Multiresidue Methods for the Determination of Organic Micropollutants and Their Metabolites in Fish Matrices.

Two analytical methods were developed for the determination of 48 organic compounds and 20 of their main by-products in fish matrices. The targeted compounds belong to various chemical classes of metabolizable (phthalates, polycyclic aromatic hydrocarbons, insecticides [pyrethroids and N,N-diethyl-meta-toluamide]) and legacy (organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers) pollutants. Analyses were performed by gas and liquid chromatography-tandem mass spectrometry in multiple reaction monitoring (MRM) and dynamic MRM, respectively. Method performances were satisfactory, with results meeting the validation criteria because they achieved good linearity responses, recovery, precision, and accuracy for most of the 68 investigated compounds. The methods were then applied on 3 feral chub (Squalius cephalus) collected from the Marne hydrographic network (France). Twenty-six parent compounds and 5 metabolites were systematically detected in fish matrices, with substantial concentration variability within and among individuals. Phthalates and pyrethroids accounted for most of the pollutant load. Metabolite concentrations in liver samples exceeded those of parent molecules in fish muscle. The present study presents 2 reliable methods for the determination of a wide range of contaminants and underlines the importance of metabolite analysis for a more comprehensive understanding of pollutant bioaccumulation and fate in aquatic organisms. Environ Toxicol Chem 2019;38:1866-1878. © 2019 SETAC.

Contamination of soils by metals and organic micropollutants: case study of the Parisian conurbation.

Soils are playing a central role in the transfer and accumulation of anthropogenic pollutants in urbanized regions. Hence, this study aimed at examining the contamination levels of selected soils collected within and around the Paris conurbation (France). This also evaluated factors controlling contamination. Twenty-three trace and major elements as well as 82 organic micropollutants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalates (PAEs), polybrominated diphenyl ethers (PBDEs), alkylphenols (APs), and perfluoroalkylated substances (PFASs) were analyzed. Results reinforced the concern raised by the occurrence and levels of metals such as Zn, Pb, Cu, and Hg, identified as metallic markers of anthropogenic activities, but also pointed out the ubiquitous contamination of soils by organic micropollutants in the 0.2-55,000-µg/kg dw range. For well-documented compounds like PAHs, PCBs, and to a lesser extent PBDEs, contents were in the range of background levels worldwide. The pollutant stock in tested soil was compared to the annual atmospheric input. For PAHs; Pb; and to a lesser extent Zn, Cu, Cd, Hg, Sb, PAEs, and APs, a significant stock was observed, far more important than the recent annual atmospheric fluxes. This resulted from both (i) the persistence of a fraction of pollutants in surface soils and (ii) the cumulative atmospheric inputs over several decades. Regarding PBDEs and PFASs, stronger atmospheric input contributions were observed, thereby highlighting their recent dispersal into the environment.

First characterization of the endocrine-disrupting potential of indoor gaseous and particulate contamination: comparison with urban outdoor air (France).

The composition of endocrine-disrupting compounds (EDCs) in the ambient air of indoor environments has already been described, but little is known about the inherent endocrine-disrupting potential of indoor air contamination. We therefore aimed to study the distribution of bioactive EDCs in the gaseous and particulate phases of indoor air using a cellular bioassay approach that integrates the interaction effects between chemicals. Organic air extracts, both gaseous and particulate, were taken from three indoor locations (office, apartment, and children's day care) in France and sampled in two different seasons in order to study their interference with the signaling of estrogen, androgen, and thyroid receptors. The experiments were also conducted on aerial extracts from an outdoor site (urban center). We found that gaseous and/or particulate extracts from all locations displayed estrogenicity, anti-androgenicity, and thyroidicity. Overall, indoor air extracts had a higher endocrine-disrupting potential compared to outdoor ones, especially during winter and in the day care. The biological activities were predominant for the gaseous extracts and tended to increase for the particulate extracts in cool conditions. In conclusion, our data confirmed the presence of bioactive EDCs in a gaseous state and highlighted their indoor origin and concentration, especially in the cold season.

Occurrence of antibiotics in rural catchments.

The transfer of 23 antibiotics from domestic and hospital sources was investigated in two elementary river watersheds receiving wastewater treatment plant (WWTP) discharges, in relation with the hydrological cycle and seasonal conditions. Antibiotic concentrations in the effluent of a WWTP treating wastewaters from both hospital and domestic sources (18-12 850 ng L-1) were far higher than those from domestic sources exclusively (3-550 ng L-1). In rivers, upstream of the WWTP discharges, fluoroquinolones only were found at low concentrations (≤10 ng L-1). Their presence might be explained by transfer from contaminated agricultural fields located on the river banks. Immediately downstream of the WWTP discharge, antibiotic occurrence increased strongly with mean concentrations up to 1210 ng L-1 for ofloxacin and 100% detection frequencies for vancomycin, sulfamethoxazole, trimethoprim and three fluoroquinolones. Dilution processes during high-flow periods led to concentrations 14 times lower than during low-flow periods. Downstream of the discharge, the antibiotic dissipation rate from the water column was higher for fluoroquinolones, in relation with their high sorption upon suspended matter and sediment. Only five antibiotics (vancomycin and four fluoroquinolones ciprofloxacin, norfloxacin, ofloxacin and enoxacin) were partly distributed (11%-36%) in the particulate phase. Downstream of the discharge, antibiotic contents in sediment ranged from 1700 to 3500 ng g-1 dry weight, fluoroquinolones accounting for 97% of the total.

Fate of antibiotics from hospital and domestic sources in a sewage network.

Investigation of domestic and hospital effluents in a sewage system of an elementary watershed showed that antibiotics belonging to eight classes were present with concentrations ranging from

Cat serum contamination by phthalates, PCBs, and PBDEs versus food and indoor air.

A wide variety of endocrine disrupting compounds (EDCs) with semi-volatile properties are emitted to indoor air and, thus, humans might get exposed to these compounds. Pet cats spend the major part of their lifetime at home and might integrate indoor contamination so that they could mirror the human exposure. Three classes of EDCs, polybromodiphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and phthalates (PAEs), were simultaneously considered and quantified in the serum of cats (Felis silvestris catus) living in the Paris area (France). The main compound concentrations by decreasing importance order were as follows: for PAEs, di-n-butyl phthalate (79,900 ng L(-1)) next di-iso-butyl phthalate (53,200 ng L(-1)), di-iso-nonyl phthalate (43,800 ng L(-1)), and di-ethylhexyl phthalate (32,830 ng L(-1)); for PCBs, CB153 (1378 ng L(-1)) next CB52 (509 ng L(-1)), CB101 (355 ng L(-1)), CB110 (264 ng L(-1)), and CB118 (165 ng L(-1)); and for PBDEs, BDE 153/154 (35 ng L(-1)) next BDE47 (10.7 ng L(-1)). Total serum concentrations as mean ± standard deviation were 107 ± 98 µg L(-1) for ∑9PAEs, 2799 ± 944 ng L(-1) for ∑19PCBs, and 56 ± 21 ng L(-1) for ∑9BDEs. The three chemical groups were found in cat food: 0.088 ng g(-1) for ∑9BDEs, 1.7 ng g(-1) for ∑19PCBs, and 2292 ng g(-1) for ∑9PAEs and in indoor air: 0.063 ng m(-3) for ∑9BDEs, 1.5 ng m(-3) for ∑19PCBs, and 848 ng m(-3) for ∑9PAEs. Contaminant intake by food ingestion was approximately 100-fold higher than that by indoor air inhalation.

A new analytical protocol for the determination of 62 endocrine-disrupting compounds in indoor air.

The objective of this study was to develop and validate a new analytical protocol for simultaneous determination of 62 semi-volatile organic compounds in both phases of indoor air. Studied compounds belong to several families: polybrominated diphenyl ethers, polychlorinated biphenyls, hexachlorobenzene, pentachlorobenzene, phthalates, polyaromatic hydrocarbons, parabens, tetrabromobisphenol A, bisphenol A, hexabromocyclododecane, triclosan, alkylphenols, alkylphenol ethoxylates, synthetic musks (galaxolide and tonalide) and pesticides (lindane and cypermethrin). A medium volume sampling system was used to collect simultaneously these endocrine-disrupting compounds (EDCs) from the gaseous and particulate phases. An accelerated solvent extraction method was optimized to obtain all EDCs in a single extract by atmospheric phase. Their extraction from the sorbents and their analysis by liquid and gas chromatography-mass spectrometry (LC/MS/MS, GC/MS and GC/MS/MS) was validated using spiked sorbents (recovery study and analytical uncertainty analysis by fully nested design). The developed protocol achieved low limits of quantification (<0.5ng m(-3)) and low uncertainty values (<5ng m(-3)) for all compounds. Once validated, the method was applied to indoor air samples from four locations (a house, an apartment, a day nursery and an office) and compared to literature to confirm its efficiency. All target EDCs were quantified in the samples and were primarily present in the gaseous phase. The major contaminants found in indoor air were, in descending order, phthalates, synthetic musks, alkylphenols and parabens.

Endocrine disrupting compounds in gaseous and particulate outdoor air phases according to environmental factors.

This study investigated, for the first time in France, the spatial and temporal patterns of 55 endocrine disrupting chemicals (EDCs) in ambient air at three sites (urban, suburban and forest) under two climatic periods (warm/cold) for 2 successive years. All EDCs, except tetrabromobisphenol A (TBBPA), were encountered with various frequencies of up to 100%. Phthalate diesters (PAEs) were the most abundant chemicals with total concentrations as the sum of compounds, ranging from 10 to 100 ng m(-3) of total air, followed by alkylphenols (APs) and polycyclic aromatic hydrocarbons (PAHs), which were both approximately 1 ng m(-3). Polychlorinated biphenyl (PCBs) and bisphenol A (BPA) concentrations were notably lower (approximately 0.1 ng m(-3)). Air concentrations, depending on the considered compounds, were from 1.2 to 2 times higher in the urban than the suburban area and from 2 to 5 times higher in the urban than the forest site. PAH emissions were higher in the cold period, due to combustion processes. This finding is contrary to the other EDCs that are more abundant in the summer and governed by volatilisation. Most of the EDCs were largely distributed in the gaseous phase (>80% in the summer). The octanol/air partition coefficient (KOA) and vapour pressure (Vp) were relevant parameters for predicting EDC partitioning and direct relationships (p < 0.001) were observed i) between log K particle/gas partitioning (log Kp) and log KOA and ii) between EDC ratios in the gaseous phase and log vapour pressure (log Vp).

Fate of phthalates and BPA in agricultural and non-agricultural soils of the Paris area (France).

This study (i) investigated the concentration levels of nine phthalates and bisphenol A (BPA) in sludge samples originating from a French wastewater treatment plant (WWTP), (ii) studied the distribution of target compounds according to soil depth and calculated their half-lives, and (iii) compared the contamination level of the agricultural soil with those of soils with other land uses. The sludge contamination levels varied from a few hundred nanograms per gram dry weight (dw) for diethyl phthalate (DEP), di-iso-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and butyl-benzyl phthalate (BBP) to a few micrograms per gram dw for diethylhexyl phthalate (DEHP), di-iso-nonyl phthalate (DiNP), and di-iso-decyl phthalate (DiDP). After sludge application, an 8-fold increase for DEHP level and a 3-fold increase for BPA level occurred in the surface horizon of the soil. The mean distribution of phthalates according to the depth showed a positive gradient for the low molecular weight compounds and inversely, a negative gradient for the highest ones. The half-lives in the 0-20-cm soil horizon were 64 days for DEHP and 36 days for BPA. A predictive environmental concentration (PEC) of 0.3 µg g(-1) dw was estimated for DEHP, while the experimental value was 0.16 µg g(-1) dw, suggesting degradation processes in soil and/or formation of non-extractable residues. Comparisons of contamination levels for soils from different origins (urban, rural, agricultural, and forest) showed that the urban soil remained the most contaminated one, prior to the agricultural soil after treatment.

BPA and phthalate fate in a sewage network and an elementary river of France. Influence of hydroclimatic conditions.

Our purpose was to characterize the fate of bisphenol A (BPA) and phthalate contamination simultaneously in a sewage network and a watercourse, in relation with hydrological and climatic conditions. An elementary catchment of the Seine basin, receiving effluents from a wastewater treatment plant (WWTP), was chosen because of its basic hydrological features. BPA and DEHP concentrations in the WWTP inputs were 4 and 33 µg L(-1) whereas in the outputs, they were only 0.4 and 2 µg L(-1), respectively. Contaminant ratios in the suspended sediment phase of the WWTP inputs ranged from 0.5% to 88%, related to their molecular properties. BPA and phthalates were effectively removed in the WWTP (>90% for both compounds), by degradation and decantation. Upstream of the discharge, river concentrations ranged from 0.002 to 0.175 µg L(-1) for BPA and from 0.16 to 0.90 µg L(-1) for DEHP. Downstream from the WWTP outputs, concentrations ranged from 0.11 to 0.79 µg L(-1) for BPA and from 0.31 µg L(-1) to 1.7 µg L(-1) for DEHP: the WWTP discharge led to contaminant increases of 3.8 and 2 times, respectively. Far downstream, concentrations were lower ranging from 0.11 to 0.19 µg L(-1) for BPA and from 0.36 µg L(-1) to 1.1 µg L(-1) for DEHP. BPA and phthalates displayed opposite seasonal variations with a decrease for the first one and an increase for the second one during summer. BPA contamination in the Charmoise river derived mainly from the WWTP, while phthalate contamination was attributed to both WWTP discharges and diffuse sources such as atmospheric bulk deposition.

Combining measurements and modelling to quantify the contribution of atmospheric fallout, local industry and road traffic to PAH stocks in contrasting catchments.

Various sources supply PAHs that accumulate in soils. The methodology we developed provided an evaluation of the contribution of local sources (road traffic, local industries) versus remote sources (long range atmospheric transport, fallout and gaseous exchanges) to PAH stocks in two contrasting subcatchments (46-614 km²) of the Seine River basin (France). Soil samples (n = 336) were analysed to investigate the spatial pattern of soil contamination across the catchments and an original combination with radionuclide measurements provided new insights into the evolution of the contamination with depth. Relationships between PAH concentrations and the distance to the potential sources were modelled. Despite both subcatchments are mainly rural, roadside areas appeared to concentrate 20% of the contamination inside the catchment while a local industry was found to be responsible for up to 30% of the stocks. Those results have important implications for understanding and controlling PAH contamination in rural areas of early-industrialized regions.

Polychlorinated biphenyls, polybrominated diphenyl ethers, and phthalates in roach from the Seine River basin (France): impact of densely urbanized areas.

Endocrine disruptors (EDs) from three chemical classes-polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and phthalates-were investigated in the Seine River and one tributary, the Orge River, upstream and downstream of urban areas. The impact of urban areas was characterized by a concentration increase of all compounds in the Seine River and for phthalates and PBDEs in the Orge River. In the Seine River, from upstream (Marnay) to downstream (Triel) of urban areas, water concentration increases were greater for diethylhexyl phthalate (DEHP) (6 times, p < 0.05) and ∑tri-hexa BDE (5 times [p < 0.05]) than for ∑7PCBi (2.6 times). Simultaneously, sediments displayed a strong accumulation of contaminants downstream and compared with upstream values, their concentrations increased greatly: 202-fold for DEHP, 69-fold for BDE209, 25-fold for ∑tri-hexa-BDE, and 11-fold for ∑7PCBi. Variations of fish ED concentrations gave an indication of their habitat contamination increase observed downstream of densely urbanized areas of the Seine River, especially for PBDEs (∑tri-hexa-PBDEs = 14-fold increase ≤15.7 ± 6.9 ng g(-1) dry weight [dw; p < 0.001]) and for PCBs (∑7PCBi eightfold increase ≤211 ± 55 ng g(-1) dw [p < 0.01]). PCA results highlighted relationships between the different ED classes. A correlation (p < 0.05) was observed between PCB and PBDE fish concentrations, suggesting common sources and similar absorption mechanisms. For PCBs, which were poorly biodegraded, the bioaccumulation factor was strongly correlated (p < 0.001) to molecular hydrophobicity, whereas for PBDEs a negative correlation (p < 0.05) was observed related active debromination processes. This multichemical study investigates for the first time the occurrence of a wide range of EDs in roach, which was chosen as a sentinel species for this survey of surface water contamination.

Mass balance and decontamination times of Polycyclic Aromatic Hydrocarbons in rural nested catchments of an early industrialized region (Seine River basin, France).

Accumulation of Polycyclic Aromatic Hydrocarbons (PAHs) in soils and their subsequent release in rivers constitute a major environmental and public health problem in industrialized countries. In the Seine River basin (France), some PAHs exceed the target concentrations, and the objectives of good chemical status required by the European Water Framework Directive might not be achieved. This investigation was conducted in an upstream subcatchment where atmospheric fallout (n=42), soil (n=33), river water (n=26) and sediment (n=101) samples were collected during one entire hydrological year. PAH concentrations in atmospheric fallout appeared to vary seasonally and to depend on the distance to urban areas. They varied between 60 ng·L(-1) (in a remote site during autumn) and 2,380 ng·L(-1) (in a built-up area during winter). PAH stocks in soils of the catchment were estimated based on land use, as mean PAH concentrations varied between 110 ng·g(-1) under woodland and 2,120 ng·g(-1) in built-up areas. They ranged from 12 to 220 kg·km(-2). PAH contamination in the aqueous phase of rivers remained homogeneous across the catchment (72 ± 38 ng·L(-1)). In contrast, contamination of suspended solid was heterogeneous depending on hydrological conditions and population density in the drainage area. Moreover, PAH concentrations appeared to be higher in sediment (230-9,210 ng·g(-1)) than in the nearby soils. Annual mass balance calculation conducted at the catchment scale showed that current PAH losses were mainly due to dissipation (biodegradation, photo-oxidation and volatilization) within the catchments (about 80%) whereas exports due to soil erosion and riverine transport appeared to be of minor importance. Based on the calculated fluxes, PAHs appeared to have long decontamination times in soils (40 to 1,850 years) thereby compromising the achievement of legislative targets. Overall, the study highlighted the major role of legacy contamination that supplied the bulk of PAHs that are still found nowadays in the environment.

Bages-Sigean and Canet-St Nazaire lagoons (France): physico-chemical characteristics and contaminant concentrations (Cu, Cd, PCBs and PBDEs) as environmental quality of water and sediment.

Environmental characteristics in water and sediments of two contrasted coastal Mediterranean lagoons, Bages-Sigean and Canet-St Nazaire, were measured over a three season survey. The urban pollution (treatment plant discharges) is very important in Canet-St Nazaire lagoon reflecting untreated sewages, while in Bages-Sigean, the northern part appears more impacted due to larger anthropogenic inputs. Dissolved Cd concentrations are on the whole similar in both lagoons, whereas Cu concentrations are by far higher in lagoon Canet-St Nazaire. Cu concentrations appear to be highly dependent on dissolved organic carbon whereas salinity seems to control Cd variations. Concerning the sediments, the confined northern part of lagoon Bages-Sigean shows organic carbon and total nitrogen enrichment whereas lipid concentrations are much higher in the Canet-St Nazaire lagoon. Cu complexation seems to be strongly related to organic matter as evidenced by the two significant positive relationships, on one hand between Cu and organic carbon, and on the other hand, between Cu and lipids. On the contrary, Cd concentrations appear to be mainly controlled by carbonates. PCBs and PBDEs were detected only in sediments and show relatively low concentrations compared to similar lagoon environments. Regarding the sediment quality guidelines, Cd, Cu and PCBs in both lagoons did not exceed any Probable Effect Concentration (PEC).

Identification of antimicrobial resistant bacteria in rivers: insights into the cultivation bias.

In the present study, the antimicrobial resistant (AR) bacteria were quantified and identified in different river samples using in parallel a culture-based approach and a culture-independent one. The objective was to evaluate the importance of the cultivation bias when studying antimicrobial resistance among environmental bacteria. Three different river samples covering a gradient of anthropic influence were tested and three different antimicrobial compounds were used as selective agents: amoxicillin, tetracycline and sulfamethoxazole. From a quantitative point of view, our results highlight the importance of the culture media used, as for the same sample and the same selective agent significant differences were observed in the counts of culturable AR bacteria depending on the culture media used. The identification of AR bacteria through culture or culture-independent methods put on evidence AR bacterial communities that differ dramatically: γ-proteobacteria and more specifically Aeromonadaceae dominated among the isolates while ß-proteobacteria (Comamonadaceae), dominated among the sequences obtained without culture. Altogether these results highlight the necessity to develop a methodological consensus preferably without culture, to approach this important topic in the coming years.

The effect of environmental and therapeutic concentrations of antibiotics on nitrate reduction rates in river sediment.

The use of antibiotics in both human and veterinary medicine has led to increased presence of these compounds and antibiotic resistance in the environment. In this study, the effect of low, environmentally relevant (mg L(-1)) concentrations of vancomycin (VA), flumequine (FLU), and sulfamethoxazole (SMX) on nitrate reduction rates was studied in river sediments. Nitrate reduction rates were determined by supplying intact sediments for several weeks with both nitrate and antibiotics (ng L(-1), µg L(-1), and mg L(-1) concentrations), including a non-amended control. Furthermore the concentrations of the three investigated antibiotics were measured in the initial (natural) sediments and the sediments supplied with the antibiotics. The antibiotic concentrations in the sediments decreased (on average 62% for FLU and 93% for SMX) during the experiments, indicating loss of antibiotics due to sorption or (bio) degradation. Nitrate reduction rates were not affected by environmental concentrations of VA, FLU and SMX. FLU and SMX only partially inhibited nitrate reduction rates at high, therapeutic concentrations by 41 and 39% respectively. The three tested antibiotics significantly enhanced the production of nitrite, an intermediate in dissimilatory nitrate reduction. Nitrite production increased 1.9 and 1.4 fold for environmental VA concentrations (107 and 187 µg L(-1) respectively), application of 58 mg L(-1) SMX resulted in a 7.5 fold increase and augmented 16 and 8.5 fold in the presence of respectively 13 µg L(-1) and 52 mg L(-1) FLU. Even though inhibition of nitrate reduction rates was observed at therapeutic antibiotic concentrations, nitrate reduction proceeded under all experimental conditions, indicating the presence of resistance toward these antibiotics among the nitrate reducing bacteria. The accumulation of nitrite suggests that the nitrite reduction step was more affected than the overall nitrate reduction process.

Bioaccumulation of polybrominated diphenyl ethers by the freshwater benthic amphipod Gammarus pulex.

This study reports on the relationship between polybrominated diphenyl ether (PBDE) levels in water, sediment, and the benthic macroinvertebrate Gammarus pulex, which plays a major ecological role in freshwater ecosystems. Samples were taken in a periurban watershed (near Paris, France), and PBDEs were systematically detected in sediment (≤727 ng g(-1) OC) and G. pulex (≤264 ng g(-1) lipids). PBDEs were also occasionally detected in the water column at low levels (∑ PBDEs < 1.5 ng L(-1)). The log values of bioaccumulation factors were in the range 7.8 ± 0.1-8.3 ± 0.4 L kg(-1) for tetra- and penta-BDEs, which were the only ones quantified in the dissolved phase of river water. Meanwhile, levels of individual tri- to hepta-PBDE congeners in G. pulex generally positively correlated with sediment levels, suggesting an equilibrium situation. Biota-to-sediment accumulation factors (BSAFs) of tri-hepta BDEs were congener specific and were in the range 0.5 ± 0.3-2.6 ± 1.2. For several PBDEs, BSAF values deviated from the expected range, likely because of in vivo metabolism.

Occurrence of polybrominated diphenyl ethers, polychlorinated biphenyls, and phthalates in freshwater fish from the Orge river (Ile-de France).

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and phthalates were investigated from July 2009 to April 2010 in three fish species from the Orge river, which flows in a densely populated area of Ile-de-France. In two Cyprinidae (roach and chub) and one Percidae (perch), muscle contents in increasing order ranged as follows: 12-18 ng g(-1) dw for PBDEs (Σtri-hepta), 120-170 ng g(-1) dw for PCBs (Σ7), and 2,250-5,125 ng g(-1) dw for phthalates (Σ7). No variation was observed between contaminant contents and lipid levels. No biomagnification was found according to the trophic level for PBDEs and PCBs, whereas for phthalates the highest contents were found in perch. Seasonal variations were observed with the lowest PBDE and PCB contents occurring in July after spawning in roach and perch (p < 0.001). PBDE content followed a decreasing trend-gonad > liver > muscle-whatever the period. For PCBs, gonad and liver contents remained greater than that of muscle (p < 0.05). Our results indicate a preferential accumulation of halogenated compounds in gonad and liver outside the reproduction period. Bioaccumulation factors for PCBs in muscle were significantly correlated to their chlorination degree in perch (p < 0.01) and roach (p < 0.01). In roach, that correlation slope was by decreasing importance order as follows: gonad > liver > muscle. The biota-sediment accumulation factors varied from 0.1 to 29.2, from 1.6 to 4.8, and from 1 to 123.5 for PBDEs, PCBs, and phthalates, respectively. These results contribute to document the use of freshwater fish as bioindicators of river quality.

Phyt'Eaux Cités: application and validation of a programme to reduce surface water contamination with urban pesticides.

This paper presents first results of Phyt'Eaux Cités, a program put in place by the local water supply agency, the SEDIF (Syndicat des Eaux d'Ile-de-France), in collaboration with 73 local authorities, private societies and institutional offices (365 km(2)). The challenges included: measurement of the previous surface water contamination, control of urban pesticide applications, prevention of pesticide hazard on users and finally a overall reduction of surface water contamination. An inquiry on urban total pesticide amount was coupled with a surface water bi-weekly monitoring to establish the impact of more than 200 molecules upon the Orge River. For 2007, at least 4400 kg and 92 type of pesticides (essentially herbicides) were quantified for all urban users in the Phyt'Eaux Cités perimeter. At the outlet of the Orge River (bi-weekly sampling in 2007), 11 molecules were always detected above 0.1 µg L(-1). They displayed the mainly urban origin of pesticide surface water contamination. Amitrole, AMPA (Aminomethyl Phosphonic Acid), demethyldiuron, diuron, glyphosate and atrazine were quantified with a 100% of frequency in 2007 and 2008 at the Orge River outlet. During the year, peaks of contamination were also registered for MCCP, 2,4 MCPA, 2,4 D, triclopyr, dichlorprop, diflufènican, active substances used in large amount in the urban area. However, some other urban molecules, such as isoxaben or flazasulfuron, were detected with low frequency. During late spring and summer, contamination patterns and load were dominated by glyphosate, amitrole and diuron, essentially applied by cities and urban users. Both isoproturon and chlortoluron were quantified during autumn and winter months according to upstream agricultural practices. In conclusion, 3 years after the beginning of this programme, the cities reduced the use of 68% of the total pesticide amount. An improvement on surface water quality was found from 2008 and during 2009 for all pesticides. In particular, glyphosate showed a decrease of the load above 60% in 2008, partly related to the Phyt'Eaux Cités action.

Influence of hydrological parameters on organohalogenated micropollutant (polybrominated diphenyl ethers and polychlorinated biphenyls) behaviour in the Seine (France).

The temporal dynamics of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were investigated in a heavily urbanized river (Seine River, Paris, France) from November 2009 to May 2010. Pollutant concentrations were in the range of 0.2 to 3.8 ng l(-1) (median 1.1) and 0.4 to 3.6 ng l(-1) (median 1.1) for ∑ tri-deca BDEs and ∑ 7PCBs, respectively. In addition, for both PBDEs and PCBs, the partitioning between the particulate and dissolved phases was investigated. Due to their low water solubility, PBDEs were mainly (>70%) bound to particles. In contrast, only 54% of ∑ 7PCBs occurred in the particulate phase, and their partitioning was influenced by the degree of chlorination. During the sampling period, PBDE/PCB fluxes were quite similar and ranged from 3 to 128 and from 6 to 125 g day(-1), respectively. The annual mass flow of PBDEs and PCBs was estimated to 10 kg for both. Contrary to PCBs and BDE-209, the temporal evolution of ∑ tri-hepta BDEs was related to particulate organic matter content, which is controlled by river flow variations. This suggests that they exhibit different sources or behavior in the Seine River.