Transport patterns and hydrodynamic context of the MERITE-HIPPOCAMPE cruise: Implications for contaminants distribution and origin.

This study aims at characterizing the hydrodynamic context and transport patterns that prevailed during the MERITE-HIPPOCAMPE cruise to assist in the interpretation of in-situ observations. The main physical attributes and structures (mesoscale eddies as well as fine-scale fronts and filaments) are analyzed based on various physical diagnostics. They were computed from satellite data and data-assimilative model outputs to describe ocean dynamics. The Northern and Algerian Currents were prominent features during the cruise while the western basin is divided by the vertically-tilted Balearic front. Temperature and salinity were used to distinguish different water masses at both surface and sub-surface. Sea-level anomalies, relative vorticity, and Okubo-Weiss parameter distributions have shown the presence of marked eddies around stations St10 and St11. Furthermore, Finite-Size Lyaponuv Exponents revealed that the former was rather located on a fine-scale filament near the edge of a cyclonic eddy while the latter was closer to the core of an anticyclone. Nearshore thermal fronts were detected with the Belkin and O'Reilly Algorithm (BOA), especially around stations St17 and St19. The potential coastal sources of contaminants were tested using Lagrangian Origin Maps (LOM), suggesting that stations St1, St2, St4, St11, and St15 were most likely influenced by coastal waters. Additionally, an atmospheric reanalysis combined with a Lagrangian dispersal model allowed for estimating wet deposition events of contaminants while tracking the fate of water masses where rainfall took place. Finally, we provide a set of explanatory quantitative and qualitative variables for future statistical analyses that aim at explaining the distribution of both chemical and biological samples collected during the cruise.

Bioconcentration, bioaccumulation and biomagnification of mercury in plankton of the Mediterranean Sea.

Plankton plays a prominent role in the bioaccumulation of mercury (Hg). The MERITE-HIPPOCAMPE campaign was carried out in spring 2019 along a north-south transect including coastal and offshore areas of the Mediterranean Sea. Sampling of sea water and plankton by pumping and nets was carried out in the chlorophyll maximum layer. Two size-fractions of phytoplankton (0.7-2.7 and 2.7-20 µm) and five of zooplankton (between 60 and >2000 µm) were separated, and their total mercury (THg) and monomethylmercury (MMHg) contents were measured. Bioconcentration of THg was significantly higher in the smallest phytoplankton size-fraction dominated by Synechococcus spp. The bioaccumulation and biomagnification of MMHg in zooplankton was influenced by size, food sources, biochemical composition and trophic level. MMHg was biomagnified in the plankton food web, while THg decreased toward higher trophic levels. Higher MMHg concentrations were measured in oligotrophic areas. Plankton communities in the Southern Mediterranean Sea had lower MMHg concentrations than those in the Northern Mediterranean Sea. These results highlighted the influence of environmental conditions and trophodynamics on the transfer of Hg in Mediterranean plankton food webs, with implications for higher trophic level consumers.

Hydrocarbons in size-fractionated plankton of the Mediterranean Sea (MERITE-HIPPOCAMPE campaign).

Aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs, respectively) were analyzed in the dissolved fraction (<0.7 µm) of surface water and in various particulate/planktonic size fractions (0.7-60, 60-200, 200-500 and 500-1000 µm) collected at the deep chlorophyll maximum, along a North-South transect in the Mediterranean Sea in spring 2019 (MERITE-HIPPOCAMPE campaign). Suspended particulate matter, biomass, total chlorophyll a, particulate organic carbon, C and N isotopic ratios, and lipid biomarkers were also determined to help characterizing the size-fractionated plankton and highlight the potential link with the content in AHs and PAHs in these size fractions. Æ©28AH concentrations ranged 18-489 ng L-1 for water, 3.9-72 µg g-1 dry weight (dw) for the size fraction 0.7-60 µm, and 3.4-55 µg g-1 dw for the fractions 60-200, 200-500 and 500-1000 µm. AH molecular profiles revealed that they were mainly of biogenic origin. Æ©14PAH concentrations were 0.9-16 ng L-1 for water, and Æ©27PAH concentrations were 53-220 ng g-1 dw for the fraction 0.7-60 µm and 35-255 ng g-1 dw for the three higher fractions, phenanthrene being the most abundant compound in planktonic compartment. Two processes were evidenced concerning the PAH patterns, the bioreduction, i.e., the decrease in concentrations from the small size fractions (0.7-60 and 60-200 µm) to the higher ones (200-500 µm and 500-1000 µm), and the biodilution, i.e., the decrease in concentrations in plankton at higher suspended matter or biomass, especially for the 0.7-60 and 60-200-µm size fractions. We estimated the biological pump fluxes of Æ©27PAHs below 100-m depth in the Western Mediterranean Sea at 15 ± 10 ng m-2 day-1, which is comparable to those previously reported in the South Pacific and Indian Ocean.

Assessing the bioavailability of black carbon-derived dissolved organic matter for marine heterotrophic prokaryotes.

Here we investigated the bioavailability of black carbon (BC)-derived dissolved organic matter (DOM) for a natural mixed community of marine heterotrophic prokaryotes. We ran an in vitro biodegradation experiment that took place over 3 months and exposed a community of organisms collected in the northwestern Mediterranean Sea (Bay of Marseille, France) to three different soluble fractions of BC prepared in the laboratory from various fossil fuel combustion particulates: standard diesel (DREF), oxidized diesel (DREF-OX), and natural samples of ship soot (DSHIP). Over the course of the three months, we observed significant decreases in the concentrations of dissolved organic carbon (DOC; from 9 to 21 %), dissolved BC (DBC; from 22 to 38 %) and dissolved polycyclic aromatic hydrocarbons (d-PAH; from 24 to 64 %) along with variability in the growth dynamics and activity of the heterotrophic prokaryotic community. The heterotrophic prokaryotic community exposed to DREF-OX treatment showed the highest values of respiration and production and the highest cell abundance, associated with the highest decrease in DOC (21 %) and d-PAH (64 %) concentrations. In the DREF and DSHIP treatments, prokaryotic activity was oriented towards anabolism. DREF treatment led to the highest decrease in DBC concentration (38 %). DSHIP treatment, which presented a substantially different d-PAH and dissolved metals content to the other two treatments, showed the lowest decreases in DOC, DBC and d-PAH concentrations, as well as the lowest prokaryotic activity and biomasses. Our results indicate that BC-derived DOM, including the most condensed fraction of this material, is partly bioavailable and therefore likely to be assimilated by marine prokaryotes. The origin of BC/soot deposited at the ocean surface turns out to be a key parameter that dictates the efficiency of biodegradation of its dissolved fraction by heterotrophic prokaryotes.

Zooplankton biomass, size structure, and associated metabolic fluxes with focus on its roles at the chlorophyll maximum layer during the plankton-contaminant MERITE-HIPPOCAMPE cruise.

Recent studies have demonstrated that plankton can be a key pathway for the uptake and transfer of contaminants entering the marine environment up to top predators. The plankton-contaminant MERITE-HIPPOCAMPE cruise was devoted to quantifying contaminants in water and the whole plankton size range (10 size fractions) at 10 stations along a north-south transect in the western Mediterranean Sea from the French to the Tunisian coasts through the Provençal and Algerian basins. Pumping and filtering devices and net sampling have been used for collecting very high amounts of small particles and planktonic organisms in the chlorophyll maximum layer (CML). The present paper characterizes the zooplankton components for which the contaminant measurements were carried out. At each station, a horizontal towed Hydro-Bios net with a 60 µm mesh-size net was used to discriminate 5 size-fractions from 60 µm to a few mm. For each size-fraction, one part of the sample was used for dry weight measurements and the other one for estimating the contribution to biomass of detritus, phytoplankton, and among zooplankton of the major taxonomic groups based on the imagery tools ZOOSCAN and FLOWCAM. In each zooplankton size fraction, metabolic rates were calculated from the size spectrum to estimate trophic and excretion fluxes flowing through this fraction. These observations were compared to a similar analysis of tows in the upper layer (vertical) and the surface layer (horizontal). The total sampled biomass concentration at the CML was higher than in the water column (COL) and much higher than at the surface (SURF) in most of the stations, but in the CML and COL a substantial contribution was due to detritus mostly concentrated in the smallest size-fractions (60-200 µm and 200-500 µm). Absolute values of zooplankton biomass show neither a clear spatial pattern nor a significant difference between strata. The CML layer was dominated by copepods similarly to COL and SURF, but presented a higher contribution of nauplii and a near absence of appendicularians. At some stations, crustaceans and gelatinous plankton could be important contributors to CML. The zooplankton biomass composition of the two smallest fractions (<500 µm) was dominated by nauplii, small copepods and, occasionally, by small miscellaneous organisms (mostly pteropodes). In contrast, clear differences between stations appeared for the largest fractions (>500 µm) due to large crustaceans, gelatinous organisms, and chaetognaths. These changes in biomass composition according to size fractions suggest a progressive trophic shift from dominant herbivory in the smallest fractions to more contrasted trophic structure (including carnivory) in the largest fractions. The daily carbon demand and the N and P excretion of zooplankton were on average higher at the CML but with no significant difference with COL. The zooplankton grazing represented 2.7 to 22.7 % of the phytoplankton stock per day, whereas its excretion represented a daily N and P recycling compared to dissolved inorganic nitrogen and phosphorus stocks ranging respectively from 0.2 to 19 % and from 0 to 21 %. This information should help in the interpretation of the content of various contaminants in zooplankton fractions.

Hydrocarbons in the atmospheric gas phase of a coastal city in Tunisia: Levels, gas-particle partitioning, and health risk assessment.

Many studies have focused on aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (AHs and PAHs) in different environmental compartments, especially atmospheric particles (aerosols), due to their adverse effects on the environment and human health. However, much less information is currently available on the content of AHs and PAHs in the atmospheric gas phase, which is a major reservoir of volatile and photoreactive compounds. Here, for the first time, we assessed the levels, gas-particle partitioning, human health risks and seasonal variations of AHs and PAHs in the atmospheric gas-phase of Bizerte city (Tunisia, North Africa) over a one-year period (March 2015-January 2016). Σ34PAH concentration in the gas phase over the period ranged from 6.7 to 90.6 ng m-3 and on average was 2.5 times higher in the cold season than in the warm season. Σ28AH concentration in the gas phase over the period ranged from 14.0 to 35.9 ng m-3, with no clear seasonal variations. In the gas phase, hydrocarbons were dominated by low-molecular-weight (LMW) compounds, i.e. 3- and 4-ring for PAHs and < n-C24 for AHs. Gas-phase concentrations of PAHs and AHs accounted for up to 80 % of the total (gas + particle phases) atmospheric concentrations of PAHs and AHs. Further analysis of gas-particle partitioning showed that LMW hydrocarbons preferential accumulated in the gas phase, and that gas-particle partitioning was not in equilibrium but dominated by absorption processes into the aerosol organic matter. Benzo[a]pyrene toxic equivalency quotient (BaP-TEQ) in the gas phase represented on average 37 % of the total atmospheric BaP-TEQ concentration, which was always higher in the cold season. Atmospheric gas is a significant factor in the risks of cancer associated with inhalation of ambient air. The Monte Carlo simulation-based exposure assessment model predicted that outdoor air exposure to PAHs does not pose a cancer risk to infants, but the children, adolescent, and adult populations may face a lower cancer risk during the warm season and a higher risk in the cold season.

Contamination of planktonic food webs in the Mediterranean Sea: Setting the frame for the MERITE-HIPPOCAMPE oceanographic cruise (spring 2019).

This paper looks at experiential feedback and the technical and scientific challenges tied to the MERITE-HIPPOCAMPE cruise that took place in the Mediterranean Sea in spring 2019. This cruise proposes an innovative approach to investigate the accumulation and transfer of inorganic and organic contaminants within the planktonic food webs. We present detailed information on how the cruise worked, including 1) the cruise track and sampling stations, 2) the overall strategy, based mainly on the collection of plankton, suspended particles and water at the deep chlorophyll maximum, and the separation of these particles and planktonic organisms into various size fractions, as well as the collection of atmospheric deposition, 3) the operations performed and material used at each station, and 4) the sequence of operations and main parameters analysed. The paper also provides the main environmental conditions that were prevailing during the campaign. Lastly, we present the types of articles produced based on work completed by the cruise that are part of this special issue.

Spatial variations of biochemical content and stable isotope ratios of size-fractionated plankton in the Mediterranean Sea (MERITE-HIPPOCAMPE campaign).

Plankton represents the main source of carbon in marine ecosystems and is consequently an important gateway for contaminants into the marine food webs. During the MERITE- HIPPOCAMPE campaign in the Mediterranean Sea (April-May 2019), plankton was sampled from pumping and net tows at 10 stations from the French coast to the Gulf of Gabès (Tunisia) to obtain different size fractions in contrasted regions. This study combines various approaches, including biochemical analyses, analyses of stable isotope ratios (δ13C, δ15N), cytometry analyses and mixing models (MixSiar) on size-fractions of phyto- and zooplankton from 0.7 to >2000 µm. Pico- and nanoplankton represented a large energetic resource at the base of pelagic food webs. Proteins, lipids, and stable isotope ratios increased with size in zooplankton and were higher than in phytoplankton. Stable isotope ratios suggest different sources of carbon and nutrients at the base of the planktonic food webs depending on the coast and the offshore area. In addition, a link between productivity and trophic pathways was shown, with high trophic levels and low zooplankton biomass recorded in the offshore area. The results of our study highlight spatial variations of the trophic structure within the plankton size-fractions and will contribute to assess the role of the plankton as a biological pump of contaminants.

Distribution and accumulation of metals and metalloids in planktonic food webs of the Mediterranean Sea (MERITE-HIPPOCAMPE campaign).

Particle-size classes (7 fractions from 0.8 to 2000 µm) were collected in the deep chlorophyll maximum along a Mediterranean transect including the northern coastal zone (bays of Toulon and Marseilles, France), the offshore zone (near the North Balearic Thermal Front), and the southern coastal zone (Gulf of Gabès, Tunisia). Concentrations of biotic metals and metalloids (As, Cd, Cr, Cu, Fe, Mn, Ni, Sb, V, Zn) bound to living or dead organisms and faecal pellets were assessed by phosphorus normalisation. Biotic metals and metalloids concentrations (except Cr, Mn, and V) were higher in the offshore zone than in the coastal zones. In addition, biotic Sb and V concentrations appeared to be affected by atmospheric deposition, and biotic Cr concentrations appeared to be affected by local anthropogenic inputs. Essential elements (Cd, Cu, Fe, Mn, Ni, V, Zn) were very likely controlled both by the metabolic activity of certain organisms (nanoeukaryotes, copepods) and trophic structure. In the northern coastal zone, biomagnification of essential elements was controlled by copepods activities. In the offshore zone, metals and metalloids were not biomagnified probably due to homeostasis regulatory processes in organisms. In the southern coastal zone, biomagnification of As, Cu, Cr, Sb could probably induce specific effects within the planktonic network.

Isotopic compositions of copper and zinc in plankton from the Mediterranean Sea (MERITE-HIPPOCAMPE campaign): Tracing trophic transfer and geogenic inputs.

This study uses Cu and Zn isotopic compositions as proxies of sources and metal transfers in the planktonic food webs from the Mediterranean Sea. Plankton was collected in spring 2019 in the deep chlorophyll maximum (DCM) along a North-South transect including coastal and offshore zones (MERITE-HIPPOCAMPE campaign). δ65Cu and δ66Zn were determined on four planktonic size fractions from 60 to 2000 µm. Combined δ65Cu and δ66Zn with geochemical tracers (Ti, particulate organic phosphorus) showed that geogenic particles were ubiquitous with plankton assemblages. The δ15N ecological tracer showed that planktonic food web was enriched in heavy isotopes of Cu and Zn in the higher trophic levels. δ65Cu were correlated with picoplankton in the offshore zone, and with zooplankton in the southern coastal zone. Firmicutes bacteria were found correlated with δ66Zn in northern and southern coastal zones suggesting decomposition of particulate matter at the DCM. These findings suggest that biogeochemical process may impact Cu and Zn isotopy in the planktonic community.

Ultraphytoplankton community structure in subsurface waters along a North-South Mediterranean transect.

Here we assessed the subsurface ultraphytoplanktonic (< 10 µm) community along a North-South round-trip Mediterranean transect as part of a MERITE-HIPPOCAMPE cruise campaign in April-May 2019. Temperature, salinity, and nutrient concentrations in subsurface waters (2-5 m depth) were also measured along the transect. The subsurface ultraphytoplankton community structure was resolved with a spatial resolution of few kilometers and temporal resolution of 30-min intervals using automated pulse shape recording flow cytometry. The subsurface waters were clustered into seven areas based on temperature and salinity characteristics. Synechococcus were by far the most abundant group in all prospected zones, and nanoeukaryotes were the main biomass component, representing up to 51 % of ultraphytoplanktonic carbon biomass. Apparent net primary productivity (NPP) followed a decreasing gradient along the transect from north to south and was mostly sustained by Synechococcus in all zones. These findings are likely to have implications in terms of the trophic transfer of contaminants in planktonic food webs, as they highlight the potential role of nanoplankton in contaminants bioaccumulation processes and the potential role of Synechococcus in a likely transfer via grazing activities.

Sinking Trichodesmium fixes nitrogen in the dark ocean.

The photosynthetic cyanobacterium Trichodesmium is widely distributed in the surface low latitude ocean where it contributes significantly to N2 fixation and primary productivity. Previous studies found nifH genes and intact Trichodesmium colonies in the sunlight-deprived meso- and bathypelagic layers of the ocean (200-4000 m depth). Yet, the ability of Trichodesmium to fix N2 in the dark ocean has not been explored. We performed 15N2 incubations in sediment traps at 170, 270 and 1000 m at two locations in the South Pacific. Sinking Trichodesmium colonies fixed N2 at similar rates than previously observed in the surface ocean (36-214 fmol N cell-1 d-1). This activity accounted for 40 ± 28% of the bulk N2 fixation rates measured in the traps, indicating that other diazotrophs were also active in the mesopelagic zone. Accordingly, cDNA nifH amplicon sequencing revealed that while Trichodesmium accounted for most of the expressed nifH genes in the traps, other diazotrophs such as Chlorobium and Deltaproteobacteria were also active. Laboratory experiments simulating mesopelagic conditions confirmed that increasing hydrostatic pressure and decreasing temperature reduced but did not completely inhibit N2 fixation in Trichodesmium. Finally, using a cell metabolism model we predict that Trichodesmium uses photosynthesis-derived stored carbon to sustain N2 fixation while sinking into the mesopelagic. We conclude that sinking Trichodesmium provides ammonium, dissolved organic matter and biomass to mesopelagic prokaryotes.

Occurrence, origin and potential ecological risk of dissolved polycyclic aromatic hydrocarbons and organochlorines in surface waters of the Gulf of Gabès (Tunisia, Southern Mediterranean Sea).

We investigated the occurrence, origin, and potential ecological risk of dissolved polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCBs) and organochlorine pesticides (OCPs) in 27 surface water samples collected from a highly anthropized and industrialized area in the Gulf of Gabès (Tunisia, Southern Mediterranean Sea) in October-November 2017. The results demonstrated a wide range of concentrations (ng L-1) with the following decreasing order: Æ©16 PAHs (17.6-71.2) > Æ©20 PCBs (2.9-33.7) > Æ©6 DDTs (1.1-12.1) > Æ©4 HCHs (1.1-14.8). Selected diagnostic ratios indicated a mixture of both pyrolytic and petrogenic sources of PAHs, with a predominance of petrogenic sources. PCB compositions showed distinct contamination signatures for tetra- to hepta-chlorinated PCBs, characteristic of contamination by commercial (Aroclor) PCB mixtures. The dominant OCP congeners were γ-HCH, 2,4'-DDD and 2,4'-DDE, reflecting past use of Lindane and DDTs in the study area. Agricultural, industrial and domestic activities, as well as atmospheric transport are identified as potential sources of PAHs, PCBs and OCPs in surface waters of the Gulf of Gabès. Toxic equivalents (TEQs) suggested a low carcinogenic potential for PAHs in seawater samples (mean of 0.14 ng TEQ L-1). Evaluation of risk coefficients revealed low risk for PAHs and PCBs, and moderate to severe risk for OCPs.

Efficiency of benthic diatom-associated bacteria in the removal of benzo(a)pyrene and fluoranthene.

We investigated the efficiency of a benthic diatom-associated bacteria in removing benzo(a)pyrene (BaP) and fluoranthene (Flt). The diatom, isolated from a PAH-contaminated sediment of the Bizerte Lagoon (Tunisia), was exposed in axenic and non-axenic cultures to PAHs over 7 days. The diversity of the associated bacteria, both attached (AB) and free-living bacteria (FB), was analyzed by the 16S rRNA amplicon sequencing. The diatom, which maintained continuous growth under PAH treatments, was able to accumulate BaP and Flt, with different efficiencies between axenic and non-axenic cultures. Biodegradation, which constituted the main process for PAH elimination, was enhanced in the presence of bacteria, indicating the co-metabolic synergy of microalgae and associated bacteria in removing BaP and Flt. Diatom and bacteria showed different capacities in the degradation of BaP and Flt. Nitzschia sp. harbored bacterial communities with a distinct composition between attached and free-living bacteria. The AB fraction exhibited higher diversity and abundance relative to FB, while the FB fraction contained genera with the known ability of PAH degradation, such as Marivita, Erythrobacter, and Alcaligenes. Moreover, strains of Staphylococcus and Micrococcus, isolated from the FB community, showed the capacity to grow in the presence of crude oil. These results suggest that a "benthic Nitzschia sp.-associated hydrocarbon-degrading bacteria" consortium can be applied in the bioremediation of PAH-contaminated sites.

Chemical composition and in vitro aryl hydrocarbon receptor-mediated activity of atmospheric particulate matter at an urban, agricultural and industrial site in North Africa (Bizerte, Tunisia).

As recognized risk factor to pose a health threat to humans and wildlife globally, atmospheric particulate matter (PM) were collected from a North African coastal city (Bizerte, Tunisia) for one year, and were characterized for their chemical compositions, including mercury (HgPM), as well as organic contaminants (polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs)), organic carbon (OC) and organic nitrogen (ON), determined in a previous study. Then, we applied an in vitro reporter gene assay (DR-CALUX) to detect and quantify the dioxin-like activity of PM-associated organic contaminants. Results showed that average HgPM concentration over the entire sampling period was found to be 13.4 ± 12 pg m-3. Seasonal variation in the HgPM concentration was observed with lower values in spring and summer and higher values in winter and autumn due to the variation of meteorological conditions together with the emission sources. Principal component analysis suggested that fossil fuel combustion and a nearby cement factory were the dominant anthropogenic HgPM sources. Aryl hydrocarbon receptor (AhR)-mediated activities were observed in all organic extracts of atmospheric PM from Bizerte city (388.3-1543.6 fg m-3), and shows significant positive correlations with all PM-associated organic contaminants. A significant proportion of dioxin-like activity of PM was related to PAHs. The dioxin-like activity followed the same trend as PM-associated organic contaminants, with higher dioxin-like activity in the cold season than in the warm season, indicating the advantage and utility of the use of bioassays in risk assessment of complex environmental samples.

Occurrence, distribution and ecological risk of trace metals and organic pollutants in surface sediments from a Southeastern European river (Somesu Mic River, Romania).

The increasing contamination of fresh water resources by trace metals and persistent organic pollutants is a major environmental concern. In the present study, we investigated, for the first time, the distribution, sources and ecological risk of trace metals and organic pollutants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), in surface sediments from a Southeastern European river (Somesu Mic River, Romania). Concentrations of Cd, Cr, Cu, Pb, Ni and Zn ranged from 0.04 to 0.4, 9.4 to 43.15, 7.2 to 65.6, 12.3 to 131.4, 14.7 to 47.7 and 42.1 to 236.8 mg kg-1 dw, respectively. Concentrations of total PAHs, PCBs and OCPs ranged from 24.8 to 575.6, 2.7 to 252.7 and 2.1 to 44.3 ng g-1 dw, respectively. Some sediment parameters, i.e., pH, total organic carbon (TOC) and total organic matter (OM) contents, played a significant role in the spatial distribution of contaminants. A combined analysis based on diagnostic ratios and multivariate analyses revealed PAHs originating mainly from pyrolytic sources. PCB compositions showed distinct contamination signatures for tri- to tetra-chlorinated PCBs, characteristic of contamination by Aroclor-1016 and -1254 technical mixtures. The dominant OCP congeners were α-HCH and p,p'-DDD, reflecting past use of technical HCHs and DDTs in agricultural practices. Metal source and pollution status was assessed using geoaccumulation index and enrichment factor, which indicate widespread pollution by Pb, Cd, Zn, Ni and Cu. The use of Sediments Quality Guidelines (SQGs), mean effect range-median quotient (m-ERM-Q) and toxic equivalent factor (TEF) indicated that the highest ecological risks occurred for PCBs and DDTs. This work presents not only initial baseline information on the extent of organic and inorganic contaminations in a river of ecological and economical interest, but also provides a diagnostic ratio/statistical combined approach that can be used to evaluate sediment quality in similar environments.

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 0.5-17.8 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.

Natural and anthropogenic particulate-bound aliphatic and polycyclic aromatic hydrocarbons in surface waters of the Gulf of Gabès (Tunisia, southern Mediterranean Sea).

Particulate-bound aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs) were investigated in the surface waters of the Gulf of Gabès (Tunisia, southern Mediterranean Sea). Samples were collected off the Sfax and Gabès-Ghannouch coasts. Concentrations in total resolved n-alkanes ranged from 0.03 to 3.2 µg L-1, and concentrations in total parents + alkylated PAHs ranged from bdl to 108.6 ng L-1. The highest concentrations were recorded in the southern Sfax. AHs were mainly of biogenic origin with odd n-alkane predominance, although an anthropogenic contribution was also detected. The PAH molecular patterns revealed a mixed origin with the presence of low molecular weight and alkylated compounds, characteristic of uncombusted oil-derived products, and the presence of high molecular weight compounds, typical of combustion residues. Rainfall events induced an increase in PAH concentrations by a factor 1.5-23.5. The particle-water partition coefficients (Koc) suggest that the partitioning of PAHs between the particulate and dissolved phases is driven by hydrophobicity and organic matter composition.

Characterization and sources of colored dissolved organic matter in a coral reef ecosystem subject to ultramafic erosion pressure (New Caledonia, Southwest Pacific).

The eastern lagoon of New Caledonia (NC, Southwest Pacific), listed as a UNESCO World Heritage site, hosts the world's second longest double-barrier coral reef. This lagoon receives river inputs, oceanic water arrivals, and erosion pressure from ultramafic rocks, enriched in nickel (Ni) and cobalt (Co). The aim of this study was to characterize colored dissolved organic matter (CDOM), as well as to determine its main sources and its possible relationships (through the use of Pearson correlation coefficients, r) with biogeochemical parameters, plankton communities and trace metals in the NC eastern lagoon. Water samples were collected in March 2016 along a series of river/lagoon/open-ocean transects. The absorption coefficient at 350nm (a350) revealed the influence of river inputs on the CDOM distribution. The high values of spectral slope (S275-295, >0.03m-1) and the low values of specific ultraviolet absorbance (SUVA254, <4Lmg-C-1m-1) highlighted the photodegradation of CDOM in surface waters. The application of parallel factor analysis (PARAFAC) on excitation-emission matrices (EEMs) allowed the identification of four CDOM components: (1) one humic- and one tyrosine-like fluorophores. They had terrestrial origin, exported through rivers and undergoing photo- and bio-degradation in the lagoon. These two fluorophores were linked to manganese (Mn) in southern rivers (r=0.46-0.50, n=21, p<0.05). (2) A tryptophan-like fluorophore, which exhibited higher levels offshore. It would be potentially released from the coral reef. (3) A second tyrosine-like ("tyrosine 2-like") fluorophore. Linked to Prochlorococcus cyanobacteria (r=0.39, n=47, p<0.05), this fluorophore would have an oceanic origin and enter in the lagoon through its southern and northern extremities. It also displayed relationships with Ni and Co content (r=0.53-0.54, n=21, p<0.05). This work underlines the diversity of CDOM sources in the NC eastern lagoon.