Javier Castro-Jiménez

Atmospheric concentrations, occurrence and deposition of persistent organic pollutants (POPs) in a Mediterranean coastal site (Etang de Thau, France)

Atmospheric concentrations and deposition fluxes of PCDD/F and PCB have been evaluated over a 1-year period in a Mediterranean coastal lagoon (Etang de Thau, France). Indicative PBDE air concentrations in the hot season are also reported in this work. ∑2,3,7,8-PCDD/Fs and ∑18PCBs (gas+particulate) air concentrations ranged from 67 to 1700 fg m(-3) and from 13 to 95 pg m(-3), respectively whereas ∑8PBDEs (gas+particulate) summer time levels varied from 158 to 230 pg m(-3). The PCDD/F and PCB atmospheric occurrence over Thau lagoon and subsequent inputs to the surface waters are determined by an assemble of factors, being the seasonality of atmospheric concentration, the air mass origin and meteorological conditions important drivers. Total (wet+dry) ∑2,3,7,8-PCDD/Fs and ∑18PCBs deposition fluxes to Thau Lagoon waters are 117 and 715 pg m(-2)d(-1), respectively.

On the use of the partitioning approach to derive Environmental Quality Standards (EQS) for persistent organic pollutants (POPs) in sediments : A review of existing data

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.

Toxicity assessment of atmospheric particulate matter in the Mediterranean and Black Seas open waters.

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.

Modelling the influence of thermal stratification and complete mixing on the distribution and fluxes of polychlorinated biphenyls in the water column of Ispra Bay (Lake Maggiore)

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.

Occurrence, Loading, and Exposure of Atmospheric Particle-Bound POPs at the African and European Edges of the Western Mediterranean Sea

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 (∑18PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (∑17PCDD/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 (∑27PBDEs) 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.

Levels and risk assessment of hydrocarbons and organochlorines in aerosols from a North African coastal city (Bizerte, Tunisia)

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 0.5-17.8u202fngu202fm-3, 6.7-126.5u202fngu202fm-3, 0.3-11u202fpgu202fm-3 and 0.2-3.6u202fpgu202fm-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.

Marine vegetation analysis for the determination of volatile methylsiloxanes in coastal areas

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 458u202f±u202f26u202fng·g-1dw (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.

Seasonal soil/snow-air exchange of semivolatile organic pollutants at a coastal arctic site (Tromsø, 69°N)

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.

Atmospheric particle-bound organophosphate ester flame retardants and plasticizers in a North African Mediterranean coastal city (Bizerte, Tunisia)

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 ∑9OPE concentrations of ~100-1060u202fpgu202fm-3 (470u202fpgu202fm-3, median) with TCPPs, EHDPP and TiBP exhibiting the higher median concentrations (~110, 100 and 85u202fpgu202fm-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 (∑9OPEs) were 18-180u202fngu202fm-2u202fd-1. Up to ~9u202fkgu202fy-1 of OPEs (~1u202fkgu202fy-1 of new organic anthropogenic phosphorus coming from OPEs) can be loaded to the shallow and enclosed Bizerte lagoon (~130u202fkm2), considered as the most important aquaculture area in Tunisia, with yet unknown implications for the environmental exposure and impacts in the ecosystem functioning.

Zooplankton and Plastic Additives—Insights into the Chemical Pollution of the Low-Trophic Level of the Mediterranean Marine Food Web

Marine litter such as microplastics pose a variety of problems once they reach the environment via improper waste disposal or spills, among others. While microplastics are often ingested by marine organisms, marine life is not only threatened by the physical damage plastic items can cause but also by the possible chemical pollution resulting from the leaching of plastic additives or other adsorbed chemicals on the plastics surface during long-range transport. Plastic additives include plasticizers, flame retardants and colour pigments. The demonstrated toxicity of some of these molecules has led to national and international legislations limiting or banning their use. However, a wide variety of substances are still found in plastic products and little is known about their impact on the marine and terrestrial environment.