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International audience; 2,4,6-tribromophenol (TBP) is implied in the production of brominated flame retardants but is also a major chlorination by-product in seawater. A growing number of studies indicate that TBP is highly toxic to the marine biota, but the contribution of anthropogenic sources among natural production is still under question concerning its bioaccumulation in marine organisms. Here, several water sampling campaigns were carried out in the industrialized Gulf of Fos and clearly showed the predominant incidence of industrial chlorination discharges on the TBP levels in water, at the 1-10 ng L-1 level in average and reaching up to 580 ng L-1 near the outlets. The bioaccumulation of TBP was measured in 90 biota samples of the Gulf of Fos. The concentrations found in European conger muscle tissues (140 to 1000 ng g-1 lipid weight, in average), purple sea urchin gonads (830 to 880 ng g-1 lipid weight, in average), and Mediterranean mussel body (1500 to 2000 ng g-1 lipid weight, in average) were above all published references. Significant correlations with fish length (European conger) and gonad somatic index (purple sea urchin) were also identified. Comparatively, fish, urchins and mussels from other Mediterranean sites analyzed within this study showed a lower bioaccumulation level of TBP, consistently with what found elsewhere. Industrial outflows were thus identified as hotspots for TBP in seawater and marine organisms. The environmental risk assessment indicated a high potential toxicity in the industrial Gulf of Fos, in particular near the outlets, and a limited threat to human but toxicological references are lacking.

International audience; This study explores how chemical and microbial properties of litters can be affected by coastal environments across the Mediterranean basin. A litterbag experiment including Pinus halepensis Mill. and Pistacia lentiscus L., collected from both inland and coastal areas was set up in France, Greece and Algeria. Control litterbags were left in their sampling sites and a transfer of litterbags from inland to coastal area was performed to test whether the effect of the specific constraints of coastal environments varies according to the country and the litter type. After 10 months, litter chemical composition (CP/MAS 13 C-NMR) and microbial activities (cellulase, respiration, Biolog) and structure (TRFLP) were analysed. Coastal conditions led to various responses: i) litter aromaticity differed in the coastal zones depending on the country (high in Greek coastal area, low in Algerian coastal zone), ii) less functionally-diversified microbial communities were found in Greek coastal area compared to French and Algerian coasts, iii) genetic diversity and richness were strongly impacted after transfer to the coastal zone whatever the country. The type of litter shaped microbial communities: i) at a local scale i.e. in either coastal or inland area, catabolic profiles and cellulase activities varied with the plant species, ii) at a regional scale, the effect of coastal conditions differed with the plant species (basal respiration, Shannon-Weaver index, catabolic diversity H', cellulases and catabolic profiles). Thus, litter microbial properties differed in coastal environments across the Mediterranean basin and plant litter type plays a major role in microbial properties at large spatial scale.

International audience; This study highlights the trace metal and metalloid (TMM) accumulation in Rosmarinus officinalis L. and its chemical responses when exposed to high levels of contamination. R. officinalis individuals growing along a gradient of mixed TMM soil pollution, resulting from past industrial activities, were analysed. Several plant secondary metabolites, known to be involved in plant tolerance to TMM or as a plant health indicator, were investigated. The levels of thiol compounds and phytochelatin precursors (cysteine and glutathione) in the shoots were measured in the laboratory, while a portable non-destructive instrument was used to determine the level of phenolic compounds and chlorophylls directly on site. The level of Pb, As, Sb and Zn contaminations within the soil and plants was also determined.The results highlighted a decrease of TMM translocation with increases of soil contamination. The concentration of TMM in the shoots followed the Mitscherlich equation and reached a plateau at 0.41, 7.9, 0.37, 51.3 mg kg−1 for As, Pb, Sb and Zn, respectively. In the shoots, the levels of thiols and phenols were correlated to concentrations of TMM. Glutathione seems to be the main thiol compounds involved in the tolerance to As, Pb and Sb. Phenols indices, using non-destructive measurements, may be considered as an easy way to establish a proxy to estimate the TMM contamination level of the R. officinalis shoots. The study highlights metabolic processes that contribute to the high potential of R. officinalis for phytostabilisation of TMM in contaminated areas in the Mediterranean.

International audience; The spatial distribution patterns, origins and environmental and health risks of metal trace elements (As, Cd, Co, Cr, Cu, Ni, Pb, Zn) have been analyzed through the spiking and the analysis of 84 soils sampled in the region of Arzew (Algeria). This city gathers one of the biggest petroleum harbors of Algeria and gathers in the same platform several industries, coexisting with residential and agricultural areas. The mean concentration of all the metals studied exceed their corresponding backgrounds levels and/or exceed the ecological Predicted No effect Concentration (PNEC) values. The geo-accumulation and the potential ecological risk indices indicate a low to moderate risk for As, Co, Cu, Ni and Zn, and a moderate to considerable risk for Cr and Pb. According to the health risk assessment results, the carcinogenic risks due to Cr exceed the acceptable level in all the functional areas, and when considering combined effects of metals, the hazard index obtained show a high potential carcinogenic risk to the local children.

International audience; Chlorination of seawater is one of the most effective technologies for industrial biofouling control. However, chlorination leads to the formation of halogenated chlorination byproducts (CBPs) associated with potential risks to environmental and human health. The present study investigated the occurrence and distribution of CBPs in the Gulf of Fos, a semi-enclosed bay where chlorinated effluents of multiple industrial plants are discharged. Seawater samples (surface and bottom) were collected at 24 sampling stations, with some near industrial outlets and others dispersed throughout the bay. Sediment samples were also collected at 10 sampling stations. Physicochemical parameters including water temperature, pH, salinity, bromide content, and free and total residual oxidant were determined. Several chemical classes of CBPs including trihalomethanes, haloacetic acids, haloacetonitriles, trihaloacetaldehydes, and halophenols were analyzed. Bromoform was the most abundant CBP in seawater, and it was detected at most of the sampling stations of the bay with highest concentrations occurring near the industrial effluent outlets. Dibromoacetic acid was the second most abundant CBP at most of the sites followed by dibromoacetonitrile. Other detected CBPs included tribromoacetic acid, bromochloroacetonitrile, and bromal hydrate. To our knowledge, the concentration of the latter CBP was reported here for the first time in the context of industrial seawater chlorination. In sediments, two bromine-containing halophenols (2-chloro-4-bromophenol and 2,4,6-tribromophenol) were detected at two sampling stations. Ecotoxicological assays and risk assessment studies based on the detected environmental concentrations are warranted to elucidate the impacts of marine CBP contamination.

In this paper, a new thin-layer chromatography (TLC) method for the determination of individual volatile fatty acids (VFAs) is presented. The experimental procedure is based on the derivatization of VFAs with activating agents and a naphthalene-based amine to form an amide derivative, followed by fast TLC separation of these VFA derivatives and visualization with phosphomolybdic acid at room temperature. Quantification is then performed by densitometric measurements using free software after taking TLC pictures in a home-made black box for homogeneous and reproducible lighting of the plates. Optimization of the experimental conditions enables fast determination (20 minutes for 3 samples) of VFAs with detection limits (1.5–2.5 mg L−1) and relative standard deviations (4.6–6.7%) satisfactory enough for our analytical purpose using low-cost instruments with easy to find materials and software. The protocol was then applied to real samples (aqueous extracts of sewage sludge composts) and the results were compared with gas chromatography analysis with good agreement between the two methods.

International audience; Water chlorination is the most widely used technique to avoid microbial contamination and biofouling. Adding chlorine in bromide-rich waters leads to the rapid oxidation of bromide ions and leads to the formation of brominated disinfection by products (bromo-DBPs) that exert adverse effects on various biological models. Bromo-DBPs are regularly encountered within industrialized embayments, potentially impacting marine organisms. Of these, bromoform, tribromoacetic acid and tribromophenol are among the most prevalent. In the present study, we tested the potential toxicity and genotoxicity of these disinfection by-products, using sea urchin, Paracentrotus lividus, embryos. We highlighted that tribromophenol showed higher toxicity compared to bromoform and tribromoacetic acid. Furthermore, a synergistic effect was detected when tested in combination. Pluteus cells exposed for 1h to mixtures of DPBs at several concentrations demonstrated significant DNA damage. Finally, when compared to a non-exposed population, sea urchins living in a bromo-DPB-polluted area produced more resistant progenies, as if they were locally adapted. This hypothesis remains to be tested in order to better understand the obvious impact of bromo-DBPs environments on marine wildlife.

International audience; 9 In this paper, a new spectrofluorimetric method for the determination of nitrate in aqueous 10 compost extracts is presented. The microplate procedure is based on the reduction of nitrate 11 to ammonium by means of Zn powder under acidic conditions and the following derivatization 12 of ammonium with o-phtaladehyde (OPA) and N-acetylcysteine (NAC) to give a fluorescent 13 derivative. Optimization work allowed performing the reduction in 30 min on a small sample 14 volume (150 µL) and using a little quantity of metal (20 mg). The use of strong acids is also 15 avoided. Excellent limit of detection was achieved (1.3 µM = 0.08 mg.L-1 NO3-) along with good 16 precision levels (4.2 and 14.3 % for 50 and 5 µM, respectively) and a satisfactory linear 17 dynamic range (4-100 µM). A good agreement between data coming from our method and 18 from ion-exchange chromatography was found on real compost samples, indicating a good 19 level of accuracy. 20 21 22

International audience; Abbreviations: Br-DPBs (brominated disinfection by-products); CHBr 3 (bromoform); CHCl 3 (chloroform), CHCl 2 Br (dichlorobromomethane), CHClBr 2 (dibromochloromethane); Clf (free residual chlorine); NPOC (Non Purgeable Organic Carbon); PCA (Principal Component Analysis); T water (temperature of water); T air (temperature of air); TTHMs (total trihalomethanes = sum of THM-4); Abstract Water and air quality of eight seawater swimming pools using chlorine disinfection was measured during four sampling campaigns, spread on one full-year, and in four thalassotherapy centres located in Southeast of France. Concentrations of trihalomethanes (THMs) in air and in water as well as concentrations of parameters, including non purgeable organic carbon (NPOC), free residual chlorine (Cl f), pH, Kjeldhal Nitrogen (KN), salinity, conductivity, bromide ions and, water and air temperature, were measured. Water and air samples were collected in triplicates morning-at the opening of the pools-, noon and night-at the closing of the pools-, in summer and winter. Data analysis was performed by Principal Component Analysis (PCA) and rotated component matrix, from both data quality and other parameters such as TOC, aromaticity (UV 254), pH, hygrometry, and free residual chlorine (Cl f). This statistical analysis demonstrates a high correlation between TOC, Cl f and UV 254 and THM levels found in air and water, particularly for the major ones (CHBr 3 in water : 300.0 µg.L-1 mean, 1029.0 µg.L-1 maximum; CHBr 3 in air : 266.1 µg.m-3 mean, 1600.0 µg.m-3 maximum, and CHClBr 2 in water: 18.9 µg.L-1 mean, 81.0 µg.L-1 maximum; CHClBr 2 in air : 13.6 µg.m-3 mean, 150.0 µg.m-3 maximum). These high levels of bromoform (CHBr 3) are particularly worrisome in such health institutions, even these levels do not exceed the Permissible Exposure Limit (PEL) of 5 mg.m-3 as an 8 hour time-weighted average currently 2 fixed by various administrations, such as Occupational Safety and Health Administration (OSHA).

International audience; An undesirable consequence of disinfection is the formation of chemical contaminants known as disinfection byproducts (DBPs). Chronic exposure to DBPs has been linked to adverse health effects. The occurrence of DBPs in chlorinated pools filled with seawater (such as thalassotherapy pools and pools in spas) has received little attention so far. The present study evaluated the speciation and levels of disinfection byproducts in indoor swimming pools filled with seawater and treated with chlorine. Water and air samples were collected from three indoor swimming pools located in Southern France. Several classes of DBPs including trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetaldehydes were analyzed in water. Halogenated volatile organic compounds were analyzed in air. Extractable organic halide (EOX) contents were determined using combustion micro-coulometry system. The speciation of DBPs identified in the three pools was predominantly brominated. The mean (arithmetic) concentration of bromoform, dibromoacetic acid, tribromoacetic acid, dibromoacetonitrile and bromal hydrate in the three pools were 79.2, 72.9, 59.9, 26.9 and 10.0 µg/L, respectively. By weight, HAAs represented the most abundant chemical class followed by THMs. In air, bromoform was the most abundant THM occurring at a mean concentration of 133.2 µg/m 3 in the three pools. The mean EOX level was 706 µgCl-/L for the three pools. In average, the quantified DBPs accounted for only 14% of EOX, thus 86% of EOX remained unknown. Further research is warranted to identify the unknown DBPs.

International audience; Disinfection treatments are critical to conserve the microbiological quality of swimming pool water and to prevent water-borne infections. The formation of disinfection byproducts (DBPs) in swimming pools is an undesirable consequence resulting from reactions of disinfectants (e.g. chlorine) with organic and inorganic matter present in pool water, mainly brought by bathers. A considerable body of occurrence studies has identified several classes of DBPs in swimming pools with more than 100 compounds detected, mainly in chlorinated freshwater pools. Trihalomethanes (THMs), haloacetic acids (HAAs), haloacetaldehydes (HALs) are among the major DBPs in swimming pools. Other DBPs such as haloacetonitriles (HAN), haloamines, nitrosamines, and halobenzoquinones have also been detected. Researchers have been interested in identifying the precursors responsible for the formation of DBPs. In swimming pools, anthropogenic organic loads brought by swimmers increase the complexity of pool water chemistry. When human inputs (e.g. sweat, urine, hair, skin and personal care products) containing very diverse organic compounds are introduced to pools by swimmers, they react with chlorine resulting in the formation of complex mixtures of DBPs. The overwhelming majority of the total organic halide (TOX) content is still unknown in swimming pools. Exposure of swimmers to DBPs can take place through multiple routes, depending on the chemical properties of each DBP. Toxicological studies have shown that swimming pool water can be mutagenic with different potencies reported in different studies. Many DBPs have been shown to be genotoxic 2 and carcinogenic. DBPs were also shown to induce reproductive and neurotoxic adverse effects in animal studies. Epidemiologic studies in humans have shown that exposure to DBPs increases the risk of respiratory adverse effects and bladder cancer. Association between DBPs and other health effects are still inconclusive. Data gathered in the present review (occurrence, toxicity, and toxicological reference values) could be used in conducting chemical risk assessment studies in swimming pools.

International audience; 10 The development of 3D printing in recent years opens up a vast array of possibilities in the field 11 of flow analysis. In the present study, a new 3D-printed flow system has been developed for 12 the selective spectrophotometric determination of lead in natural waters. This system was 13 composed of three 3D-printed units (sample treatment, mixing coil and detection) that might 14 have been assembled without any tubing to form a complete flow system. Lead was determined 15 in a two-step procedure. A preconcentration of lead was first carried out on TrisKem Pb Resin 16 located in a 3D-printed column reservoir closed by a tapped screw. This resin showed a high 17 extraction selectivity for lead over many tested potential interfering metals. In a second step, 18 lead was eluted by ammonium oxalate in presence of 4-(2-pyridylazo)-resorcinol (PAR), and 19 spectrophotometrically detected at 520 nm. The optimized flow system has exhibited a linear 20 response from 3 to 120 µg.L-1. Detection limit, coefficient of variation and sampling rate were 21 evaluated at 2.7 µg.L-1 , 5.4% (n=6) and 4 sample.h-1 , respectively. This flow system stands out 22 by its fully 3D design, portability and simplicity for low cost analysis of lead in natural waters. 23 24

International audience; Water disinfection treatments result in the formation of disinfection byproducts (DBPs) that have been linked to adverse human health outcomes including higher incidence of bladder and colorectal cancer. However, data about the genotoxicity of DBPs is limited to only a small fraction of compounds. Chloral hydrate (CH) and bromal hydrate (BH) are two trihaloacetaldehydes commonly detected in disinfected waters, but little is known about their genotoxicity, especially BH.We investigated the genotoxicity of CH and BH using a test battery that includes three in vitro genotoxicity assays.We conducted the Ames test using Salmonella bacterial strains TA97a, TA98, TA100 and TA102, and the alkaline comet assay and the micronucleus test both using Chinese hamster ovary cells. We carried out the tests in the absence and presence of the metabolic fraction S9 mix.CH did not exhibit statistically significant genotoxic effects in any of the three assays. In contrast, BH exhibited mutagenic activity in the Salmonella strain TA100 and induced statistically significant DNA lesions in CHO cells as appeared in the comet assay. The genotoxic potential of BH in both assays decreased in the presence of the metabolic fraction S9 mix. BH did not induce chromosomal damage in CHO cells.Our results show that BH exhibited genotoxic activity by causing mutations and primary DNA damage while CH did not induce genotoxic effects. Our findings highlight concerns about the higher genotoxicity of brominated DBPs in comparison to their chlorinated analogues.

This paper aims to improve the understanding of organic amendments distribution on different fractions of soil organic matter (SOM) and the knowledge of processes controlling the temporal evolution of organic matter (OM) in the first layer of a calcareous soil of two adjacent plots, one control and one treated with 3 kg m − 2 of organic amendment. An appropriate fractionation procedure of SOM, consisting in sequential extractions by water, hydrochloric acid, sodium hydroxide and potassium pyrophosphate extractions, was applied. Dissolved organic carbon (DOC), UV and fluorescence spectroscopic properties of organic matter reveal quantitative and qualitative aspects. Spectral indexes such as SUVA 254 (specific UV absorbance), E 2 /E 3 and FI (fluorescence index) were used to examine annual changes of SOM in the different fractions. Extractions with pyrophosphate, and in a lesser amount with sodium hydroxide, represented the major part of DOC, for both control and treated soils. Yields of sequential extractions ranged from 16.1% to 16.4% of TOC for these two soils. Compost inputs resulted in evolution of quantitative and qualitative results, especially for water extractable organic matter (WEOM) and pyrophosphate extracts mainly during the first 3 months of this field experiment. Study of annual changes of DOC, SUVA 254 and E 2 /E 3 index values in treated soil indicated a priming effect during the weeks after compost spreading, in relation with a revitalizing effect of microbial activity. Contributions of organo-mineral interactions and rainfall regulated WEOM amount throughout the year, and the activity of microbial communities in soil seemed to play a significant role on WEOM production. FI index values demonstrated microbial origin for WEOM, and for OM extracted either with acid or with sodium hydroxide. At the contrary, pyrophosphate extracts revealed that OM came essentially from terrestrial origin, which corresponds to the most complex and aromatic compounds. It was found that sodium hydroxide extracted less aromatic SOM, but higher molecular weight compounds. 3D fluorescence spectra revealed the presence of four main types of fluorophores according to the different extracts: humic, fulvic and marine-like compounds (A, C and M) common to all extracts, and lignin-like compounds (H) specific to pyrophosphate extracts only in treated soil at the beginning of the experiment due to initial compost effect. PCA on quantitative and qualitative data for WOEM fraction revealed essentially that meteorological aspects, with temperature and precipitation variations, were an important parameter over the year of experimentation, and that compost input impacted significantly WEOM amounts at the beginning of the experiment.

International audience; This paper describes an investigation of linear alkylbenzene sulfonates (LAS) and nonylphenol ethoxylates (NPEO) and their metabolites in the vicinity of the Marseille sewage outfall (wastewater treatment plant with a capacity of 1.860 million inhabitant equivalents, Northwestern Mediterranean, southeast of France). This analytical survey describes their occurrence in the subsurface and sea surface layers and investigates their possible fates in this marine environment. The results indicated the presence of LAS in both layers and up to 3 km from the discharge point, whereas the concentration of sulfophenyl carboxylic acids, which are the main metabolites of LAS, was only significant near the sewer outfall and in the surface layer. The NPEO were present only in minor quantities, especially near the discharge point, and no other selected metabolites were detected. The fate of the surfactants in question was then assessed by two types of experiments according to their potential means of degradation under natural conditions. Biodegradation assays were conducted according to a protocol defined by the United States Environmental Protection Agency (''Biodegradability in sea water, 835.3160''), with variations in the substrate input frequencies. Photodegradation experiments were carried out in a solar simulator reactor. These results demonstrated the low photodegradability and rapid primary biodegradation of LAS (with half-life times between 10.3 and 11.5 days) in the coastal area under study, although some LAS metabolites were more recalcitrant to biodegradation in this specific environment, which was also validated by linear alkylbenzene analysis in the two selected sediment stations.

International audience; Industrial effluents discharged into the environment may have ecotoxic effects even if they come up to regulatory standards. Chemical evaluation of treatment performance by end-of-pipe treatment systems is thus not sufficient, especially when mixtures of metallic and organic contaminants are concerned. Given that contamination may alter biological characteristics of the environment, biomonitoring studies may provide information on integrated ecotoxical effects. However, there is a need for bioassays purpose-designed for direct use at industrial sites. Many biomonitoring tools already exist and have been proved to be efficient for evaluating the ecotoxicity of contaminated waters, but most of them require laboratory equipment. In this study, an experiment in microcosms under controlled conditions of pollution was carried out to assess the morphological responses of five helophytes exposed to mixtures of organic and/or metallic pollutants. The criteria of plant growth and development, i.e. aerial elongation and leaf senescence, that were the most relevant for reflecting the ecotoxicity of contaminant mixtures and that could be monitored on-site with a user-friendly method, were then selected. Focusing on these selected criteria, a new bioindicator tool, named the Helophyte Development Index (HDI), was created. Our results suggest that the HDI is a promising tool to use on-site for assessing the ecological state of waters released in aquatic environment by industrial factories, following the recommendations of the European Water Agency. (C) 2015 Elsevier B.V. All rights reserved.

International audience; This paper presents a simple, accurate and multi-sample method for the determination of proline in wines thanks to a 96-well microplate technique. Praline is the most abundant amino acid in wine and is an important parameter related to wine characteristics or maturation processes of grape. In the current study, an improved application of the general method based on sodium hypochlorite oxidation and o-phthaldialdehyde (OPA)-thiol spectrofluorometric detection is described. The main interfering compounds for specific proline detection in wines are strongly reduced by selective reaction with OPA in a preliminary step under well-defined pH conditions. Application of the protocol after a 500-fold dilution of wine samples provides a working range between 0.02 and 2.90 g L-1, with a limit of detection of 7.50 mg L-1. Comparison and validation on real wine samples by ion-exchange chromatography prove that this procedure yields accurate results. Simplicity of the protocol used, with no need for centrifugation or filtration, organic solvents or high temperature enables its full implementation in plastic microplates and efficient application for routine analysis of proline in wines. (C) 2013 Elsevier Ltd. All rights reserved.

In the Mediterranean area, surface waters often have low discharge or renewal rates, hence metal contamination from industrialised catchments can have a high negative impact on the physico-chemical and biological water quality. In a context of climate and anthropological changes, it is necessary to provide an integrative approach for the prevention and control of metal pollution, in order to limit its impact on water resources, biodiversity, trophic network and human health. For this purpose, introduction of constructed wetlands (CWs) between natural aquatic ecosystems and industrialised zones or catchments is a promising strategy for eco-remediation. Analysis of the literature has shown that further research must be done to improve CW design, selection and management of wetland plant species and catchment organisation, in order to ensure the effectiveness of CWs in Mediterranean environments. Firstly, the parameters of basin design that have the greatest influence on metal removal processes must be identified, in order to better focus rhizospheric processes on specific purification objectives. We have summarised in a single diagram the relationships between the design parameters of a CW basin and the physico-chemical and biological processes of metal removal, on the basis of 21 mutually consistent papers. Secondly, in order to optimise the selection and distribution of helophytes in CWs, it is necessary to identify criteria of choice for the plant species that will best fit the remediation objectives and environmental and economic constraints. We have analysed the factors determining plant metal uptake efficiency in CWs on the basis of a qualitative meta-analysis of 13 studies with a view to determine whether the part played by metal uptake by plants is relevant in comparison with the other removal processes. Thirdly, we analysed the parameters to consider for establishing suitable management strategies for CWs and how they affect the whole CW design process. Finally, we propose monitoring and policy measures to facilitate the integration of CWs within Mediterranean industrialised catchments. Keywords: Constructed wetlands, Metal pollution, Plant species selection, Design methodologies, Management strategies, Industrialized Mediterranean Catchments

International audience; Water disinfection technologies based on ultraviolet (UV) radiations emitted by Light-Emitting Diodes (LED), as a wastewater tertiary treatment, have been shown to be promising for water reuse. Here, we assessed the fate of two ubiquitous pollutants, carbamazepine and anthracene, in soil watered with either UV-LED treated wastewaters or irrigation water. After 3 months, anthracene and carbamazepine were transformed two and three times faster respectively, in soils watered with UV-LED wastewater than in soils watered with tap water (probably because of the addition of organic matter by the effluent). Laccase activity was induced in the presence of the pollutants and anthraquinone was found as anthracene product of oxidation by laccases. Moreover, the addition of these pollutants into soil did not affect the functional diversity of autochthonous microbial communities assessed by Ecolog plates. Cellulase, protease and urease activities increased in soils watered with UV-LED treated wastewaters (UV-LED WW), showing transformation of organic matter from the effluent and lipase activity increased by anthracene addition, confirming the potential role of these enzymes as indicators of hydrocarbon contamination.

International audience; Soil microbial activity Faecal indicator Catabolic activity Enzymatic activities a b s t r a c t Advanced oxidation processes based on UV radiations have been shown to be a promising wastewater disinfection technology. The UV-LED system involves innovative materials and could be an advantageous alternative to mercury-vapor lamps. The use of the UV-LED system results in good water quality meeting the legislative requirements relating to wastewater reuse for irrigation. The aim of this study was to investigate the impact of watering with UV-LED treated wastewaters (UV-LED WW) on soil parameters. Solid-state 13 C NMR shows that watering with UV-LED WW do not change the chemical composition of soil organic matter compared to soil watered with potable water. Regarding microbiological parameters, laccase, cellulase, protease and urease activities increase in soils watered with UV-LED WW which means that organic matter brought by the effluent is actively degraded by soil microorganisms. The functional diversity of soil microorganisms is not affected by watering with UV-LED WW when it is altered by 4 and 8 months of watering with wastewater (WW). After 12 months, functional diversity is similar regardless of the water used for watering. The persistence of faecal indicator bacteria (coliform and enterococci) was also determined and watering with UV-LED WW does not increase their number nor their diversity unlike soils irrigated with activated sludge wastewater. The study of watering-soil microcosms with UV-LED WW indicates that this system seems to be a promising alternative to the UV-lamp-treated wastewaters. ª

International audience; Wastewater reuse for irrigation is an interesting alternative for many Mediterranean countries suffering from water shortages. The development of new technologies for water recycling is a priority for these countries. In this study we test the efficiency of UV-LEDs (Ultraviolet-Light-Emitting Diodes) emitting UV-A or UV-C radiations, used alone or coupled, on bacterial and chemical indicators. We monitored the survival of fecal bioindicators found in urban wastewaters and the oxidation of creatinine and phenol which represent either conventional organic matter or the aromatic part of pollution respectively. It appears that coupling UV-A/UV-C i) achieves microbial reduction in wastewater more efficiently than when a UV-LED is used alone, and ii) oxidizes up to 37% of creatinine and phenol, a result comparable to that commonly obtained with photoreactants such as TiO 2 .

International audience; Despite evidence of formation of brominated compounds in seawater swimming pools treated with chlorine, no data about exposure levels to these compounds have been reported. To address this issue, a survey has been carried out in four establishments (representing 8 pools) fed with seawater and devoted to relaxing and cure treatments (thalassotherapy centres located in Southeast of France). Carcinogenic and mutagenic brominated disinfection byproducts (trihalomethanes -THM- and halogenated acetic acids -HAA-) were quantified at varying levels, statistically related to organic loadings brought by bathers, and not from marine organic matter, and also linked to activities carried out in the pools (watergym vs swimming). Bromoform and dibromoacetic acid, the most abundant THM and HAA detected, were measured at levels up to 18-fold greater than the maximum contaminant levels of 60 and 80 mu g/L fixed by US.EPA in drinking waters. The correlations between these disinfection byproducts and other environmental factors such as nitrogen, pH, temperature, free residual chlorine, UV254, chloride and bromide concentrations, and daily frequentation were examined. Because thalassotherapy and seawater swimming pools (hotels, cruise ships, ...) are increasing in use around the world and because carcinogenic and mutagenic brominated byproducts may be produced in chlorinated seawater swimming pools, specific care should be taken to assure cleanliness of users (swimmers and patients taking the waters) and to increase water circulation through media filters to reduce levels of brominated byproducts. (C) 2011 Elsevier Ltd. All rights reserved.

International audience; The development of new technologies for water recycling is a priority for arid and semi-arid countries such as those of the Mediterranean basin. The aim of this study was to test the efficiency of UV-A and UV-C light emitting diodes (UV-LEDs) on bacteria inactivation. We used Escherichia coli and Enterococcus faecalis, bioin-dicators of fecal pollution typically found in urban wastewaters. An experimental design was performed to discriminate weight of factors influencing bacteria inactivation yields and reactivation phenomena. Four parameters were tested on simple bacterial cultures: pH, bacterial density, exposure time and wavelength. It appears that the exposure time and wavelength used have a significant effect on the response. The 280/ 365 nm or 280/405 nm coupled wavelengths, have the most important bactericidal effect, and we also note the absence of bacterial reactivation after 60 s of exposure to UV.

International audience; This paper presents a simple, accurate and multi-sample method for the determination of volatile fatty acids (VFAs) thanks to a 96-well microplate technique. A procedure using an activating reagent of the carboxylic function (water-soluble carbodiimide EDC) and a fluorescent amino labeling reagent (N-(1-naphthyl)ethylenediamine, EDAN) allows the formation of an isoindole derivative that needs to be separated from initial fluorescent amine for efficient VFAs determination. Isolation of these fluorescent VFA-derivatives was carried out by use of the fluorescent quenching of EDAN with o-phthaldialdehyde (OPA). Quenching was most efficient at pH around 7 and by heating at 40 degrees C within the microplate reader. This optimized procedure has been applied to various carboxylic acids and other organic compounds, demonstrating that VFA exhibit the highest fluorescence responses with homogeneous results for the main ones (acetic, propionic and butyric acid, all mass concentration expressed as acetic acid equivalents). This protocol was calibrated against acetic acid and determination of VFA was thus possible in the range 3.9-2000 mg L-1 (acetic acid equivalents). Subsequent application to real samples (sewage sludges or anaerobically digested samples) and comparison to gas chromatography analyses gave accurate results, proving the great potential of our high-throughput microplate-based technique for the analysis of VFA. (C) 2011 Elsevier B.V. All rights reserved.

International audience; In the present work, a solid phase extraction (SPE) is hyphenated with an automatic MSFIA system to improve the selenite determination based on the reaction of selenite with aromatic o-diamines (such as 2,3-diaminonaphthalene (DAN)) to form the piazselenol complex. This reaction is greatly influenced by acid concentration, temperature, the time needed for colour development, and presence of foreign ions.For these reasons a thermostatic bath, glycine, and Na2-EDTA are used as heater, buffer, and masking agent, respectively. The principle of the determination is based on the sorption of the piazselenol onto a C18 membrane disk, followed by its elution by acetonitrile. The piazselenol can then be detected by absorptiometry or fluorometry, both detection techniques being tested in our system. The best detection limit (1.7 g L−1) and RSD (3.04%) are obtained by absorptiometry at 380 nm. Environmental samples were spiked and analyzed, with recoveries close to 100%.

International audience; Solid-phase extraction for cationic elements is a promising approach for water treatment or for analysis applications. However, supports that allow the selective extraction and/or preconcentration of metalloid species are still not widespread. A new chelating sorbent has been prepared by grafting 2,3-diaminonaphtalene (DAN) on Amberlite® XAD-4 resin beads via a diazo bridge. The synthesis was first carried out at a molecular level to optimise experimental conditions and to facilitate characterisation of solid sorbent by FTIR. TGA, Py-GC/MS experiments and back titration of amine functions showed that the sorbent was grafted. Se(IV) was retained by grafted Amberlite® XAD-4 with a rate of 88% at pH 2 and 80 °C. This paper presents a convenient way of grafting DAN on polystyrene-like resins and the first applications of these supports in solid-phase extraction of Se(IV).

Solid-phase extraction (SPE) of trace elements before their analysis has become a conventional pretreatment step of analytes because of their frequent low concentrations in numerous samples. Additionally, interfering compounds often accompagny analytes of interest, thus requiring a clean-up step. The preconcentration step and/or matrix removal can be efficiently improved by chemometric approaches allowing obtention of reliable results. Single variable approach is often used but is time and cost consuming, and may be the source of mistakes; multivariable approach allows to overcome these problems and increases the probability of global optimum finding. In order to obtain a set of experimental conditions for the selective extraction of Al(III) in water samples, onto a modified organic support (salicylic acid grafted on XAD-4), a multicriteria approach (response surface methodology) has been applied. The extraction method was optimized by the aid of a factorial design and a uniform shell Doehlert design for six variables: sample percolation flow rate, trace metal amount, sample volume, concentration and volume of HCl used for elution of aluminium. Results demonstrate the synergic effects of four factors and allow us to define working ranges for each parameter tested. The designed SPE procedure was then sucessfully applied to synthetic and real samples, issued from a potable water treatment unit.

International audience; Among commercially available sorbents, aromatic organic crosslinked copolymers allow to consider numerous ways of linking ligands. In this way, the grafting of salicylic acid and of its derivatives (methylene disalicylic acid and aurintricarboxylic acid) via the ketone, amide and diazo bridges on Amberlite® XAD‐4 resin and Empore™ SDB‐XC membrane have been carried out. The modified sorbents thus obtained have been appraised according to their grafing rate and their efficiency to selectively retain different metallic ions versus pH. The grafting of the sorbents permits to obtain pretty good yields. Extraction yield studies have revealed that the supports have the same behavior whatever the ligand grafted via a diazo or an amide bridge. Thus, increase of salicylic acid entity number does not improve the performance of the supports. However, bridge used during grafting seems to have an influence upon the extraction yields observed.

International audience; Fluorescence spectroscopy has potential for characterizing the water soluble fraction of soil organic matter. However, some questions remain unanswered: (i) can this technique be applied to a complex and evolving mixture of compounds and (ii) can the quality parameter obtained from fluorescence analysis be linked to climatic parameters and soil microbial activity. To answer these questions, a set of 98 soil water extracts, from a study of a 2.50-m-thick soil section in the vadose zone during a 7-month experiment was analyzed. Water-extracted organic matter (WEOM) content and the potential aerobic respiratory activity were measured in the laboratory, whereas environmental factors (rainfall soil temperature) were monitored on site. The humification index (HIX) was also calculated for the 98 samples. Results showed a significant positive correlation (R-2 = 0.87, P < 0.001) between the fluorescence signal and the WEOM content. A higher proportion of low molecular weight and size compounds was observed in the deepest layers than in the surface soils. The decrease in aerobic respiratory activity (from 0.9 to 0.4 mugO(2) g(-1)dw h(-1)) and in HIX (from 3.7 to 2.1) from the surface to the 1.5-m depth suggest that the small fluorescent compounds were more recalcitrant to biodegradation in the deep vadose zone. Heavy rainfall events (60 mm) resulted in a sharp decrease of HIX values (from 2.6 to 1.3) at the 1.5-m depth, probably the result of leaching of small compounds, whereas the WEOM content was stable (2 mg C L-1). Fluorescence spectroscopy was demonstrated to be useful for analyzing the fate of agricultural organic residues in soils

International audience; Oxidation of phenol on platinum electrodes rapidly leads to the formation of a passivating film on the surface of these electrodes. Studies of cyclic voltammetry and chronoamperometry combined with high-performance liquid chromatography (HPLC) analyses have shown that the presence of carbon black avoids these phenomena of passivation and thus allows the complete mineralization of phenol. The nature of carbon black and the pH value are two important factors which are studied here. VULCAN XC-72 R, an intrinsic p-type semiconductor, having a large specific area, showed all its efficiency when cyclic voltammetry experiments were carried out in an acid medium (pH 2.2). HPLC analyses revealed the appearance of several by-products such as hydroquinone and benzoquinone, and maleic and fumaric acids.

The study of the fate and behaviour of organic and mineral pollutants in the biosphere needs a physico-chemical characterization of the receiving medium in order to assess transport and migration kinetics of these contaminants. Among constituents of receiving media, dissolved organicmatter (DOM) -term more often used for soils- and natural organic matter (NOM) -term more often used for waters- represent one of the essential components which regulate migration, transport and fate of these pollutants.These integrative terms cover a multitude of organic molecule families which present a large number and variety of functional groups that give them a very reactive character dependent on their intrinsic properties (solubility, hydrophobicity, size, complexation ability, pKa, toxicity).This research work aims to make a contribution to the characterization of DOM by focusing more specifically to the determination and analysis of carboxylic acid, thiol and amine functional groups.The methodology retained lies on the design of alternative analytical protocols based on a fluorimetric detection of targeted functional groups, following a step of a specific derivatization procedure.This report presents the criteria that have driven choice of reagents used for the derivatization and post-derivatization fluorimetric detection of functional groups, and the optimization of reactional conditions (pH, amount of reagents, ratios of reagents according to sample volumes, reactionkinetics) by use of screening procedures, experimental and desirability designs. It presents then the design of ready-to-use microplate assays for on-site analysis of carboxylic, thiol and amine compounds, and of a fully automated flow-system for the on-line analysis of VolatileFatty Acids (VFA).Finally, it presents the conclusive trials obtained with real samples coming from various environmental matrices (sewage sludges from wastewater treatment plants, natural and composted soils, bamboos …) along with the analytical features of the different analysis system developed., L’étude du devenir des contaminants organiques et minéraux dans la biosphère nécessite une caractérisation physico-chimique du milieu récepteur afin d’évaluer les cinétiques de transport et de migration de ces contaminants. Parmi les constituants des milieux récepteurs, la matière organiquedissoute (MOD) -terme plutôt réservée aux sols- et la matière organique naturelle (MON) -terme plutôt réservées aux eaux- représentent une des composantes essentielles qui va régir la migration, le transport et le devenir de ces contaminants.Ces termes intégrateurs recouvrent une multitude de familles de molécules organiques qui présentent un nombre important et une diversité de groupements fonctionnels qui leur procurent un caractère très réactif, dépendant de leurs propriétés intrinsèques (solubilité, hydrophobicité, taille,capacité complexante, pKa, toxicité).L’objectif de ce travail de recherche est d’apporter une contribution à la caractérisation de cette MOD en s’intéressant plus particulièrement à la détermination et au dosage des groupements fonctionnels acides carboxyliques, thiols et amines.La méthodologie retenue repose sur la mise au point de protocoles analytiques alternatifs basés sur une détection par fluorescence des groupements fonctionnels ciblés, après une étape préalable de dérivation spécifique.Ce mémoire présente les critères qui ont guidé les choix des réactifs utilisés pour la dérivation et la détection post-dérivation par fluorescence des groupements fonctionnels et l’optimisation des conditions réactionnelles (pH, concentrations des réactifs, ratios des réactifs en fonction desvolumes d’échantillons, cinétiques de réaction) par la mise en oeuvre de plans de criblage, de plans d’expériences et de désirabilité.Il présente ensuite la mise au point de kits d’analyse prêt-à-l’emploi pour l’analyse sur site des composés carboxyliques, thiols et amines, et d’un système en flux totalement automatisé pour l’analyse en continu pour le suivi des Acides Gras Volatils (AGV).Enfin, il présente les essais concluants obtenus avec des échantillons réels provenant de matrices environnementales très variées (boues de stations d’épuration, sols naturels et compostés, bambous,…) ainsi que les caractéristiques analytiques des différents systèmes mis au point.