PAE while TDCP, TEHP and TiBP were the most abundant OPEs in the area. Our results also expose the contribution of additives entering the Gulf of Lion via sedimentary material from the Rhône River, with positive correlations between the total organic carbon (TOC) content in the sediment and the ∑PAEs and ∑OPEs concentrations. However, additive concentrations decreased from shore to offshore in the Rhône River discharge area, indicating an efficient dilution of the contaminants accumulated at the river mouth area., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this study, surface seawater, sediment and zooplankton samples were collected from three different sampling stations in Marseille Bay (NW Mediterranean Sea) and were analyzed for both microplastics and organic plastic additives including seven phthalates (PAEs) and nine organophosphate esters (OPEs). PAE concentrations ranged from 100 to 527 ng L -1 (mean 191 ± 123 ng L -1 ) in seawater, 12-610 ng g -1 dw (mean 194 ± 193 ng g -1 dw) in sediment and 0.9-47 μg g -1 dw (mean 7.2 ± 10 μg g -1 dw) in zooplankton, whereas OPE concentrations varied between 9 and 1013 ng L -1 (mean 243 ± 327 ng L -1 ) in seawater, 13-49 ng g -1 dw (mean 25 ± 11 ng g -1 dw) in sediment and 0.4-4.6 μg g -1 dw (mean 1.6 ± 1.0 μg g -1 dw) in zooplankton. Microplastic counts in seawater ranged from 0 to 0.3 items m -3 (mean 0.05 ± 0.05 items m -3 ). We observed high fluctuations in contaminant concentrations in zooplankton between different sampling events. However, the smallest zooplankton size class generally exhibited the highest PAE and OPE concentrations. Field-derived bioconcentration factors (BCFs) showed that certain compounds are prone to bioaccumulate in zooplankton, including some of the most widely used chlorinated OPEs, but with different intensity depending on the zooplankton size-class. The concentration of plastic additives in surface waters and the abundance of microplastic particles were not correlated, implying that they are not necessarily good indicators for each other in this compartment. This is the first comprehensive study on the occurrence and temporal variability of PAEs and OPEs in the coastal Mediterranean based on the parallel collection of water, sediment and differently sized zooplankton samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Aiming the simultaneous determination of widely used organic plastic additives in complex marine matrices, this work proposes a fast and "green" analytical protocol based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) technology. The validation of this innovative method on real matrices (i.e., sediments, mussel, fish, and Posidonia oceanica) indicated a general good performance in all of them for phthalate esters (PAEs), with low blank levels and average method recoveries varying from 54 ± 11 to 71 ± 12%. The best method performance for organophosphate ester (OPE) flame retardants and plasticizers was in biotic matrices (recoveries 52 ± 31 to 86 ± 38%). This application represents an innovative QuEChERS sequence of two dispersive solid-phase extraction (SPE) steps enabling this approach for the determination of important families of organic plastic additives in the marine environment. Indeed, our method allowed the fast screening and simultaneous determination of OPE and PAEs in various sites and matrices subject to different anthropogenic pressure in coastal NW Mediterranean Sea for the first time. ∑ 7 PAE and ∑ 9 OPE concentrations of 19-83 and 27-116 ng g -1 dw (fish), of 80-714 and 42-71 ng g -1 dw (mussels), of 192-908 and 47-151 ng g -1 dw (Posidonia oceanica), and of 11-328 and 4-10 ng g -1 dw (sediment) were measured, respectively. Our approach was sensible enough as to detect differences in the (bio)accumulation patterns of the target compounds in various species and/or sites. This application opens new perspectives for environmentally friendly marine environment monitoring and screening campaigns for organic plastic additives. Graphical abstract.

We present here a comprehensive study (1-year regular sampling) on the occurrence of major families of organic plastic additives in the Rhône River surface waters. Potential sources and contaminant export are also discussed. A total of 22 dissolved phase samples were analyzed for 22 organic additives mainly used in the plastic industry, including organophosphate esters (OPEs), phthalates (PAEs) and bisphenols (BPs). Our results indicate that PAEs were the most abundant class, with concentrations ranging from 97 to 541 ng L -1 , followed by OPEs (85-265 ng L -1 ) and BPs (4-21 ng L -1 ). Among PAEs, diethylhexyl phthalate (DEHP) was the most abundant compound, whereas TCPP (Tris(1-chloro-2-propyl) phosphate) and TnBP (Tri(n-butyl)phosphate) were the predominant OPEs. Bisphenol S was the only BP detected. 5-54 metric tons year -1 of dissolved organic plastic additives of emerging concern are estimated to be exported to the Gulf of Lion by the Rhône River, which is the main freshwater source of the Mediterranean Sea., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Four perfluoroalkyl substances (PFAS) were analyzed in 62 duplicate surface water samples from the Rhône River and Marseille Bay (France; NW Mediterranean Sea). Perfluorooctane sulfonate (PFOS) was detected in all samples and exceeded the European Environmental Quality Standard (EQS) values in over 80% of the cases. The most contaminated samples were from the Rhône River (up to 200 ng L -1 ∑ 4 PFAS), as well as those collected near a wastewater treatment plant outlet in Marseille Bay (up to 9 ng L -1 ∑ 4 PFAS). While PFOS was the predominant PFAS in Marseille Bay, remarkably high concentrations of perfluorohexanoic acid (PFHxA) were measured in the Rhône River (8-193 ng L -1 ). The relative abundances of individual compounds differed thus significantly between the Rhône River and Marseille Bay, indicating different sources. A simulation made with the MARS3D model showed that PFOS inputs from the Rhône River can enter Marseille Bay at levels > EQS., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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 macro-plastics 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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The release of emerging organic contaminants is identified among the most critical hazards to the marine environment, and plastic additives have received growing attention due to their worldwide distribution and potential deleterious effects. Here, we report dissolved surface water concentrations of two important families of plastic additives (organophosphate esters (OPEs) and bisphenols) and other related organic compounds (perfluorinated chemicals) measured in the North Atlantic from Cape Verde to the West Indies. We found that OPEs were the most abundant contaminants, reaching remarkably high concentrations in open ocean waters (1200 km offshore of the American Coast, at the location of the Amazon river plume during the sampling period), with up to 1.3 μg L -1 (Σ 9 OPEs). A Lagrangian analysis confirmed that these high concentrations of contaminants originated from the Amazon River plume and were transported more than 3000 km by the North Brazil Current and its retroflection. We thus consider the Amazon River as a major source of organic contaminants of emerging concern to the tropical North Atlantic Ocean and suggest that medium-/long-range contaminant transport occurs, most certainly facilitated by the highly stratified conditions offered by the river plume.

Volatile methylsiloxanes (VMSs) are massively produced chemicals that comprise a wide range of industrial and household applications. The presence of cyclic and linear VMSs in several environmental matrices and ecosystems indicates persistence associated with a potential of (bio)accumulation and food web transfer with possible toxicological effects. Due to the high anthropogenic pressure in its vicinities particularly in summer, coastal areas in Southern European countries are potential hotspots for the presence of VMSs. The massive afflux of tourists and consequent increase of the use of personal care products (PCPs) with VMSs in their formulations highlight the importance of VMSs assessment in such areas. In this study, different species of marine vegetation (algae and seaweed) were collected in three different geographical areas, covering the Atlantic Ocean (North coast of Portugal), as well as the Mediterranean Sea (coasts of the Region of Murcia, Spain and of the city of Marseille, France). Samples were analysed for the determination of 4 cyclic (D3, D4, D5, D6) and 3 linear (L3, L4, L5) VMSs employing a QuEChERS extraction methodology, followed by gas chromatography/mass spectrometry (GC/MS) quantification. VMSs were detected in 92% of the 74 samples analysed, with the sum of the concentrations per sample ranging from below the limit of detection (LOD) to 458 ± 26 ng·g -1 dw (dry weight). A strong predominance of cyclic VMSs over linear ones was verified in almost all samples studied, with D5 and D6 found at higher concentrations. Seasonal variation was also assessed and despite higher levels of VMSs being identified mostly in summer months, clear seasonal trends were not perceived. It was also noted that generally the higher incidence of VMSs occurred in samples from urban and industrialized areas or in the vicinities of WWTPs, suggesting a direct input from these sources in the levels of siloxanes observed., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Organophosphate ester (OPE) flame retardants and plasticizers have been detected at generally high frequencies (70-98%) for the first time in the atmosphere over the NW African coastal Mediterranean. Results from sixty air samples (total suspended particles, TSP) collected between March 2015 and January 2016 in an urban coastal site (Bizerte, Tunisia) revealed ∑ 9 OPE concentrations of ~100-1060 pg m -3 (470 pg m -3 , median) with TCPPs, EHDPP and TiBP exhibiting the higher median concentrations (~110, 100 and 85 pg m -3 , respectively). Spring generally exhibited the lowest concentrations, probably linked to the influence of local meteorological conditions and air mass trajectories to a lesser extent. Non-chlorinated OPEs generally predominated, in contrast to the most common reported situation in marine environments (i.e. higher abundance of chlorinated OPEs) pointing to the relevance of local OPE sources in the study area. TiBP levels were generally higher than those reported for other marine/coastal environments suggesting this OPE as a good tracer of local sources in Bizerte. Contrarily, the atmospheric levels of other abundant OPEs in the area (e.g. TCPP) seem to be in the range and/or lower than those reported for remote marine environments. These findings point to the interplay of different factors with solar irradiance (potentially enhancing atmospheric photochemical oxidation reactions) and meteorological conditions in the study area likely compensating potential local sources of some OPEs. Not all OPEs presented the same seasonality in terms of atmospheric concentrations and pattern. The estimated atmospheric dry deposition fluxes (∑ 9 OPEs) were 18-180 ng m -2  d -1 . Up to ~9 kg y -1 of OPEs (~1 kg y -1 of new organic anthropogenic phosphorus coming from OPEs) can be loaded to the shallow and enclosed Bizerte lagoon (~130 km 2 ), considered as the most important aquaculture area in Tunisia, with yet unknown implications for the environmental exposure and impacts in the ecosystem functioning., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Soils are a major reservoir of semivolatile organic pollutants such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), and exert a control on their atmospheric occurrence. We present here an assessment of the atmospheric occurrence and seasonality of soil/snow-air partitioning and exchange of PCBs, PAHs, hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCHs) in the arctic city Tromsø, northern Norway. The fugacities of the organic pollutants in soils and snow were determined using a soil fugacity sampler by equilibrating the air concentrations with those in the surface soil/snow. The concentrations in soils did not show a significant seasonality. Conversely, the ambient air concentrations and the soil (or snow) fugacity showed a clear seasonality for PCBs, HCH, HCB and some PAHs, related to temperature. Fugacities in soil/snow were correlated with those in the ambient gas phase, suggesting a close seasonal air-soil/snow coupling. Generally, there was a net deposition or close to equilibrium conditions during the winter, which contrasts with the net volatilization observed during the warmer periods. The chemicals with lower octanol-air partition coefficients showed a larger tendency for being volatilized and thus remobilized from this coastal arctic environment. Conversely, the more hydrophobic compounds were close to air-soil/snow equilibrium or showed a net deposition., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The aim of this study was to assess, for the first time, the concentrations, sources, dry deposition and human health risks of polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in total suspended particle (TSP) samples collected in Bizerte city, Tunisia (North Africa), during one year (March 2015-January 2016). Concentrations of PAHs, AHs, PCBs and OCPs ranged 0.5-17.8 ng m -3 , 6.7-126.5 ng m -3 , 0.3-11 pg m -3 and 0.2-3.6 pg m -3 , respectively, with higher levels of all contaminants measured in winter. A combined analysis revealed AHs originating from both biogenic and petrogenic sources, while diesel vehicle emissions were identified as dominant sources for PAHs. PCB potential sources included electronic, iron, cement, lubricant factories located within or outside Bizerte city. The dominant OCP congeners were p,p'-DDT and p,p'-DDE, reflecting a current or past use in agriculture. Health risk assessment showed that the lifetime excess cancer risk from exposure to airborne BaP was negligible in Bizerte, except in winter, where a potential risk to the local population may occur., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

To evaluate quality of life (QoL) in patients with axial spondyloarthritis (axSpA) and its association with disease activity, functionality, structural damage, and spinal mobility, using patient-reported outcomes. This was an observational, cross-sectional, and single-center study in which 100 consecutive patients with axSpA were included. We obtained from all patients' sociodemographic data and values related to disease activity, functionality, structural damage, mobility, and quality of life. The Ankylosing Spondylitis Quality of Life Questionnaire (ASQoL) was considered as the primary outcome. Pearson r statistic, Student's T test, and univariate and multivariate linear regressions were performed to relate ASQoL with the studied covariates. Mean ASQoL score in all patients was 4.02 ± 2.81, with statistically significant differences between male and female (3.61 ± 2.80 vs. 4.83 ± 2.70). Patients with high disease activity (measured by the ASAS-endorsed Disease Activity Score, ASDAS > 2.1) showed higher mean score in ASQoL than those with low disease activity (ASDAS ≤ 2.1) (3.21 ± 0.74 vs. 1.43 ± 0.43, p < 0.001). ASQoL presented a significant linear correlation with BASDAI, BASFI, and ASDAS (r > 0.60). However, disease duration was not significantly correlated with ASQoL. Finally, the 68.9% of the ASQoL variability (R 2  = 0.689) was determined by BASDAI, BASFI, and mSASSS, presenting mSASSS a negative regression coefficient (- 0.035). In our study, the impairment of QoL was mainly associated with disease activity (BASDAI) and worsening of functionality (BASFI). However, there is an inverse relationship between the worsening of QoL and structural damage. In addition, disease duration does not seem to influence the patient's welfare.

A comparative study for 62 toxic chemicals based on the simultaneous monthly collection of aerosol samples during 2015-2016 in two coastal cities at both the African (Bizerte, Tunisia) and European (Marseille, France) edges of the Western Mediterranean basin is presented. Legacy polychlorinated biphenyls (∑ 18 PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (∑ 17 PCDD/Fs) show generally higher median levels at the African edge (2.1 and 0.2 pg m -3 , respectively) compared to the European coastal site (1.0 and 0.08 pg m -3 , respectively). Contrarily, the "emerging" polybrominated diphenyl ethers' (∑ 27 PBDEs) median concentrations were higher in Marseille (∼9.0 pg m -3 ) compared to Bizerte (∼6.0 pg m -3 ). Different past usages and current emission patterns were found at both edges of the Western Mediterranean, most probably linked to the respective different regulatory frameworks for toxic chemicals. Our results indicate that the total organic carbon (TOC) and/or the elemental carbon (EC) contents in the atmospheric aerosol may have a stronger effect than the total suspended particle (TSP) content as a whole on the spatial-temporal variability and the long-range atmospheric transport potential of the studied POPs. A "jumping" of the PBDE local atmospheric stocks from the Northwestern European Mediterranean edge to the Northwestern African coast seems to be possible under favorable conditions at present. While a higher PBDE median loading is estimated for the Marseille area (∼550 ng m -2 y -1 ) compared to Bizerte (∼400 ng m -2 y -1 ), the median PCB and PCDD/F dry deposition fluxes were higher at the African site, resulting in a 3-fold higher toxic equivalent (TEQ) loading of dioxin-like pollutants (400 pg TEQ m -2 y -1 ) compared to Marseille (∼140 pg TEQ m -2 y -1 ), with potential implications for aquatic organisms. However, the inhalation exposure assessment points to a minimum risk for human health at both sites.

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 -3 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 ∑ 14 OPE ranged from 4 to 140 ng m -2 d -1 . 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.

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.)

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.

∑(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.)

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.

Polychlorinated biphenyls (PCBs) have been proposed for the inclusion in the European Water Framework Directive (WFD) priority list, currently under revision. Various screening methods have been employed for PCB determination in different environmental matrixes in the last decades, immunoassays being one of the most employed. A literature review reveals that the enzyme-linked immunosorbent assay (ELISA) is the most commonly applied immunoassay for PCB determination in the environment. However, its application to sediments is very limited. A suitability assessment of immunoassay-based analysis for PCB screening in sediments is presented in this work. The significance of available immunoassay-based test kits under the current environmental pollution scenario and their performance against the sensitivity and specificity requirements dictated by the WFD for PCB analysis in sediments is discussed. For example, current detection limits of available test kits for PCB determination in sediments may not be enough for compliance checking under the WFD. In addition, concentration expressed as Aroclor equivalents does not seem to be the way forward. A proposal for adapting available test kits in order to become more suitable tools for PCB screening in sediments is also presented in this study.

A 1D coupled hydrodynamic and contaminant fate model was applied to simulate the distribution of polychlorinated biphenyls (PCBs) in the Ispra Bay located in the southern part of Lake Maggiore (Italy). The model succeeded in representing the hydrodynamic processes occurring in the lake such as thermal stratification during summer 2005 followed by the complete mixing of the water column in February 2006. The results of the PCB fate model highlighted that these processes play a key role for the settling of particles and consequently for the distribution of PCBs in the water column as well as for the contaminant flux at the sediment-water interface. On the air-water front, the simulations emphasised that the net atmospheric PCB input fluxes are generally more important during the cold season and show peaks during periods of high wet deposition. Finally, the seasonal variability of the distribution of PCB in the water column was assessed.

A review of experimental data has been performed to study the relationships between the concentration in water, pore water and sediments for different families of organic contaminants. The objective was to determine whether it is possible to set EQS for sediments from EQS defined for surface waters in the Daughter Directive of the European Parliament (COM (2006) 397). The analysis of experimental data showed that even though in some specific cases there is a coupling between water column and sediments, this coupling is rather the exception. Therefore it is not recommendable to use water column data to assess the chemical quality status of sediments and it is necessary to measure in both media. At the moment EQS have been defined for the water column and will assess only the compliance with good chemical status of surface waters. Since the sediment toxicity depends on the dissolved pore water concentration, the EQS developed for water could be applied to pore water (interstitial water); hence, there would be no need of developing another set of EQS. The partitioning approach has been proposed as a solution to calculate sediment EQS from water EQS, but the partitioning coefficient strongly depends on sediment characteristics and its use introduces an important uncertainty in the definition of sediment EQS. Therefore, the direct measurement of pore water concentration is regarded as a better option.

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.