Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

Sampling terrigenous diffuse sources in watercourse: Influence of land use and hydrological conditions on dissolved organic matter characteristics.

Diffuse and point sources of dissolved organic matter (DOM) in streams influence its composition, interactions and fate in the aquatic ecosystem. These inputs can be very numerous at the scale of a watershed, and their identification remains a challenge, especially for diffuse sources related to land use. The complexity of the transfer mechanisms and the reactivity of DOM throughout the soil-water column continuum raise questions about the sampling of diffuse sources in watercourses. To answer this issue, we compared the characteristics of soil-extracted DOM influenced by a particular land use (homogenous sub-catchment of forest and vineyard) and DOM collected from the watercourse adjacent to the soil samples. A 28-day incubation experiment of soil extracts was designed to remove the labile fraction of DOM. During the first 3 days, between 40 and 70 % of the DOC mass was lost for both types of soils. A set of optical indicators (UV-Visible, EEM fluorescence and HPSEC/UV-fluorescence) showed that the labile fraction was mostly composed by low (<1 kDa) and high (>10 kDa) protein-like molecules. At the end of the incubation, soil-extracted DOM was mainly composed of medium molecules (1-10 kDa) associated to terrigenous humic-like compounds. Its optical and size molecular signature tended towards that in the adjacent watercourses and was specific to land use. However, the characteristics of DOM in watercourses was also influenced by the hydrological conditions, probably due to a transfer of top soil DOM during high water periods and both deep soil and autochthonous DOM during low water periods. These results were obtained by a set of indicators, including novel ones derived from HPSEC/UV-fluorescence. Finally, this study demonstrated that it is possible to sample the DOM representative of a land use directly in the river downstream of the homogeneous sub-basin by multiplying the samples during contrasting hydrological conditions.

Calibration comparison between two passive samplers -o-DGT and POCIS- for 109 hydrophilic emerging and priority organic compounds.

The Polar Organic Chemical Integrative Samplers (POCIS) is the most widely used passive sampler for hydrophilic compounds, but unsuitable for certain ionic organic contaminants. The Diffusive Gradient in Thin-Film technique (o-DGT) has shown positive results for both ionic and hydrophilic compounds. However, a calibration step is now needed to evaluate kinetic constant of accumulation for a wide range of molecules. In this study, o-DGT and POCIS were compared for the sampling of three families of micropollutants of potential risk to aquatic environments: 53 pesticides, 36 pharmaceuticals and 20 hormones. A calibration experiment was conducted to compare the kinetic models and constants from a scientific and practical perspective. The results are discussed in a single table that summarizes the performance of both passive samplers for the 109 compounds of interest. The advantage of o-DGT is that it allows linear accumulation for 72 compounds versus only 33 with POCIS. The mean times to equilibrium obtained with o-DGT are higher than those obtained with POCIS. These results confirm that the presence of a diffusion gel delays the achievement of equilibrium during compound accumulation. Therefore, o-DGT can be considered for situations where POCIS cannot be used due to non-linear accumulation over a typical 14-day deployment period. However, overall sampling rates and mass transfer coefficients also appear reduced with o-DGT, which is explained by the smaller exchange surface area, as well as the consideration of an additional diffusive layer in this device. This paper also showed that the most appropriate membrane to sample polar compounds with o-DGT was a polyethersulfone polymer with a pore size of 5 µm.

Effect of a karst system (France) on extended spectrum beta-lactamase (ESBL)-producing Escherichia coli.

Karst aquifers are an important water resource worldwide particularly exposed to anthropogenic pollution, including antibiotic-resistance. The release of antibiotic-resistant bacterial pathogens in the environment is a major public health challenge worldwide. In this One Health study, we aimed to determine the effect of karst on antibiotic-resistant bacteria. For this purpose, we determined the concentrations of extended-spectrum ß-lactamases-producing Escherichia coli (ESBL-Ec) for 92 weeks in a rural karst hydrosystem providing drinking water. ESBL-Ec isolates (n = 130) were sequenced by whole genome sequencing. We analysed the isolates at different levels of granularity, i.e., phylogroup, sequence type, presence of antibiotic-resistance genes, mutations conferring antibiotic-resistance, and virulence genes. The ESBL-Ec concentrations were spatially and temporally heterogeneous in the studied karst hydrosystem. ESBL-Ec isolates survived in the karst and their concentrations were mostly explained by the hydrodynamic of the hydrosystem. We demonstrate that the studied karst has no filtration effect on ESBL-Ec, either quantitatively (i.e., in the ESBL-Ec concentrations) or qualitatively (i.e., in the genetic characteristics of ESBL-Ec isolates).

Determination of diffusion coefficients in agarose and polyacrylamide gels for 112 organic chemicals for passive sampling by organic Diffusive Gradients in Thin films (o-DGT).

The diffusive gradient in thin film technique was recently adapted to organic compounds. The diffusional coefficient (D) is a key parameter needed to calculate the time-weighted average concentration. In this study, two methods are used for D measurement in two gels (agarose and polyacrylamide): the diffusion cell method (Dcell) and the slice stacking method (Dstack). Thus, D were discussed and compared for 112 organic compounds, including pesticides, hormones, and pharmaceuticals. Dstack tends to be higher than Dcell. It could be explained by the presence of a non-negligible diffusive boundary layer thickness in diffusion cell. Consequently, the use of sampling rates (RS) should be more adequate to determine water concentration, for a given bulk flow velocity. Dstack also corresponds to the diffusion in gel only, allowing the determination of the maximal RS, and would be considered as a reference value that can be adjusted to in situ conditions, by applying the appropriate DBL thickness. The range and variability of D values found in the literature and obtained in this work were discussed. Relationships between D and compound physicochemical properties (molecular mass, log Dow, polar surface area, van der Waals volume) were investigated. We did not find clear and robust correlation between D and any single physicochemical property, for the set of compounds tested.

Inter-laboratory mass spectrometry dataset based on passive sampling of drinking water for non-target analysis.

Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using one pre-defined method and one locally (i.e. in-house) developed method. The data generated represents a valuable resource (i.e. benchmark) for future developments of algorithms and workflows for NTA experiments.

A pilot experiment to assess the efficiency of pharmaceutical plant wastewater treatment and the decreasing effluent toxicity to periphytic biofilms.

Pharmaceutical industry effluents are complex and highly variable in time. Assessing the efficiency of a pharmaceutical industry wastewater treatment plant (WWTP) and the resulting decrease in effluent toxicity and ecological risk is thus not straightforward. We set up an original in situ pilot directly connected to a pharmaceutical WWTP to monitor the chronic toxicity of successive effluents using natural periphytic biofilms. Their structural and functional responses to effluent exposure were assessed by combining (i) a molecular approach to characterize the bacterial and diatom diversity and (ii) functional measurements of photosynthetic and enzyme activities. Effluent contamination by pharmaceuticals strongly decreased after the quaternary treatment (activated carbon). Most of the structural biological characteristics improved with cumulative WWTP treatment (bacterial diversity, microbial genetic structure, and biological diatom index), showing community recovery along the treatment process. However, functional parameters did not show clear links with treatment steps, suggesting that microbial activities were not solely driven by pharmaceuticals produced during the experimental period. Operationally, this type of pilot system offers a useful tool for biomonitoring approaches and offers new approaches for industrial managers to assess the ecological risk of production effluents in receiving water.

Role of Biofilms in Contaminant Bioaccumulation and Trophic Transfer in Aquatic Ecosystems: Current State of Knowledge and Future Challenges.

In freshwater environments, microbial assemblages attached to submerged substrates play an essential role in ecosystem processes such as primary production, supported by periphyton, or organic matter decomposition, supported by microbial communities attached to leaf litter or sediments. These microbial assemblages, also called biofilms, are not only involved in nutrients fluxes but also in contaminants dynamics. Biofilms can accumulate metals and organic contaminants transported by the water flow and/or adsorbed onto substrates. Furthermore, due to their high metabolic activity and their role in aquatic food webs, microbial biofilms are also likely to influence contaminant fate in aquatic ecosystems. In this review, we provide (1) a critical overview of the analytical methods currently in use for detecting and quantifying metals and organic micropollutants in microbial biofilms attached to benthic substrata (rocks, sediments, leaf litter); (2) a review of the distribution of those contaminants within aquatic biofilms and the role of these benthic microbial communities in contaminant fate; (3) a set of future challenges concerning the role of biofilms in contaminant accumulation and trophic transfers in the aquatic food web. This literature review highlighted that most knowledge on the interaction between biofilm and contaminants is focused on contaminants dynamics in periphyton while technical limitations are still preventing a thorough estimation of contaminants accumulation in biofilms attached to leaf litter or sediments. In addition, microbial biofilms represent an important food resource in freshwater ecosystems, yet their role in dietary contaminant exposure has been neglected for a long time, and the importance of biofilms in trophic transfer of contaminants is still understudied.

Direct photodegradation of 36 organic micropollutants under simulated solar radiation: Comparison with free-water surface constructed wetland and influence of chemical structure.

Micropollutants such as pharmaceuticals and pesticides are still found in treated municipal effluent and are discharged into the natural environment. Natural direct photodegradation may be one pathway for removing these micropollutants in treatment processes such as free-water surface constructed wetlands (CW). This work was set out to evaluate the half-life (t1/2) of direct photodegradation of 36 micropollutants under controlled conditions of light exposure close to solar radiation. The results allowed to classify the micropollutants into three groups (fast, medium and slow). Seven micropollutants were classified in the fast group with t1/2 between 0.05 h and 0.79 h, 24 in the medium group with t1/2 between 5.3 h and 49.7 h, and five in the slow group with t1/2 between 56 h and 118 h. The t1/2 values obtained in laboratory were compared with those from a CW receiving treated wastewater. Correction factors were calculated to adjust the in situ data for the light intensity in laboratory and improved the correspondence especially for the micropollutants of the fast and medium groups. Finally, an innovative method based on statistical tests highlighted the chemical functions characteristic of micropollutants sensitive to photodegradation (OH-CË­O, CË­N-O-, =N-OH, -CH=N, -O-PË­O, -CË­C-) and with low sensitivity (-O-R, -Cl).

Hydro-climatic drivers of land-based organic and inorganic particulate micropollutant fluxes: The regime of the largest river water inflow of the Mediterranean Sea.

Land-based micropollutants are the largest pollution source of the marine environment acting as the major large-scale chemical sink. Despite this, there are few comprehensive datasets for estimating micropollutant fluxes released to the sea from river mouths. Hence, their dynamics and drivers remain poorly understood. Here, we address this issue by continuous measurements throughout the Rhône River basin (∼100,000 km2) of 1) particulate micropollutant concentrations (persistant organic micropollutants: polychlorobiphenyls [PCBi] and polycyclic aromatic hydrocarbons [PAHs]; emerging compounds: glyphosate and aminomethylphosphonic acid [AMPA]; and trace metal elements [TME]), 2) suspended particulate matter [SPM], and 3) water discharge. From these data, we computed daily fluxes for a wide range of micropollutants (n = 29) over a long-term period (2008-2018). We argue that almost two-thirds of annual micropollutant fluxes are released to the Mediterranean Sea during three short-term periods over the year. The watershed hydro-climatic heterogeneity determines this dynamic by triggering seasonal floods. Unexpectedly, the large deficit of the inter-annual monthly micropollutant fluxes inputs (tributaries and the Upper Rhône River) compared to the output (Beaucaire station) claims for the presence of highly contaminated missing sources of micropollutants in the Rhône River watershed. Based on a SPM-flux-averaged micropollutant concentrations mass balance of the system and the estimates of the relative uncertainty of the missing sources concentration, we assessed their location within the Rhône River catchment. We assume that the potential missing sources of PAHs, PCBi and TME would be, respectively, the metropolitan areas, the alluvial margins of the Rhône River valley, and the unmonitored Cevenol tributaries.

Impact of dam flushing operations on sediment dynamics and quality in the upper Rhône River, France.

The Rhône River (France) has been used for energy production for decades and 21 dams have been built. To avoid problems due to sediment storage, dam flushing operations are periodically organized. The impacts of such operations on suspended particulate matter (SPM) dynamics (resuspension and fluxes) and quality (physico-chemical characteristics and contamination), were investigated during a flushing operation performed in June 2012 on 3 major dams from the Upper Rhône River. The concentrations of major hydrophobic organic contaminants (polychlorinated biphenyls, polycyclic aromatic hydrocarbons - PAHs, bis(2-ethylhexyl)phthalate [DEHP] and 4-n-nonylphenol), trace metal elements, particulate organic carbon (POC) and particle size distribution were measured on SPM samples collected during this event as well as on those obtained from 2011 to 2016 at a permanent monitoring station (150 km downstream). This allows to compare the SPM and contaminant concentrations and fluxes during the 2012 dam flushing operations with those during flood events and baseflow regime. At equal water discharge, mean SPM concentrations during flushing were on average 6-8 times higher than during flood events recorded from 2011 to 2016. While of short duration (19 days), the flushing operations led to the resuspension of SPM and contributed to a third of the mean annual SPM flux. The SPM contamination was generally lower during flushing than during baseflow or flood, probably due to the fact that flushing transports SPM only issued from resuspended sediment, with no autochtonous particles nor eroded soil. The only exception are PAHs and DEHP with higher concentrations during flushing, which must be issued from the resuspension of legacy-contaminated sediments stored behind the dams before the implementation of emission regulations. During flushing, the variations of POC and contaminant concentrations are also mostly driven by particle size. Finally, we propose a list of recommendations for the design of an adequate monitoring network to evaluate the impact of dam flushing operations on large river systems.

Kinetic accumulation processes and models for 43 micropollutants in "pharmaceutical" POCIS.

The "pharmaceutical" polar organic integrative sampler (POCIS) is a passive sampler composed of an outer polyethersulfone (PES) membrane and an inner receiving Hydrophilic-Lipophilic Balance (HLB) phase. Target micropollutants can accumulate in the POCIS HLB phase following different uptake patterns. Two of the most common ones are a first-order kinetic uptake (Chemical Reaction Kinetic 1, CRK1 model), and a first-order kinetic uptake with an inflexion point (CRK2 model). From a previous study, we identified 30 and 13 micropollutants following CRK1 and CRK2 accumulation model in the POCIS HLB phase, respectively. We hypothesized that uptake in the outer PES membrane of POCIS may influence the uptake pathway. Thus, novel measurements of uptake in PES membrane were performed for these micropollutants to characterise kinetic accumulation in the membrane with and without the HLB phase. We determined, for the first time, the membrane-water distribution coefficient for 31 micropolluants. Moreover, the lag times for molecules to breakthrough the POCIS membrane increased with increasing hydrophobicity, defined by the octanol-water dissociation constant Dow. However, Dow alone was insufficient to predict whether uptake followed a CRK1 or CRK2 model in the POCIS HLB phase. Thus, we performed a factorial discriminant analysis considering several molecular physico-chemical properties, and the model of accumulation for the studied micropollutants can be predicted with >90% confidence. The most influent properties to predict the accumulation model were the log Dow and the polar surface area of the molecule (>70% confidence with just these two properties). Molecules exhibiting a CRK1 uptake model for the POCIS HLB phase tended to have log Dow>2.5 and polar surface area <50Ǻ2.

Removal efficiencies and kinetic rate constants of xenobiotics by ozonation in tertiary treatment.

This study gives a full overview of the chemical oxidation by ozone of selected xenobiotics usually present in effluents of conventional wastewater treatment plants. A qualitative and quantitative overview of literature data was made, and describes the ozonation efficiency and processes for the elimination of 12 xenobiotics (pesticides and pharmaceuticals). A database was built, compiling literature results of experimental ozonation assays in laboratory and real-scale conditions. Special attention was paid to selecting the data and compiling reliable results on removal efficiencies and kinetic parameters. An original study was performed in a semi-batch reactor applying ozone on secondary effluent spiked beforehand with a cocktail of 12 xenobiotics. The results of this study were compared with the literature data to evaluate the influence of the kinetic competition of xenobiotics in spiked wastewater in the determination of kinetic rate constants. These 12 xenobiotics were classified into three groups (high-/medium-/low-oxidizable) according to the ranges of their direct kinetic rate constants (kO3). A best effective ozone dose between 0.2 and 0.4 gO3 gDOC-1 is proposed for the elimination of xenobiotics. The predominant elimination pathway between direct and indirect oxidation was identified for each xenobiotic.

Rethinking micropollutant removal assessment methods for wastewater treatment plants - how to get more robust data?

This paper covers the pitfalls, recommendations and a new methodology for assessing micropollutant removal efficiencies in wastewater treatment plants. The proposed calculation rules take into account the limit of quantification and the analytical and sampling uncertainty of measured concentrations. We identified six cases for which a removal efficiency value is reliable and four other cases where result is highly variable (uncertain) due to very low or unquantified concentrations in effluent or when the influent-effluent concentrations differential is below the measurement uncertainty. The influence of the proposed calculation rules on removal efficiency values was scrutinized using actual results from a research project. The paper arrives at detailed recommendations for limiting the impact of other sources of uncertainty during sampling (sampling strategy, cleaning and field blank), chemical analyses (suspended solids and sludge) and data processing according to the targeted objectives.

A review of the photodegradability and transformation products of 13 pharmaceuticals and pesticides relevant to sewage polishing treatment.

Many xenobiotics are only partially treated by conventional wastewater treatment plants. Photodegradation is one promising solution currently being investigated to improve their removal from effluents. We present an in-depth review of the photodegradation kinetic parameters of selected pesticides and pharmaceuticals and assess whether the data available in the literature are applicable to polishing treatment processes under sunlight. We made a thorough inventory of literature data describing the photodegradation of pesticides and pharmaceuticals in water, the laboratory, pilot plants, and in situ conditions. To this end, we built a database compiling results on photodegradation experiments from 70 scientific publications covering 13 xenobiotics commonly found in secondary effluents. Special care was taken to compile reliable data on photolysis kinetic parameters (half-life and kinetic rate constant) and removal efficiencies. We also include a comprehensive description of experimental operating conditions and an up-to-date inventory of known phototransformation products. As practical outputs we (i) propose a classification for the xenobiotics according to their photodegradability: fast-, medium- and slow-photodegradable, (ii) compare kinetic parameters in direct and indirect photodegradation conditions, and (iii) list 140 phototransformation products formed by direct or indirect photodegradation. We conclude by identifying gaps in the literature that need to be filled to adapt these available results to the conditions of polishing processes.

Prediction of the Fate of Organic Compounds in the Environment From Their Molecular Properties: A Review.

A comprehensive review of quantitative structure-activity relationships (QSAR) allowing the prediction of the fate of organic compounds in the environment from their molecular properties was done. The considered processes were water dissolution, dissociation, volatilization, retention on soils and sediments (mainly adsorption and desorption), degradation (biotic and abiotic), and absorption by plants. A total of 790 equations involving 686 structural molecular descriptors are reported to estimate 90 environmental parameters related to these processes. A significant number of equations was found for dissociation process (pKa), water dissolution or hydrophobic behavior (especially through the KOW parameter), adsorption to soils and biodegradation. A lack of QSAR was observed to estimate desorption or potential of transfer to water. Among the 686 molecular descriptors, five were found to be dominant in the 790 collected equations and the most generic ones: four quantum-chemical descriptors, the energy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecular orbital (ELUMO), polarizability (α) and dipole moment (µ), and one constitutional descriptor, the molecular weight. Keeping in mind that the combination of descriptors belonging to different categories (constitutional, topological, quantum-chemical) led to improve QSAR performances, these descriptors should be considered for the development of new QSAR, for further predictions of environmental parameters. This review also allows finding of the relevant QSAR equations to predict the fate of a wide diversity of compounds in the environment.

Comparison of five integrative samplers in laboratory for the monitoring of indicator and dioxin-like polychlorinated biphenyls in water.

This study aimed at evaluating and comparing five integrative samplers for the monitoring of indicator and dioxin-like polychlorinated biphenyls (PCBs) in water: semi-permeable membrane device (SPMD), silicone rubber, low-density polyethylene (LDPE) strip, Chemcatcher and a continuous-flow integrative sampler (CFIS). These samplers were spiked with performance reference compounds (PRCs) and then simultaneously exposed under constant agitation and temperature in a 200 L stainless steel tank for periods ranging from one day to three months. A constant PCB concentration of about 1 ng·L(-1) was achieved by immersing a large amount of silicone rubber sheets ("dosing sheets") spiked with the target PCBs. The uptake of PCBs in the five samplers showed overall good repeatability and their accumulation was linear with time. The samplers SPMD, silicone rubber and LDPE strip were the most promising in terms of achieving low limits of quantification. Time-weighted average (TWA) concentrations of PCBs in water were estimated from uptake of PCBs using the sampling rates calculated from the release of PRCs. Except for Chemcatcher, a good agreement was found between the different samplers and TWA concentrations ranged between 0.4 and 2.8 times the nominal water concentration. Finally, the influence of calculation methods (sampler-water partition coefficients, selected PRCs, models) on final TWA concentrations was studied.

Determination of uptake kinetics and sampling rates for 56 organic micropollutants using "pharmaceutical" POCIS.

The literature increasingly reports sampling rates (Rs) for Polar Organic Chemical Integrative Samplers (POCIS) but the data obtained come from various calibration systems that are not always well-defined (agitation, temperature, measured micropollutant concentrations in water,…). In order to obtain accurate laboratory Rs for priority and emerging substances, POCIS need to be exposed in a robust and well-defined calibration system. Thus, we built a flow-through calibration system containing tap water spiked with 56 organic micropollutants (alkylphenols and phenols, hormones, pesticides, pharmaceuticals, UV filter). POCIS were immersed for up to 28 days. Tap water micropollutant concentrations and additional parameters (temperature, pH, conductivity, dissolved organic carbon, flow velocities) were kept constant and controlled throughout the calibration experiment. Based on the observed uptake kinetics, we distinguished four types of micropollutant accumulation patterns: curvilinear accumulation (30 molecules, group 1), accumulation with an inflexion point (13 molecules, group 2), random accumulation (eight molecules, group 3), and no or very low accumulation (five molecules, group 4). Rs was calculated for 43 out of 56 micropollutants (groups 1 and 2). Calculated Rs values ranged from 0.030 L/d to 0.398 L/d. POCIS can supply TWA concentrations for hormones, pesticides, several pharmaceuticals, a few alkylphenols, and the UV filter. Our Rs results are generally less than two fold-different (higher or lower depending on target molecule) to the literature data using the same type of calibration system or for micropollutants with log Kow>2.65. We found a quadratic correlation between Rs and log D for betablockers, herbicides and hormones.

Spatial and temporal trends in PCBs in sediment along the lower Rhône River, France.

Despite increasingly strict control of polychlorinated biphenyl (PCB) releases in France since the mid-1970s, PCB contamination of fish recently has emerged as a major concern in the lower Rhône River basin. We measured PCB concentrations in Rhône sediment to evaluate the effects of PCB releases from major urban and industrial areas, sediment redistribution by large floods, and regulatory controls on PCB trends from 1970 to present. Profiles of PCBs (the sum of seven indicator PCB congeners) were reconstructed from sediment cores collected from an off-river rural reference site and from three depositional areas along the Rhône upstream and downstream from the city of Lyon, France. Core chronology was determined from radionuclide profiles and flood deposits. PCB concentrations increased progressively in the downstream direction, and reached a maximum concentration in 1991 of 281 µg/kg at the most downstream site. At the rural reference site and at the upstream Rhône site, PCB concentrations peaked in the 1970s (maximum concentration of 13 and 78 µg/kg, respectively) and have decreased exponentially since then. PCB concentrations in the middle and downstream cores were elevated into the early 1990s, decreased very rapidly until 2000, and since then have remained relatively stable. Congener profiles for three time windows (1965-80, 1986-93, and 2000-08) were similar in the three sediment cores from the Rhône and different from those at the rural reference site. The results indicate that permitted discharges from a hazardous-waste treatment facility upstream from Lyon might have contributed to high concentrations into the 1980-90s, but that industrial discharges from the greater Lyon area and tributaries to the Rhône near Lyon have had a greater contribution since the 1990s. There is little indication that PCB concentration in sediments downstream from Lyon will decrease over at least the short term.

Evaluating the polar organic chemical integrative sampler for the monitoring of beta-blockers and hormones in wastewater treatment plant effluents and receiving surface waters.

Wastewater treatment plants (WWTP) are known to be a source of surface water contamination by organic compounds such as pharmaceuticals. The objective of the present work was to study the suitability of the polar organic chemical integrative sampler (POCIS) to monitor beta-blockers and hormones in effluents and surface waters. Four sampling campaigns were carried out in French rivers (the Saône, the Ardières, the Bourbre, and the Seine) between November 2007 and September 2008. Passive samplers were exposed in surface waters, upstream and downstream of WWTP outflows, and in effluents. Exposures lasted for up to 24 d to study the uptake kinetics directly in situ, and repeatability was assessed by exposure of triplicates. A good agreement was found between POCIS and water samples. With the exception of atenolol, beta-blockers showed a linear uptake during at least three weeks, and their sampling rates could be determined in situ. These sampling rates were then used to calculate time-weighted average concentrations of beta-blockers in the Seine River with an overall good accuracy and repeatability. Such calculations could not be performed for hormones because of their variable occurrences and low concentrations in water and POCIS. Polar organic chemical integrative sampler therefore seems to be a suitable tool for monitoring beta-blockers in surface waters impacted by WWTP effluents. Longer exposure durations would be necessary to determine the suitability of POCIS for monitoring hormones. Finally, preliminary assays on the use of several deuterated compounds as performance reference compounds showed promising results for deuterated atenolol.