Disentangling fine particles (PM2.5) composition in Hanoi, Vietnam: Emission sources and oxidative potential.

A comprehensive chemical characterization of fine particulate matter (PM2.5) was conducted at an urban site in one of the most densely populated cities of Vietnam, Hanoi. Chemical analysis of a series of 57 daily PM2.5 samples obtained in 2019-2020 included the quantification of a detailed set of chemical tracers as well as the oxidative potential (OP), which estimates the ability of PM to catalyze reactive oxygen species (ROS) generation in vivo as an initial step of health effects due to oxidative stress. The PM2.5 concentrations ranged from 8.3 to 148 µg m-3, with an annual average of 40.2 ± 26.3 µg m-3 (from September 2019 to December 2020). Our results obtained by applying the Positive Matrix Factorization (PMF) source-receptor apportionment model showed the contribution of nine PM2.5 sources. The main anthropogenic sources contributing to the PM mass concentrations were heavy fuel oil (HFO) combustion (25.3 %), biomass burning (20 %), primary traffic (7.6 %) and long-range transport aerosols (10.6 %). The OP activities were evaluated for the first time in an urban site in Vietnam. The average OPv levels obtained in our study were 3.9 ± 2.4 and 4.5 ± 3.2 nmol min-1 m-3 for OPDTT and OPAA, respectively. We assessed the contribution to OPDTT and OPAA of each PM2.5 source by applying multilinear regression models. It shows that the sources associated with human activities (HFO combustion, biomass burning and primary traffic) are the sources driving OP exposure, suggesting that they should be the first sources to be controlled in future mitigation strategies. This study gives for the first time an extensive and long-term chemical characterization of PM2.5, providing also a link between emission sources, ambient concentrations and exposure to air pollution at an urban site in Hanoi, Vietnam.

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.

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.

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.

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.

Remobilization of polycyclic aromatic hydrocarbons and organic matter in seawater during sediment resuspension experiments from a polluted coastal environment: Insights from Toulon Bay (France).

Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0-2 cm (diagenetically new organic matter, OM) and 30-32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (<63 µm), enriched in organic carbon (8.2 and 6.3%, respectively) and in PAHs (concentration of Σ34 PAHs: 38.2 and 35.7 × 103 ng g-1, respectively). The resuspension of these sediments led to an increase in concentrations of dissolved Σ34 PAHs, dissolved organic carbon (DOC) and dissolved humic- and tryptophan-like fluorophores in seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4-6 ring PAHs, especially benzo(g,h,i)perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (Koc) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (Kow) (i.e., measured Koc > Koc predicted from Kow). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5-6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon.

Spatio-temporal variability of fluorescent dissolved organic matter in the Rhône River delta and the Fos-Marseille marine area (NW Mediterranean Sea, France).

The spatio-temporal variability of fluorescent dissolved organic matter (FDOM) and its relationships with physical (temperature, salinity) and chemical (nutrients, chlorophyll a, dissolved and particulate organic carbon, nitrogen and phosphorus) parameters were investigated in inland waters of the Rhône River delta and the Fos-Marseille marine area (northwestern Mediterranean, France). Samples were taken approximately twice per month in two inland sites and three marine sites from February 2011 to January 2012. FDOM was analysed using fluorescence excitation-emission matrices (EEMs) coupled with parallel factor analysis (PARAFAC). In inland waters, humic-like components C1 (λEx/λEm: 250 (330)/394 nm) and C3 (λEx/λEm: 250 (350)/454 nm) dominated over one tryptophan-like component C2 (λEx/λEm: 230 (280)/340 nm), reflecting a background contribution of terrigenous material (~67% of total fluorescence intensity, in quinine sulphate unit (QSU)) throughout the year. In marine waters, protein-like material, with tyrosine-like C4 (λEx/λEm: <220 (275)/<300 nm) and tryptophan-like C5 (λEx/λEm: 230 (280)/342 nm), dominated (~71% of total fluorescence intensity, in QSU) over a single humic-like component C6 (λEx/λEm: 245 (300)/450 nm). In inland waters of the Rhône River delta, humic-like components C1 and C3 were more abundant in autumn-winter, very likely due to inputs of terrestrial organic matter from rainfalls, runoffs and wind-induced sediment resuspension. In marine sites, intrusions of the Berre Lagoon and Rhône River waters had a significant impact on the local biogeochemistry, leading to higher fluorescence intensities of humic- and protein-like components in spring-summer. On average, the fluorescence intensities of FDOM components C4, C5 and C6 increased by 33-81% under lower salinity. This work highlights the complex dynamics of FDOM in coastal waters and confirms the link between marine FDOM and the Rhône River freshwater intrusions on larger spatial and temporal scales in the Fos-Marseille marine area.

Influence of PAHs among other coastal environmental variables on total and PAH-degrading bacterial communities.

We evaluated the relative impact of anthropogenic polycyclic aromatic hydrocarbons (PAHs) among biogeochemical variables on total, metabolically active, and PAH bacterial communities in summer and winter in surface microlayer (SML) and subsurface seawaters (SSW) across short transects along the NW Mediterranean coast from three harbors, one wastewater effluent, and one nearshore observatory reference site. At both seasons, significant correlations were found between dissolved total PAH concentrations and PAH-degrading bacteria that formed a gradient from the shore to nearshore waters. Accumulation of PAH degraders was particularly high in the SML, where PAHs accumulated. Harbors and wastewater outfalls influenced drastically and in a different way the total and active bacterial community structure, but they only impacted the communities from the nearshore zone (<2 km from the shore). By using direct multivariate statistical analysis, we confirmed the significant effect of PAH concentrations on the spatial and temporal dynamic of total and active communities in this area, but this effect was putted in perspective by the importance of other biogeochemical variables.

Top-Down Control of Diesel-Degrading Prokaryotic Communities.

Biostimulation through the addition of inorganic nutrients has been the most widely practiced bioremediation strategy in oil-polluted marine waters. However, little attention has so far been paid to the microbial food web and the impact of top-down control that directly or indirectly influences the success of the bioremediation. We designed a mesocosm experiment using pre-filtered (<50 µm) surface seawater from the Bay of Banyuls-sur-Mer (North-Western Mediterranean Sea) and examined the top-down effect exerted by heterotrophic nanoflagellates (HNF) and virus-like particles (VLP) on prokaryotic abundance, activity and diversity in the presence or absence of diesel fuel. Prokaryotes, HNF and VLP abundances showed a predator-prey succession, with a co-development of HNF and VLP. In the polluted system, we observed a stronger impact of viral lysis on prokaryotic abundances than in the control. Analysis of the diversity revealed that a bloom of Vibrio sp. occurred in the polluted mesocosm. That bloom was rapidly followed by a less abundant and more even community of predation-resistant bacteria, including known hydrocarbon degraders such as Oleispira spp. and Methylophaga spp. and opportunistic bacteria such as Percisivirga spp., Roseobacter spp. and Phaeobacter spp. The shift in prokaryotic dominance in response to viral lysis provided clear evidence of the 'killing the winner' model. Nevertheless, despite clear effects on prokaryotic abundance, activity and diversity, the diesel degradation was not impacted by top-down control. The present study investigates for the first time the functioning of a complex microbial network (including VLP) using a nutrient-based biostimulation strategy and highlights some key processes useful for tailoring bioremediation.

'Rare biosphere' bacteria as key phenanthrene degraders in coastal seawaters.

By coupling DNA-SIP and pyrosequencing approaches, we identified Cycloclasticus sp. as a keystone degrader of polycyclic aromatic hydrocarbons (PAH) despite being a member of the 'rare biosphere' in NW Mediterranean seawaters. We discovered novel PAH-degrading bacteria (Oceanibaculum sp., Sneathiella sp.) and we identified other groups already known to possess this function (Alteromonas sp., Paracoccus sp.). Together with Cycloclasticus sp., these groups contributed to potential in situ phenanthrene degradation at a rate >0.5 mg l(-1) day(-1), sufficient to account for a considerable part of PAH degradation. Further, we characterized the PAH-tolerant bacterial communities, which were much more diverse in the polluted site by comparison to unpolluted marine references. PAH-tolerant bacteria were also members of the rare biosphere, such as Glaciecola sp. Collectively, these data show the complex interactions between PAH-degraders and PAH-tolerant bacteria and provide new insights for the understanding of the functional ecology of marine bacteria in polluted waters.

Identification and quantification of known polycyclic aromatic hydrocarbons and pesticides in complex mixtures using fluorescence excitation-emission matrices and parallel factor analysis.

Polycyclic aromatic hydrocarbons (PAHs) and pesticides are among the most widespread organic contaminants in aquatic environments. Because of their aromatic structure, PAHs and pesticides have intrinsic fluorescence properties in the ultraviolet/blue spectral range. In this study, excitation-emission matrix (EEM) fluorescence spectroscopy and parallel factor (PARAFAC) analysis were used to characterise and discriminate fluorescence signatures of nine PAHs and three pesticides at the µg L(-1) level in the presence of humic substances (0.1-10 mgCL(-1)). These contaminants displayed a diversity of fluorescence signatures regarding spectral position (λEx: 220-335 nm, λEm: 310-414 nm), Stokes shift (39-169 nm) and number of peaks (1-8), with detection limits ranging from 0.02 to 1.29µgL(-1). The EEM/PARAFAC method applied to mixtures of PAHs with humic substances validated a seven-component model that included one humic-like fluorophore and six PAH-like fluorophores. The EEM/PARAFAC method applied to mixtures of pesticides with humic substances validated a six-component model that included one humic-like fluorophore and three pesticide-like fluorophores. The EEM/PARAFAC method adequately quantified most of the contaminants for humic substance concentrations not exceeding 2.5 mg CL(-1). The application of this method to natural (marine) samples was demonstrated through (1) the match between the Ex and Em spectra of PARAFAC components and the Ex and Em spectra of standard PAHs, and (2) the good linear correlations between the fluorescence intensities of PARAFAC components and the PAH concentrations determined by GC-MS.

Spatial and seasonal variabilities of dissolved hydrocarbons in surface waters from the Northwestern Mediterranean Sea: results from one year intensive sampling.

Dissolved aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analysed from surface water collected in continental, harbour and off-shore marine sites from Marseilles coastal area (Northwestern Mediterranean Sea) from February 2011 to February 2012. AH and PAH concentrations were in the range of 0.04-0.53 µgl(-1) and 8.1-405 ngl(-1), respectively. They both displayed seasonal and spatial variations in their concentrations and molecular composition. The lowest AH concentrations were found in summer and the highest PAH concentrations in winter. Both natural and anthropogenic (pyrogenic and petrogenic) hydrocarbon sources were identified. In winter, concentrations and composition patterns highlighted an increase in the signature of unburned and combusted fossil fuels, while they suggested an enhancement of weathering processes in summer months. Hydrocarbon inputs to the dissolved phase seemed to originate mainly from the atmosphere and the Rhône River. Hydrocarbon additional sources were identified only at the harbour site, emphasising the intense shipping traffic and industrial activities occurring in one of the most important Mediterranean harbours. This study underscores the strong dynamics of dissolved hydrocarbons and the uncoupling of the sources, transport and removing processes affecting AHs and PAHs. It also demonstrates the pertinence of taking this dynamics into account for the budget assessments of organic pollutants in coastal environments.

Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea.

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05-0.41 and 0.04-4.3 µg l(-1) in the SSW, peaking up to 38 and 1366 µg l(-1) in the SML, respectively. Dissolved and particulate PAHs ranged 1.9-98 and 1.9-21 ng l(-1) in the SSW, amounting up 217 and 1597 ng l(-1) in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9-11.5 in the dissolved phase.

Characterization of dissolved organic matter in a coral reef ecosystem subjected to anthropogenic pressures (La Réunion Island, Indian Ocean) using multi-dimensional fluorescence spectroscopy.

La Saline fringing reef is the most important coral reef complex of La Réunion Island (southwestern Indian Ocean; 21°07'S, 55°32'E). This ecosystem is subjected to anthropogenic pressures through river inputs and submarine groundwater discharge (SGD). The goal of this study was to characterize the pool of fluorescent dissolved organic matter (FDOM) in different water bodies of La Saline fringing reef ecosystem using excitation-emission matrix (EEM) spectrofluorometry. From EEMs, we identified the different fluorophores by the peak picking technique and determined two fluorescence indices issued from the literature: the humification index (HIX) and the biological index (BIX). The main known fluorophores were present within the sample set: humic-like A, humic-like C, marine humic-like M, tryptophan-like T1 and T2, and tyrosine-like B1 and B2. In some samples, unknown fluorophores ("U") were also detected. The surface oceanic waters located beyond the reef front displayed a typical oligotrophic marine signature, with a dominance of autochthonous/biological material (presence of peaks: T1>B1>A>T2>M>C; HIX: 0.9±0.4; BIX: 2.3±1.1). In the reef waters, the autochthonous/biological fingerprint also dominated even though the content in humic substances was higher (same relative distribution of peaks; HIX: 1.6±0.6; BIX: 1.0±0.1). Sedimentary and volcanic SGD showed very different patterns with a strong terrestrial source for the former (A>T1>C>B1 and A>C>B1; HIX: 9.8±2.0; BIX: 0.8±0.0) and a weak terrestrial source for the latter (A>B1>U3>B2>C and A>U4>C; HIX: 2.4±0.3; BIX: 0.9±0.0). In the Hermitage River, both humic substances and protein-like material were abundant (T1>A>U5>B1>C>B2; HIX: 2.3; BIX: 1.4). We provide evidences for the presence of anthropogenic DOM in some of these water bodies. Some oceanic samples (presence of peaks U1 and U2) were likely contaminated by oil-derived PAHs from ships navigating around the reef front, whereas the Hermitage River was highly impacted by sewage effluents, numerous in this coastal area of La Réunion Island. We conclude that multi-dimensional fluorescence spectroscopy (EEM) coupled to the determination of HIX and BIX is a good tool for assessing the origin and distribution of DOM in the coral reef ecosystems submitted to anthropogenic impacts.