Effects of metals and persistent organic pollutants on the fitness and health of juveniles of the endangered european sturgeon Acipenser sturio Exposed to W1ater and sediments of the garonne and dordogne rivers.

The last remaining population of European sturgeon (Acipenser sturio) lives in the Gironde-Garonne-Dordogne (France) catchment (GGD). Captive young individuals are released into the GGD hydrosystem each year, as part of a restocking programme. This study aims to assess the health status of juveniles A. sturio to current conditions in the GGD hydrosystem, to evaluate their capacity to survive and grow in a moderately anthropized ecosystems. 3-month-old farmed sturgeons were exposed for one month in experimental conditions that mimic the environmental conditions in the Garonne and Dordogne rivers, followed by five months of depuration. After one month of exposure, fish exposed to Dordogne and Garonne waters bioaccumulated higher levels of metals and persistent organic pollutants, displayed a reduced hepato-somatic index, and had depleted levels of lipids and glycogen content in their liver, when compared with the Reference group. However, metabolic and swimming performance, as well as the costs of swimming were not impaired. After the 5 months depuration, a significant decrease of K was observed for all exposure conditions. HSI also decreased with time. The overall health status and adaptive capacity of juvenile A. sturio appeared to be maintained over the experimental 6 months' period. Juveniles of A. sturio seem to have the adaptive capacity to survive and grow in the GGD hydrosystem, after being released as part of a restocking programme.

Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. 2. Time Evolution and Effect of Particle Acidity.

The present work is an extensive laboratory study of organosulfate (OS) formation from the reaction of α-pinene oxidation products or proxies with acidified ammonium sulfate aerosols in three different acidity conditions ((NH4)2SO4 0.06 M; (NH4)2SO4/H2SO4 0.06 M/0.005 M; (NH4)2SO4/H2SO4 0.03 M/0.05 M). The kinetics of the reactions of α-pinene, α-pinene oxide, isopinocampheol, pinanediol, and myrtenal with ammonium sulfate particles were studied using a quasi-static reactor. The reaction of α-pinene oxide with the highly acidic ammonium sulfate particles was determined to be 7, 10, 21, and 24 times faster than for isopinocampheol, α-pinene, pinanedial, and myrtenal, respectively, for an OS precursor concentration of 1 ppm and after 1 h reaction time. The effective rate coefficients for OS formation from α-pinene oxide were determined to be 2 orders of magnitude higher in highly acidic conditions than for the two other acidity conditions. For α-pinene oxide reactions with highly acidic ammonium sulfate particles, OS formation was observed to increase linearly with (i) the time of reaction up to 400 min (r2 > 0.95) and (ii) α-pinene oxide gas-phase concentration. However, OS formation from α-pinene oxide reactions with slightly acidic or pure ammonium sulfate particles was limited, with a plateau ([OS]max = 0.62 ± 0.03 µg) reached after around 15-20 min. Organosulfate dimers (m/z 401 and m/z 481) were detected not only with highly acidic particles but also with slightly acidic and pure ammonium sulfate particles, indicating that oligomerization processes do not require strong acidity conditions. Dehydration products of organosulfates (m/z 231 and m/z 383) were observed only under highly acidic conditions, indicating the key role of H2SO4 on the dehydration of organosulfates and the formation of olefins in the atmosphere. Finally, this kinetic study was completed with simulation chamber experiments in which the mass concentration of organosulfates was shown to depend on the available sulfate amount present in the particle phase (r2 = 0.96). In conclusion, this relative comparison between five organosulfate precursors shows that epoxide was the most efficient reactant to form organosulfates via heterogeneous gas-particle reactions and illustrates how gas-particle reactions may play an important role in OS formation and hence in the atmospheric fate of organic carbon. The kinetic data presented in this work provide strong support to organosulfate formation mechanisms proposed in part 1 ( J. Phys. Chem. A 2016 , 120 , 7909 - 7923 ).

RAD sequencing reveals within-generation polygenic selection in response to anthropogenic organic and metal contamination in North Atlantic Eels.

Measuring the effects of selection on the genome imposed by human-altered environment is currently a major goal in ecological genomics. Given the polygenic basis of most phenotypic traits, quantitative genetic theory predicts that selection is expected to cause subtle allelic changes among covarying loci rather than pronounced changes at few loci of large effects. The goal of this study was to test for the occurrence of polygenic selection in both North Atlantic eels (European Eel, Anguilla anguilla and American Eel, A. rostrata), using a method that searches for covariation among loci that would discriminate eels from 'control' vs. 'polluted' environments and be associated with specific contaminants acting as putative selective agents. RAD-seq libraries resulted in 23 659 and 14 755 filtered loci for the European and American Eels, respectively. A total of 142 and 141 covarying markers discriminating European and American Eels from 'control' vs. 'polluted' sampling localities were obtained using the Random Forest algorithm. Distance-based redundancy analyses (db-RDAs) were used to assess the relationships between these covarying markers and concentration of 34 contaminants measured for each individual eel. PCB153, 4'4'DDE and selenium were associated with covarying markers for both species, thus pointing to these contaminants as major selective agents in contaminated sites. Gene enrichment analyses suggested that sterol regulation plays an important role in the differential survival of eels in 'polluted' environment. This study illustrates the power of combining methods for detecting signals of polygenic selection and for associating variation of markers with putative selective agents in studies aiming at documenting the dynamics of selection at the genomic level and particularly so in human-altered environments.

Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. Part I: Product Identification, Formation Mechanisms and Effect of Relative Humidity.

In the present study, quasi-static reactor and atmospheric simulation chamber experiments were performed to investigate the formation of α-pinene-derived organosulfates. Organosulfates (R-OSO3H) were examined for the reactions between acidified ammonium sulfate particles exposed to an individual gaseous volatile organic compound, such as α-pinene and oxidized products (α-pinene oxide, isopinocampheol, pinanediol and myrtenal). Molecular structures were elucidated by liquid chromatography interfaced to high-resolution quadrupole time-of-flight mass spectrometry equipped with electrospray ionization (LC/ESI-HR-QTOFMS). New organosulfate products were detected and identified for the first time in the present study. Reaction with α-pinene oxide was found to be a favored pathway for organosulfate formation (C10H18O5S) and to yield organosulfate dimers (C20H34O6S and C20H34O9S2) and trimers (C30H50O10S2) under dry conditions (RH < 1%) and high particle acidity and precursor concentrations (1 ppm). The role of relative humidity on organosulfate formation yields and product distribution was specifically examined. Organosulfate concentrations were found to decrease with increasing relative humidity. Mechanistic pathways for organosulfate formation from the reactions between α-pinene, α-pinene oxide, isopinocampheol, or pinanediol with acidified ammonium sulfate particles are proposed.

Physiological effects of PFAS exposure in seabird chicks: A multi-species study of thyroid hormone triiodothyronine, body condition and telomere length in South Western France.

There is growing evidence that poly and perfluoroalkyl substances (PFAS) exposure leads to the disruption of thyroid hormones including thyroxine (T4) and triiodothyronine (T3), and may affect telomeres, repetitive nucleotide sequences which protect chromosome ends. Many seabird species are long-lived top predators thus exhibit high contaminant levels, and PFAS-disrupting effects on their physiology have been documented especially in relation to the endocrine system in adults. On the contrary, studies on the developmental period (i.e., chicks), during which exposure to environmental contaminants may have a greater impact on physiological traits, remain scarce to this date. We carried out a multi-species study with the aim to assess whether and to which extent chicks of four gull species (herring gull, great and lesser black-backed gull, yellow-legged gull) in South Western France are contaminated by PFAS, and to bring further evidence about their potential physiological consequences. Linear PFOS showed concentrations of concern as it was generally >10 times higher than the other PFAS, and exceeded a threshold toxicity level (calculated from previous studies in birds) in almost all sampled chicks. Nonetheless, in herring gull male chicks, total T3 levels were significantly and negatively associated with perfluorodecanoate (PFDA) and perfluorododecanoate (PFDoDA) and positively associated with perfluorotetradecanoate (PFTeDA) in female chicks. Total T3 levels were also positively associated with PFDoDA in great black backed gull male chicks and with perfluorotridecanoate (PFTrDA) in lesser black backed gull chicks. In lesser and great black-backed gulls, both females and males showed significant negative associations between several PFAS and their body condition, and a positive association between telomere length and L-PFOS in the yellow-legged gull was also found. These results corroborate previous findings and need to be further explored as they suggest that PFAS may interfere with the physiological status of chicks during the developmental period, potentially inducing long-lasting consequences.

Occurrence of priority and emerging organic compounds in fishes from the Rhone River (France).

The main objective of this study was to collect new data on the occurrence, levels of priority and emerging organic compounds in freshwater fish sampled in the Rhone River. The 34 studied contaminants included alkylphenols, bisphenol A, polybromodiphenylethers (PBDE), perfluorinated compounds, hexabromocyclododecanes (HBCD), hexachlorobenzene and hexachlorobutadiene (HCBD). About 50 fish samples (individual specimens or pooled fish) were collected from three sites located upstream and downstream of the Lyon metropolitan area in the Rhone River (France). Four species were caught at each site, namely: the barbel (Barbus barbus), the common bream (Abramis brama), the white bream (Blicca bjoerkna) and the chub (Squalius cephalus). Some contaminants were quantified in all the 32 fish samples analysed: 4-nonylphenol, α-HBCD, the six PBDE congeners (28, 47, 99, 100, 153, 154), perfluorooctanesulfonate (PFOS) and perfluorodecanoic acid. Twenty three of the 32 samples had a concentration of PFOS above the Environmental Quality Standards (EQS) (up to six times higher than the EQS), and all the 32 samples had concentrations of PBDE above the EQS (up to 4,000 times higher, with the sum of six PBDE varying from 4.5 to 182 ng/g dry weight). Clearly, the interest to consider PFOS and HBCD as new priority substances is confirmed. In contrast, the pertinence of a priority status for HCBD, which was never quantified in our study, might have to be reconsidered in the future.

Occurrence and fate of relevant substances in wastewater treatment plants regarding Water Framework Directive and future legislations.

The next challenge of wastewater treatment is to reliably remove micropollutants at the microgram per litre range. During the present work more than 100 substances were analysed through on-site mass balances over 19 municipal wastewater treatment lines. The most relevant substances according to their occurrence in raw wastewater, in treated wastewater and in sludge were identified, and their fate in wastewater treatment processes was assessed. About half of priority substances of WFD were found at concentrations higher than 0.1 µg/L in wastewater. For 26 substances, potential non-compliance with Environmental Quality Standard of Water Framework Directive has been identified in treated wastewater, depending on river flow. Main concerns are for Cd, DEHP, diuron, alkylphenols, and chloroform. Emerging substances of particular concern are by-products, organic chemicals (e.g. triclosan, benzothiazole) and pharmaceuticals (e.g. ketoprofen, diclofenac, sulfamethoxazole, carbamazepine). About 80% of the load of micropollutants was removed by conventional activated sludge plants, but about two-thirds of removed substances were mainly transferred to sludge.

Heavy metals and organochlorinated compounds in the European eel (Anguilla anguilla) from the Adour estuary and associated wetlands (France).

Heavy metals and organic pollutants were investigated in the Adour estuary (South West France) and associated wetlands using the European eel (Anguilla anguilla) as a bioindicator. Heavy metals (Cu, Cd, Zn, Pb, and Ag) were measured in soft tissue of yellow eels. Mercury (total Hg and MeHg) and organochlorinated compounds (7 PCBs, 11 OCPs) were analysed in muscle. Concentrations in muscle were in agreement with moderately contaminated environments in Europe and were below the norms fixed for eel consumption for heavy metals and OCPs. Analyses of liver showed a higher pressure of Ag and Zn in the downstream estuary than in the freshwater sites whereas Cd was lower in the estuary probably because of the salinity influence. According to quality classes 100% of eels from freshwater sites indicated clean or slightly polluted environments. However, total mercury concentrations were close to the thresholds fixed by the European Community in the downstream estuary, whereas the sum of PCBs was found to be greatly above the fixed value. 100% of the individuals from the estuary were classified in quality classes corresponding to polluted or highly polluted sites. These first results highlight the need of further investigations focused on mercury and PCBs in this area taking the seasonal temperature influence into account for a better understanding of the pollution distribution and the possible threat on the eel population from the Adour basin.

Limiting the emissions of micro-pollutants: what efficiency can we expect from wastewater treatment plants?

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet the environmental quality standards set by new regulations like the Water Framework Directive. The present work assessed the efficiency of different types of primary, secondary and tertiary processes for the removal of more than 100 priority substances and other relevant emerging pollutants through on-site mass balances over 19 municipal wastewater treatment lines. Secondary biological processes proved to be in average 30% more efficient than primary settling processes. The activated sludge (AS) process led to a significant reduction of pollution loads (more than 50% removal for 70% of the substances detected). Biofilm processes led to equivalent removal efficiencies compared to AS, except for some pharmaceuticals. The membrane bioreactor (MBR) process allowed to upgrade removal efficiencies of some substances only partially degraded during conventional AS processes. Preliminary tertiary processes like tertiary settling and sand filtration could achieve significant removal for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient (close to 100%) to complete the removal of polar pesticides and pharmaceuticals; less polar substances being better retained by reverse osmosis.

On-site evaluation of the removal of 100 micro-pollutants through advanced wastewater treatment processes for reuse applications.

The next challenge of wastewater treatment is to reliably remove micro-pollutants at the microgram per litre range in order to meet reuse applications and contribute to reach the good status of the water bodies. A hundred priority and relevant emerging substances were measured to evaluate at full-scale the removal efficiencies of seven advanced treatment lines (one membrane bioreactor process and six tertiary treatment lines) that were designed for reuse applications. To reliably compare the processes, specific procedures for micro-pollutants were applied for sampling, analysis and calculation of removal efficiencies. The membrane bioreactor process allowed to upgrade the removal efficiencies of about 20% of the substances measured, especially those that were partially degraded during conventional processes. Conventional tertiary processes like high rate clarification, sand filtration and polishing pond achieved significant removal for some micro-pollutants, especially for adsorbable substances. Advanced tertiary processes, like ozonation, activated carbon and reverse osmosis were all very efficient to complete the removal of polar pesticides and pharmaceuticals; metals and less polar substances were better retained by reverse osmosis.

Passive samplers for chemical substance monitoring and associated toxicity assessment in water.

The European legislation, and in particular the Water Framework Directive requires the development of cost efficient monitoring tools that can provide the required information for the assessment of water contamination. Passive sampling methods represent one of the novel tools that have a potential to be used in various regulatory monitoring programmes aimed at assessing the levels of chemical pollutants. These methods are particularly interesting for sampling polar organic pollutants in water because they provide representative information of the water quality over extended time periods (days to weeks) in environments with fluctuating contaminant concentrations. This is achieved by integrative sampling of pollutants over the whole sampler deployment period. These tools can be coupled to toxicity testing using bioassays that give information on toxic and ecotoxic hazards associated to substances that are present, these substances being identified or not. In this study the polar organic chemical integrative sampler (POCIS) was used in surface water to evaluate the water contamination by polar organic compounds and their potential toxicity.

Development in the European flounder (Platichthys flesus) of a q-PCR assay for the measurement of telomere length, a potential biomarker of pollutant effects for biomonitoring studies.

Telomeres protect the coding sequence of chromosome ends and Telomere Length (TL) has been proposed as a biomarker of cellular aging, cumulative stress exposure and life-span in humans. With the aim to propose new biomarkers, a q-PCR protocol was adapted for the measurement of TL in the European flounder Platichthys flesus. The protocol was then applied in 2-year-old flounders from the Seine Estuary. The absolute TL in the flounder is 54 ± 13 kbp per genome (mean ± standard error). Considering relative or absolute TL, no correlation was observed with DNA damage and any of the measured contaminant concentrations (trace elements, metabolites of polycyclic aromatic hydrocarbons, polychlorobiphenyls, organochlorinated pesticides, polybrominated diphenyl ethers, perfluoroalkyl substances). Because sampling was limited, further investigations are required to state a possible impact of chemical pollution on flatfish telomeres. This is motivated by correlations observed with organochlorinated compounds when decreasing statistical significance (p ≤ 0.10).

High levels of fluoroalkyl substances and potential disruption of thyroid hormones in three gull species from South Western France.

Per- and poly-fluoroalkyl substances (PFAS) raised increasing concerns over the past years due to their persistence and global distribution. Understanding their occurrence in the environment and their disruptive effect on the physiology of humans and wildlife remains a major challenge in ecotoxicological studies. Here, we investigate the occurrence of several carboxylic and sulfonic PFAS in 105 individuals of three seabird species (27 great black-backed gull Larus marinus; 44 lesser black-backed gull Larus fuscus graellsii; and 34 European herring gull Larus argentatus) from South western France. We further estimated the relationship between plasma concentrations of PFAS and i) the body condition of the birds and ii) plasma concentrations of thyroid hormone triiodothyronine (TT3). We found that great and lesser black-backed gulls from South Western France are exposed to PFAS levels comparable to highly contaminated species from other geographical areas, although major emission sources (i.e. related to industrial activities) are absent in the region. We additionally found that PFAS are negatively associated with the body condition of the birds in two of the studied species, and that these results are sex-dependent. Finally, we found positive associations between exposure to PFAS and TT3 in the great black-backed gull, suggesting a potential disrupting mechanism of PFAS exposure. Although only three years of data have been collected, we investigated PFAS trend over the study period, and found that great black-backed gulls document an increasing trend of plasma PFAS concentration from 2016 to 2018. Because PFAS might have detrimental effects on birds, French seabird populations should be monitored since an increase of PFAS exposure may impact on population viability both in the short- and long-term.

On-site evaluation of the efficiency of conventional and advanced secondary processes for the removal of 60 organic micropollutants.

The next challenge of wastewater treatment is to reliably remove micropollutants at the microgram per litre range in order to reduce the discharge for priority substances and to meet the environmental quality standards set by the European Water Framework Directive. The present work assessed the occurrence of 60 organic substances (priority substances and other relevant pollutants) in municipal wastewater and sludge. Their fate in the treatment processes and their removal efficiencies were quantified. Thorough on-site mass balances were carried out at 8 municipal wastewater treatment plants chosen among conventional and advanced secondary processes. It was found that 70% of the substances were quantified in raw wastewater and 50% in effluent, with a transfer without a limited degradation for most of them. Low loaded activated sludge (AS) process reduced the emission of more than half of micropollutants. At low sludge retention time (AS under high load), lower removal efficiencies were measured compared to low loaded AS. No influence of temperature of the biological reactor was shown. The membrane bioreactor process increased the removal efficiencies for one third of the substances that were partially removed with AS. Still, five substances were measured at concentrations exceeding the environmental quality standards at the outlet of the studied plants. In addition to efforts for source-reduction, complementary treatments need to be set-up.

Combined spatial and retrospective analysis of fluoroalkyl chemicals in fluvial sediments reveal changes in levels and patterns over the last 40 years.

Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g-1 dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g-1 dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g-1 dw), increasing to a maximum of 51 ng g-1 dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g-1 dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

Fast and efficient extraction methods for the analysis of polychlorinated biphenyls and polybrominated diphenyl ethers in biological matrices.

This paper describes fast and simple extraction methods for the determination of polychlorinated biphenyls and polybrominated diphenyl ethers in biological matrices. Four extraction protocols were tested. The first protocol used microwave-assisted extraction combined with two purification steps. The second one was similar, except that microwave-assisted extraction was replaced by accelerated solvent extraction. The third one combined extraction/purification by accelerated solvent extraction with final purification on a silica gel column. The last one combined microwave-assisted extraction with purification on an acidic silica gel column. The protocols were tested on various matrices: a spiked matrix, two certified matrices (SRM 2977, WMF 01), and natural matrices (mysids and fish). All of the protocols produced good performance in terms of recovery and reproducibility. The two last protocols showed promising results in terms of applicability to natural matrices, as they required a minimum of sample handling and minimal amounts of solvent and time. These methods allowed at least 24 samples to be handled per day, and could easily be used for routine analysis.

Demographic, endocrine and behavioral responses to mirex in the South polar skua.

Population consequences of chronic exposure to multiple pollutants at low environmental doses remain speculative, because of the lack of appropriate long-term monitoring surveys. This study integrates proximate and ultimate aspects of persistent organic pollutants (POP) burden in free-living vertebrates, by coupling hormonal and behavioral endpoints, life-history traits, and population dynamics. Blood samples (N=70) were collected in South polar skuas during two breeding periods, in 2003 and 2005, and individuals were annually monitored until 2011. Multi-state mark recapture models were used to test the effects of POP levels on demographic traits. Survival rate and long-term breeding probability were not related to individual POP levels, whereas long-term breeding success significantly decreased with increasing blood levels of mirex, an organochlorine insecticide. At the proximate level, corticosterone (stress hormone) and prolactin (parental care hormone) levels were not linked to individual POP burden. Nest defense in 2005 was significantly less intensive in chick-rearing skuas bearing higher mirex levels, suggesting reproductive behavioral impairment. Matrix population models were then built to project the rate of population decline according to increasing mirex burden. Although mirex levels were 2.8 times higher in 2003 than in 2005, the population-level effect of mirex was only detected in 2005, the year of higher corticosterone levels. The combination of endocrine traits with demographic analysis thereby enables to provide new support of synergistic interactions between pollutants and stress levels on long-term breeding outputs and population dynamics.

Assessment of the effects of discontinuous sources of contamination through biomarker analyses on caged mussels.

The present study analysed potential adverse effects of discontinuous sources of contamination, namely the discharge of a combined sewer overflow (CSO) and of runoff in an urban area, the Bay of Santander (North Iberian Peninsula). Water samples and caged mussels were used to analyse concentrations of contaminants and biological responses. Mussels (Mytilus galloprovincialis) were transplanted to a marina receiving runoff from a petrol station and to a CSO discharge site. Samples were collected in synchrony with heavy rains along 62days. Lysosomal membrane stability (LMS) and acyl-CoA oxidase (AOX) activity were measured as core biomarkers and were analysed at all sampling times. Histopathology of digestive gland and gonads, transcription levels of vitellogenin gene, volume density of black silver deposits and micronuclei formation were measured at initial and final stages of the transplant. Chemical analyses of metals, polycyclic aromatic hydrocarbons (PAHs) and endocrine disruptors were performed in water samples and mussel flesh. Mussels accumulated low concentrations of contaminants, which is in accordance with results obtained from exposure biomarkers. AOX activity decreased in all transplanted mussels after the first heavy rain, but this change seems to be related to the seasonal pattern of the enzyme activity. Mussels located close to the CSO discharge site showed a reduction in LMS after the first rain event, when compared to mussels before the transplant and to mussels from the reference location. However, this was attributable to natural environmental changes rather than to pollution. Values of the rest of analysed biomarkers were below threshold values reported for the study area.

Marine water quality assessment using transplanted oyster larvae.

Active bio-monitoring in terms of biomarkers was attempted using Crassostrea gigas larvae produced in the laboratory and transplanted using special containers to two sites at the entrance (A) and inner part (P) of the harbour of Arcachon (French Atlantic Coast). The larvae were kept in the medium for 48 h. Their physiological status and their biomarker levels : acetylcholinesterase AChE, catalase CAT and glutathione S-transferase GST activities were determined together with metallothionein MT and Thiobarbituric Acid Reactive Substances TBARS concentrations. Copper and PAH (polycyclic aromatic hydrocarbon) concentrations were determined in the exposed larvae and in the sediments collected under the containers. Cadmium, lead and zinc could be also analyzed in the sediments. Toxicity tests demonstrate that the larvae are in better physiological conditions in A compared to P. Larvae transplanted in the inner harbour (P) present relatively high GST activity (869.1+/-39.3 nmol min(-1)mg protein(-1)), TBARS (2.74+/-0.19 nmol mg protein(-1)), compared to those exposed at the harbour entrance (A). Copper measured in the sediments (65+/-1 mg kg(-1) d.w.) collected under the cages at P is higher than at A. Larvae placed in A present higher total PAH concentrations compared to the inner part. The data tend to reveal a lower copper and higher PAH contamination in A than in P. Therefore larvae, developing in the natural medium, show different responses according to their immersion sites. These responses, obtained within 48 h, may be related to the chemical contamination of the environment and may be used for seawater quality assessment in future studies.

Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs.

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.