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The concentrations and human health risk associated with alkylphenols, bisphenols, Pb, Fe, Cd, and Cr were evaluated in samples of eight different canned foods sold in Lagos, Nigeria using standard techniques. The concentrations of Pb ranged from 0.002 to 2.84 mg/kg, Fe values ranged from 1.05 to 140.34 mg/kg, Cd levels ranged from 0.03 to 0.65 mg/kg, Cr levels ranged from 0.35 to 0.77 mg/kg, and bisphenol-A (BPA) values ranged from 33.90 to 70.14 ng/g across the canned foods. The estimated daily intake (EDI) through the consumption of the different canned foods sampled ranged from 3.67x10-6 to 2.33x10-2 mg/kg/day for Pb, 1.02x10-3 to 1.43 mg/kg/day for Fe, 1.50x10-5 to 6.61x10-3 mg/kg/day for Cd, 7.80x10-5 to 7.83x10-3 mg/kg/day for Cr, and 1.70x10-5 to 5.81x10-4 mg/kg/day for BPA. Most canned food groups had EDI values that were lower than the recommended provisional tolerable daily intake for the Joint Expert Committee on Food Additives However, canned peas and canned beans had EDI values that were higher than the recommended limits for Pb, Fe, and Cr. The results from the hazard index (HI) suggest that there is a risk of a non-carcinogenic toxic effect for canned tomatoes, canned fish, canned corn, canned beans, and canned peas as their values were greater than 1. Results from this study can be used to inform regulatory decisions, guide industry standards for the production of these products and used by consumers to make informed decisions about which canned foods to purchase and consume.

Technical lignins are an attractive and renewable source for the production of aromatic chemicals. However, efficient depolymerization of technical lignins to valuable low-molecular-weight chemicals is challenging due to its recalcitrant nature. Here, we report the use of nonprecious metal-based, monometallic Ni (prereduced) and bimetallic NiMo (in situ sulfided) catalysts supported on mesoporous alumina, either as such or doped with Si, Mg, or Ti, for a solvent-free catalytic hydrotreatment (batch, 400 °C, 4 h reaction time, 100 bar initial H2 pressure) of Alcell lignin to obtain oils enriched in biobased chemicals like alkylphenols and the parent phenol. These are important building blocks in the chemical industry and are currently obtained from fossil resources. The catalysts were prepared by a one-pot evaporation-induced self-assembly (EISA) method and characterized by various techniques [N2 physisorption, X-ray diffraction (XRD), temperature-programmed desorption (TPD), temperature-programmed reduction (TPR), and transmission electron microscopy (TEM)]. The best result was obtained using a monometallic Ni catalyst with an ordered mesoporous alumina support doped with Ti, giving an oil yield of 57 wt % with 10 wt % alkylphenols on lignin intake. By comparison, it was shown that the mesoporous structure of alumina is crucial for enhanced lignin oil yields.

The high value-added products such as alkyl substituted phenols (A-Ps) are very important from lignin-derived feedstocks. Herein, the selective conversion of guaiacol, an important chemical of lignin-derived bio-oil, to A-Ps over hydrothermally synthesized bulk MoS2 (HT-MoS2) was examined under supercritical methanol conditions without any gaseous hydrogen input. HRTEM confirms the formation of MoS2 with the nanosheet-like structure and XPS analysis exhibited the presence of Mo5+ and S22- species which are likely the active species for demethoxylation (DMO) and alkylation of guaiacol. The possible reaction pathways along with their plausible intermediates of guaiacol conversion are proposed. The HT-MoS2 catalyst can be reused up to 4 catalytic runs without loss of its catalytic activity.

An effective and reliable analytical method based on molecularly imprinted solid-phase extraction (MI-SPE) and high-performance liquid chromatography with photodiode array detector was developed to simultaneously determine four phenolic compounds: bisphenol A, 2-phenylphenol, tert-octylphenol and nonylphenol. A molecularly imprinted polymer that can selectively recognize bisphenol A and alkylphenols was developed. A bulk polymerization method using bisphenol A as a template, acrylamide as functional monomer, ethylene glycol dimethacrylate as the cross-linking agent, acetonitrile as porogenic solvent and 1,1’-azobis(cyclohexanecarbonitrile) as initiator was applied. This polymer was applied for isolation and preconcentration of these phenolic compounds from surface water’s sample of Opole Region (Odra River, Nysa Kłodzka River, Mała Panew River and Turawa Lake). Bisphenol A and 2-phenylphenol were found in all water samples. Concentration of these compounds ranged 0.011–1.046 µg/mL and 0.020–0.410 µg/mL, respectively. Nonylphenol and tert-octylphenol were not detected in any samples.

The feasibility of Penicillium sp. CHY-2 isolated from pristine Antarctic soil was evaluated for the remediation of 4-tert-butylphenol (4-t-BP) contaminated soil. The strain CHY-2 completely degraded 4-t-BP present in the artificially contaminated soil within three weeks. Also, the number of indigenous bacteria and fungi present in the soil were analyzed at different time intervals using colony forming unit (CFU) analysis. The viable cell count of fungi were increased from day 10 to day 21 in the contaminated soil, and it was in accordance with the decrement of 4-t-BP concentration. The viable cell count of bacteria also increased with respect to time. The results suggested that the strain CHY-2 can be applied for the treatment of 4-t-BP contaminated soil.

In this study, seven compounds of environmental and health concern were treated by electrooxidation to determine their removal efficiencies from domestic wastewater. A batch type lab-scale reactor was used for the treatment process, and the analytes studied included two obsolete pesticides, two alkylphenols, two hormones, and bisphenol A. Titanium oxide and graphite electrodes were used as anode and cathode, respectively. Parameters of the electrooxidation process including pH of wastewater, ionic strength, applied current and treatment period were optimized by the univariate approach to maximize the removal efficiency of the analytes from wastewater. The optimum conditions were determined as nonadjusted pH of wastewater, 1.5 A current, 15 min treatment period and 5.0 g/L sodium chloride. Dispersive liquid-liquid microextraction was used to preconcentrate analytes before and after treatment in order to calculate the removal efficiency of analytes. The removal efficiency obtained under the optimum conditions was satisfactory for all seven analytes at different influent concentrations. HIGHLIGHTS Seven endocrine disrupting compounds were removed from wastewater using electrooxidation.; Electrooxidation parameters were optimized univariately.; An optimized DLLME-GC-MS method was used to analyze influent and effluent samples.; Over 95% removal efficiency was recorded for all analytes spiked to wastewater at three different concentrations.

In this work, the analysis of alkylphenols, bisphenols and alkylphenol ethoxylates in bottled waters, kombuchas and water kefir was performed through a vortex-assisted dispersive liquid–liquid microextraction method based on a natural hydrophobic eutectic solvent. For this purpose, mixtures of monoterpenes and fatty acids were employed. Different factors affecting extraction were optimized and the method was validated in terms of matrix effect, linearity, limits of detection and recovery. Recovery values varied between 70.0 and 124.3% (except for 4-tert-butylphenol: 67.0% and 4-n-nonylphenol: 60.8% in water kefir) and limits of detection were in the range 0.10 ng/L – 2.99 µg/L. Finally, 8 bottled waters, 8 kombuchas and 4 water kefirs were analyzed and 4-tert-octylphenol monoethoxylate was detected in water (20.28 ± 0.99 – 62.08 ± 3.63 µg/L). This is the first application analyzing xenobiotic contaminants in kombucha and water kefir and the first time in which the three types of compounds are simultaneously extracted by dispersive liquid–liquid microextraction., A. Santana-Mayor would like to thank Canary Agency of Economy, Industry, Trade and Knowledge of the Government of the Canary Islands for the FPI fellowship (co-financed by Agencia Canaria de Investigación, Innovación y Sociedad de la Información de la Consejería de Economía, Conocimiento y Empleo and by Fondo Social Europeo (FSE) Programa Operativo Integrado de Canarias 2014–2020, Eje 3 Tema Prioritario 74 (85%)). B. Socas-Rodríguez would like to acknowledge the Spanish Ministry of Science, Innovation and Universities for her “Juan de la Cierva” postdoctoral grant. This work has been supported by the Spanish Ministry of Economy, Industry and Competitiveness (project AGL2017-89257-P).

The objective of this study was to isolate a new bacterium and investigate its ability for degradation of various toxic organic compounds. Based on 16S rRNA gene sequence and phylogenetic analysis, the isolated strain was identified as Bacillus sp. CYR2. Degradation of various toxic compounds and growth of CYR2 strain were evaluated with 2 and 4% inoculum sizes. All the experiments were conducted for 6 days, flasks were incubated at 30oC under 180 rpm. Among the 2 and 4% inoculum sizes, bacteria showed highest growth and toxic compounds degradation at 4% inoculum size. Especially, compared to 2% inoculum size, growth of the strain CYR2 at 4% inoculum size was increased by 15.1 folds with 4-secondarybutylphenol, 9.1 folds with phenol, and 5.4 folds with 4-tertiary-butylphenol. Strain CYR2 at 4% inoculum size showed highest removal of phenol (84 ± 5%), followed by 4-tertiary-butylphenol (66 ± 3%), 4-secondary-butylphenol (63 ± 5%) and 4-nonylphenol (57 ± 6%). Compared with 2% inoculum size, degradation ability of strain CYR2 with 4% inoculum size was enhanced by 3.45 times with 4-tertiary-octylphenol, and 2.53 times with 4-tertiarybutylphenol. Our results indicated that the newly isolated Bacillus sp. CYR2 can be used for in situ bioremediation of phenol and alkylphenols contaminated water.

Removal of linear and branched alkylphenols with different alkyl chain lengths or different branchings (normal, secondary, and tertiary), some of which are suspected as endocrine disrupting chemicals, from an aqueous medium were investigated through quinone oxidation by polyphenol oxidase (PPO) and subsequent quinone adsorption on chitosan beads or powders at pH 7.0 and 40 &deg, C. PPO-catalyzed quinone oxidation increased with an increase in alkyl chain length of the alkylphenols used. Although a higher PPO dose was required for quinone oxidation of branched alkylphenols, they were completely or mostly removed by quinone adsorption on chitosan beads or powders. The apparent activity of PPO increased by a decrease in quinone concentration. On the other hand, in the homogeneous systems with solutions of chitosan and PPO at pH 6.0, longer reaction times were required to generate insoluble aggregates, and a small amount of quinone derivatives were left in the solution even under optimum conditions. These results support that the two-step reaction, that is, PPO-catalyzed quinone oxidation and subsequent quinone adsorption on chitosan beads or powders, in the heterogeneous system is a good procedure for removing linear and branched alkylphenols from aqueous medium.

Made available in DSpace on 2018-12-11T17:07:25Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-11-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Universidad de Costa Rica Previous studies using in vivo bioassay guided fractionation indicated that the herbicide diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and alkylphenol (AP)-containing surfactants were detected in fractions of extracts that induced the estrogenic biomarker, vitellogenin in fish exposed to surface water extracts from the United States. However, when the compounds were evaluated individually using in vivo estrogenic assays or in vitro estrogen receptor assays, estrogenic activity was not observed. Since APs have been shown to alter activity and content of cytochrome P450s (CYP) which convert diuron to potential estrogenic metabolites, the hepatic biotransformation of diuron was measured with and without a 7 day pretreatment of p-Octylphenol (OP) and p-Nonylphenol (NP) at low (OP 13 ng/L + NP 91 ng/L), and high concentrations (OP 65 ng/L + NP 455 ng/L) in juvenile male Nile tilapia (Oreochromus niloticus). Pre-treatment with the OP/NP (AP) mixture caused elevated levels of NADPH-catalyzed formation of 3,4-dichlorophenyl-N-methylurea (DCPMU) but not 3,4-dichlorophenylurea (DCPU). Fish were also treated with nominal concentrations of low (40 ng/L) and high (200 ng/L) diuron and each of its three degradates/metabolites: DCPMU, DCPU and 3,4-dichloroaniline (DCA). Additional treatments were conducted with APs and Diuron as a mixture at the low concentrations which mimicked concentrations observed in surface waters. Hepatic vitellogenin (Vtg) mRNA was induced by exposure to the high concentrations of Diuron, as well as DCPMU and DCPU in both concentrations. Brain cytochrome P450 aromatase activity was generally diminished by diuron, its metabolites, and the AP/diuron mixtures. 17β-Hydroxysteroid dehydrogenase (17βHSD) levels were also reduced by DCPMU and DCA in the lower concentrations, but not by higher concentrations. While the AP mixture reduced 17βHSD, the AP/diuron mixture induced testosterone (T) biosynthesis at the single concentration tested. Although CYP3A expression was induced by all diuron metabolites, it was unchanged by the AP mixture. These data indicate that mixtures of AP and diuron enhanced the formation of the metabolite (DCPMU) which induced vitellogenin, and reduced T biosynthetic enzymes (17βHSD inhibition). Overall, these data showed that APs may have induced the biotransformation of diuron to at least one metabolite, that may disrupt androgen biosynthesis and potentially alter steroid feedback pathways in the central nervous system. Department of Chemistry and Environmental Sciences Universidade Estadual Paulista (IBILCE/UNESP), Rua Cristóvão Colombo, 2265, São José do Rio Preto Department of Natural Sciences Fundação Universidade Regional de Blumenau, Av. Antonio da Veiga 140, Itoupava Seca Department of Environmental Sciences University of California Riverside Department of Chemistry and Environmental Sciences Universidade Estadual Paulista (IBILCE/UNESP), Rua Cristóvão Colombo, 2265, São José do Rio Preto FAPESP: 2011/52061-8 FAPESP: 2014/18825-9 CAPES: 3000-13-3 CNPq: 307603/2014-8 CNPq: 401884/2012-0

The distribution of per- and polyfluoroalkyl substances (PFAS), alkylphenols, organotin compounds, phthalates, alkylated polycyclic aromatic hydrocarbons, current-use pesticides (CUPs) and personal care products (PCPs) was characterized in 29 surface sediments from two Spanish Iberian continental shelf areas (14 on the Atlantic and 15 on the Mediterranean coasts). Concretely, 115 organic contaminants were determined and a specific methodology was used for each contaminant group, including contaminants of emerging concern (CECs) and traditional ones, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs). PAHs, alkylated PAHs, alkylphenols and phthalates were found in all samples, showing mean concentrations per group higher than 20 ng/g (16–4974 ng/g d.w.) in the subregions under consideration (Galician, Cantabrian, Levantine-Balearic and Strait-Alboran). CUPs and PCPs were found in the majority of samples at very low concentrations of ng/g (1.4–46.8 ng/g d.w.), whereas organotins and PFAS were found principally in sediments from the Mediterranean subregions (2.5–3.9 ng/g d.w.). Different distribution patterns were observed for the contaminant groups and subregions under consideration as a consequence of the diverse predominant sources (industrial, urban, transport and agricultural activities) and environmental behavior (mainly hydrophobicity and persistence). Risk assessment confirmed the impact of phthalates, alkylphenols, PAHs and PCBs on Atlantic ecosystems and of alkylphenols, chlorpyrifos, phthalates, TBT, PAHs, OCPs and PCBs on the Mediterranean ones. Furthermore, the presence of CUPs, PCPs and PFAS in sediments from the Spanish continental shelf located between 2 and 31 km from the coast suggested that those contaminants may also provoke adverse effects on coastal marine ecosystems between their sources and their depositional areas. Capsule Alkylphenols, phthalates and organotins may provoke adverse effects on Spanish coastal marine ecosystems from their sources to the sediment depositional areas.

Alkylphenols (APs) are a diverse class of chemicals that can cross the placental barrier and interfere with embryonic and fetal development. This work investigates the comparative toxicity, ability to inhibit aromatase activity, and to alter the lipid composition of 10 alkylphenols in the human placenta choriocarcinoma cell line JEG-3. Among the selected APs, 4-dodecylphenol (DP), 4-heptylphenol (HP), and 4-cumylphenol (CP) showed the highest cytotoxicity (EC50: 18-65 µM). Aromatase inhibition was closely related to the hydrophobicity of APs. HP significantly induced the generation of reactive oxygen species (ROS) (43-fold), inhibited placental aromatase activity (IC50: 41 µM), and induced a general dose-dependent depletion of polyunsaturated lipids (10-20 µM), which were attributed to high levels of oxidative stress. In contrast, 2,4,6-tri-tert-butylphenol (TTBP) significantly induced the intracellular accumulation of triacylglycerides (TGs), whereas DP increased the synthesis of phosphatidylcholines (PCs) and TGs at the expense of diacylglycerides (DGs). Overall, this study evidences the different modes of action of alkylphenols in human placental JEG-3 cells, describes differential lipidomic fingerprints, and highlights DP, HP, CP, and TTBP as the ones that caused the most harmful effects., Spanish National Plan for Research (Project Ref. CGL2014-52144-P) and the MIGRAPLAST project, funded by the Spanish Ministry of Economy and Competitiveness (IPT-2011-0709-060000).

An analytical method for the simultaneous determination of bisphenol A, 4-t-octylphenol, 4-n-octylphenol, and 4-n-nonylphenol in cosmetic samples has been developed. These compounds have toxic effects on human health as they have shown to produce endocrine disrupting properties. Therefore, their presence in cosmetics should be avoided according to the current European Regulations on cosmetic products. The method is based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) detection. Standard addition calibration was used to avoid matrix effects. The limits of detection values ranged between 7 and 15ngmL(-1) (threefold of the residual standard deviation of regression lines). The proposed method was validated, and good recovery (90-106%) and repeatability values (2.7-8.2%) were obtained. Finally, the method was successfully applied to ten commercially available cosmetic samples. The good analytical features of the proposed method make it useful to carry out the quality control of cosmetic products and raw materials to assure the safety of users.

International audience; Phenol hydroxylases (PHs) play a primary role in the bacterial degradation of phenol and alkylphenols. They are divided into two main classes, single-component and multi-component PHs, having distinctive catalytic subunits designated as PheA1 and LmPH, respectively. The diversity of these enzymes is still largely unexplored. Here, both LmPH and pheA1 gene sequences were examined in activated sludge from oil refinery wastewaters. Phenol, p-cresol, or 3,4-dimethylphenol (3,4-DMP) supplied as extra carbon sources were rapidly mineralized by the microbial community. Analysis of LmPH genes revealed a wide range of sequences, most of which exhibited moderate similarity with homologs found in Proteobacteria. Moreover, the LmPH diversity profiles showed a dramatic shift upon sludge treatment with p-cresol or 3,4-DMP amendment. This resulted in an enrichment in sequences similar to LmPHs from Betaproteobacteria and Gammaproteobacteria. RT-PCR analysis of RNA extracted from wastewater sludge highlighted LmPH genes best expressed in situ. A PCR approach was implemented to analyze the pheA1 gene diversity in the same microbial community. Retrieved sequences fell into four clusters and appeared to be distantly related to pheA1 genes from Actinobacteria. Altogether, our results provide evidence that phenol degraders carrying LmPH are more diverse than PheA1 carrying bacteria and suggest that PHs with best adapted substrate specificity are recruited in response to (methyl)phenol availability.

11 p.-5 fig.-2 tab. Endocrine-disrupting chemicals (EDCs) generate reproductive dysfunctions affecting the biosynthesis of steroid hormones and genes of the steroidogenic pathway. EDCs effects are mainly reported as a result of exposure to single compounds. However, humans are environmentally exposed to a mixture of EDCs. Herein, we assess chronic exposure to single alkylphenols and phthalates versus a mixture in mouse testes histology and steroidogenesis. Pregnant mice were exposed through drinking water to: 0.3 mg/Kg-body weight (BW)/day of each phthalate (DEHP, DBP, BBP), 0.05 mg/Kg-BW/day of each alkylphenol (NP, OP), or their mixture, covering from 0.5 post-coital day to weaning, continuing in the male offspring each exposure until adulthood (60 days old). Body and relative testis weight were increased in mixture-exposed mice along with histological alterations. Intratesticular testosterone (T) changed only in mice exposed to DBP, whereas estradiol (E2) levels were altered in all groups (except BBP). mRNA levels of genes encoding hormones of the steroid pathway (Cyp11a1, Hsd3b1, Cyp17a1 and Cyp19a1), cholesterol transporters (Star), and transcriptional factors (Sp1) showed that mice exposed to single or mixed compounds had alterations in at least two transcripts. However, none of the different types of exposure induced changes in all transcripts. In addition, changes at the mRNA or protein levels with single compounds were not always the same as those with a mixture. In conclusion, the effects of a chronic exposure to a mixture of EDCs on the expression of genes and proteins of the steroidogenic pathway and hormonal status were different from those exposed to single EDC. This work was supported by grants from FONDECYT (1150352) and CONICYT (21120505),Chile, and MINECO (BFU2013-42164-R), Spain.

Catalytic properties of Ti-containing porous solids were compared in the oxidation of 2,3,6-trimethylphenol (TMP) with H2O2 to produce 2,3,5-trimethyl-1,4-benzoquinone (TMBQ, vitamin E key intermediate). Mesoporous titanium-silicates with di(oligo)nuclear Ti centers, metal-organic framework MIL-125 and amorphous TiO2 demonstrated 100 % selectivity toward TMBQ. Titanium-silicates prepared by evaporation-induced self-assembly revealed superior performance in terms of product yield and catalyst reusability.

International audience; Phthalates and alkylphenols are toxics classified as endocrine disrupting compounds (EDCs). They are of particular concern due to their ubiquity and generally higher levels found in the environment comparatively to other EDCs. Industrial and domestic discharges might affect the quality of receiving waters by discharging organic matter and contaminants through treated waters and combined sewer overflows. Historically, industrial discharges are often considered as the principal vector of pollution in urban areas. If this observation was true in the past for some contaminants, no current data are today available to compare the quality of industrial and domestic discharges as regards EDCs. In this context, a total of 45 domestic samples as well as 101 industrial samples were collected from different sites, including 14 residential and 33 industrial facilities. This study focuses more specifically on 4 phthalates and 2 alkylphenols, among the most commonly studied congeners. A particular attention was also given to routine wastewater quality parameters. For most substances, wastewaters from the different sites were heavily contaminated; they display concentrations up to 1200. μg/l for di-(2-ethylhexyl) phthalate and between 10 and 100. μg/l for diethyl phthalate and nonylphenol. Overall, for the majority of compounds, the industrial contribution to the flux of contaminant reaching the wastewater treatment plants ranges between 1 and 3%. The data generated during this work constitutes one of the first studies conducted in Europe on industrial fluxes for a variety of sectors of activity. The study of the wastewater contribution was used to better predict the industrial and domestic contributions at the scale of a huge conurbation heavily urbanized but with a weak industrial cover, illustrated by Paris. Our results indicate that specific investigations on domestic discharges are necessary in order to reduce the release of phthalates and alkylphenols in the sewer systems for such conurbations. © 2014 Elsevier B.V.

Food safety can be compromised by the presence of a wide variety of substances, deriving from both natural and anthropogenic sources. Among these substances, compounds exhibiting various degrees of estrogenic activity have been widely studied in environmental samples, whereas less attention has been devoted to food matrices. The aim of the present review is to give a general overview on the recent analytical methods based on gas or liquid chromatography coupled to mass spectrometry for the determination of estrogen-like compounds in foods, including new developments, improvements and upcoming trends in the field. Attention will be focused on four representative groups of compounds, i.e. natural and synthetic estrogens, mycoestrogens, phytoestrogens, and alkylphenols.

Endocrine-disrupting chemicals are substances present in the environment that can interfere with normal hormonal balance and thus exert potentially adverse health effects on the human organism. Male reproductive system development and function may be susceptible to the effects of such environmental toxicants. Bisphenol A, phthalates and alkylphenols are important components of multiple products and are thus ubiquitously present in the environment. It has been demonstrated under laboratory conditions that they can exert detrimental effects on the male reproductive system. However, human exposure data are scarce and do not uniformly support toxicity of these substances at environmental concentrations. Despite substantial research efforts, the final answer to the problem of endocrine-disrupting chemicals is not yet in sight.Endocrine-disrupting chemicals are substances present in the environment that can interfere with the action of hormones and thus exert potentially adverse health effects on the human organism. Male reproductive system development and function may be susceptible to the effects of such environmental toxicants. Bisphenol A, phthalates and alkylphenols are important components of multiple consumer products as well as industrial processes and are thus ubiquitously present in the environment. After exposure to these substances, numerous adverse effects on male reproductive system have been demonstrated in animal studies. Thus, developmental genital anomalies as well as lower semen quality have been observed. However, human exposure data are scarce and do not uniformly support toxicity of these substances at concentrations present environmentally. Despite substantial research efforts, the final answer to the problem of endocrine-disrupting chemicals is not yet in sight.

The paper expresses an attempt to tackle the problem due to the presence of micropollutants in wastewater which may be able to disrupt the endocrine system of some organisms. These kinds of compounds are ubiquitously present in municipal wastewater treatment plant (WWTP) effluents. The aim of this paper is to compare the fate of the alkylphenols-APs (4-(tert-octyl)) phenol, t-nonylphenol and 4-p-nonylphenol and the hormones (estrone, 17ß-estradiol and 17¿-ethinylestradiol) in a submerged anaerobic membrane bioreactor (SAMBR) pilot plant and in a conventional activated sludge wastewater treatment plant (CTP). The obtained results are also compared with the results obtained in a previous study carried out in an aerobic MBR pilot plant. The results showed that the APs soluble concentrations in the SAMBR effluent were always significantly higher than the CTP ones. Moreover, the analyses of the suspended fraction revealed that the AP concentrations in the SAMBR reactor were usually higher than in the CTP reactor, indicating that under anaerobic conditions the APs were accumulated in the digested sludge. The aerobic conditions maintained both in the CTP system and in the aerobic MBR favoured the APs and hormones degradation, and gave rise to lower concentrations in the effluent and in the reactor of these systems. Furthermore, the results also indicated that the degradation of APs under aerobic conditions was enhanced working at high solid retention time (SRT) and hydraulic retention time (HRT) values. © IWA Publishing 2012., This research was financially supported by the Government of the Region of Valencia (Generalitat Valenciana), within the research project 'Application of Water Framework Directive 2000/60/EC on endocrine disruptors and priority substances in coastal areas in the Comunidad Valenciana' and by the Spanish Research Foundation (MICINN, project CTM2008-060809-C02-01/TECNO), within the research project 'Feasibility of the SAMBR technology to treat urban wastewater, and the technical and economic feasibility to industrial implementation'.

International audience; This paper investigates the occurrence of alkylphenols (APs) and polybromodiphenylethers (PBDEs) in raw wastewater during dry and wet-weather periods, and their removal by physico-chemical lamellar settling and biofiltration techniques. Due to in-sewer deposit erosion and, to a lesser extent, to external inputs, raw effluents exhibit from 1.5 to 5 times higher AP and PBDE concentrations during wet periods compared with dry ones. The lamellar settler obtains high removal of APs and PBDEs under both dry and wet-weather flows (>53% for Σ(6)AP and >89% for Σ(4)PBDE), confirming the insensitivity of this technique to varying influent conditions. Indeed, despite the higher pollutant concentrations observed in raw effluents under wet-weather flows, adjusting the addition of coagulant-flocculent allows for efficient removal. By combining physical and biological processes, the biofiltration unit treats nutrient pollution, as well as Σ(6)AP and Σ(4)PBDE contamination (58 ± 5% and 75 ± 6% respectively). Although the operating conditions of the biofiltration unit are modified during wet periods, the performance in nutrient pollution, APs and light PBDE congeners remains high. Nevertheless, lower efficiency has been noted in nitrogen pollution, i.e. no denitrification occurs, and BDE-209 (not removed during wet-weather periods). In conclusion, this study demonstrates that the combination of both techniques treats AP and PBDE pollution efficiently during dry periods, but that they are also suitable for stormwater treatment.

POCIS (polar organic chemical integrative sampler) is one of the passive sampler the most frequently used for the monitoring of dissolved organic micropollutants in surface waters. The advantage of such a passive sampling is to decrease quantification limits and to obtain a time-averaged water concentration. POCIS is used for hydrophilic molecules (log KOW < 4). The aim of this paper is to review the advantages and drawbacks of this tool for the evaluation of the river water quality downstream wastewater treatment plants outflow (WWTP). As planned in the AMPERES project, POCIS were used during 5 in situ sampling campaigns from November 2007 to September 2008 : on the Saône, the Jalle d'Eysines, the Ardières, the Bourbre and the Seine rivers. They were set up in surface waters, upstream and downstream WWTP outfow, and also within the WWTP effluent. Several chemical classes of organic molecules were studied: industrial substances such as alkylphenols and bisphenol A; also 5 estrogenic hormones; and other pharmaceuticals from various therapeutic classes, such as 9 antidepressants, 6 anti-inflammatories, 10 betablockers, 1 lipopenic, 3 bronchodilators; as well as theophylline and caffeine. POCIS were exposed for up to 28 days to study the accumulation kinetics and the linearity of uptake rates. Sampling repeatability was verified by the exposure of triplicates. To better evaluate the performance of POCIS, grab sampling was also performed at regular intervals during POCIS exposure. For the estrogenic hormones and betablockers, accumulation kinetics and sampling rates were studied in situ. Concerning alkylphenols and other pharmaceuticals, calibration was performed in the laboratory. We also tried to identify a molecule that could be used as internal surrogate or PRC (performance reference compound). Finally, POCIS is well adapted for the sampling of pharmaceuticals and alkylphenols. Its efficiency was not proved in this study for bisphenol A and estrogenic hormones. The optimal exposure duration is about 15 days. Concentration factors and decrease of quantification limits are significant except for hormones, betablockers and bronchodilators. Promising preliminary results obtained on deuterated atenolol used as PRC need to be confirmed in laboratory. This work confirms that POCIS is useful for the monitoring of hydrophilic organic molecules in river and waste waters., Le POCIS (polar organic chemical integrative sampler) est l'un des échantillonneurs intégratifs les plus utilisés pour la surveillance des micropolluants organiques dissous dans l'eau. L'avantage de ce type d'échantillonnage est d'abaisser les seuils de quantification et d'obtenir une concentration moyennée sur la durée d'exposition. Le POCIS est employé pour le suivi des molécules hydrophiles (log KOW < 4). L'objectif de cet article est de faire le point sur les avantages et inconvénients de cet échantillonneur pour l'évaluation de la qualité des eaux de surface impactées par des effluents de station d'épuration (STEP). Des POCIS ont été mis en ½uvre dans le cadre du projet AMPERES, lors de 5 campagnes d'échantillonnage réalisées entre novembre 2007 et septembre 2008 : sur la Saône, la Jalle d'Eysines, l'Ardières, la Bourbre et la Seine. Ces POCIS ont été installés dans les rivières, en amont et en aval de STEP, ainsi que dans l'effluent traité de ces mêmes stations. Plusieurs familles de molécules organiques ont été étudiées : des substances d'origine plutôt industrielle telles que les alkylphénols et le bisphénol A ; et aussi 5 hormones oestrogéniques ; et d'autres molécules pharmaceutiques appartenant à plusieurs familles thérapeutiques, telles que 9 antidépresseurs, 6 anti-inflammatoires, 10 bêtabloquants, 1 hypolipémiant, 3 bronchodilatateurs ; et enfin la théophylline et la caféine. Les POCIS ont été exposés jusqu'à 28 jours afin d'étudier in situ les cinétiques et la linéarité de l'accumulation. La répétabilité de l'échantillonnage a été vérifiée par l'exposition de triplicats de POCIS. Pour évaluer la pertinence de l'outil, des échantillons ponctuels ont été prélevés périodiquement sur chaque site pendant la durée d'exposition des POCIS. Pour ce qui concerne les hormones oestrogéniques et les bêtabloquants, les cinétiques d'accumulation et les taux d'échantillonnage ont été étudiés in situ. Pour ce qui concerne les alkylphénols et certains médicaments, ces études ont été menées en laboratoire. Enfin, des essais ont été entrepris pour trouver une molécule pouvant jouer le rôle d'étalon interne ou de PRC (performance reference compound). Le POCIS se révèle adapté pour l'échantillonnage des micropolluants d'origine pharmaceutique et des alkylphénols. Son intérêt n'a pas été démontré ici pour les hormones et le bisphénol A. La durée optimale d'exposition est d'environ 15 jours. Les facteurs de concentration ou abaissements des seuils de quantification avec le POCIS sont significatifs sauf pour les hormones, bêtabloquants et bronchodilatateurs. Des premiers résultats prometteurs sur l'aténolol deutéré utilisé comme PRC restent à confirmer en laboratoire. Les travaux confirment que l'outil est pertinent pour la surveillance de molécules organiques hydrophiles dans les eaux résiduaires et de surface.

International audience; Produced water (PW) contains numerous toxic compounds of natural origin, such as dispersed oil, metals, alkylphenols (APs), and polycyclic aromatic hydrocarbons (PAHs). In addition, PW also contains many different chemicals which have been added during the oil production process. In the study described here, cod were exposed to real PW collected from an oil production platform in the North Sea. This was done in order to best recreate the most realistic field-exposure regime in which fish will be affected by a wide range of chemicals. The biological effects found in this study therefore cannot be assigned to one group of chemicals alone, but are the result of exposure to the complex chemical mixture found in real PW. Since APs are well known to cause endocrine disruption in marine organisms, we focused our chemical analysis on APs in an attempt to better understand the long term effects of APs from PW on the biology of fish. In this study, cod were exposed to several concentrations of real PW and 17β-oestradiol (E), a natural oestrogen, at different developmental stages. Cod were exposed to PW either during the embryo and early larvae stage (up to 3 months of age) or during the early juvenile stage (from 3 - 6 months of age). Results showed that, in general, APs bioconcentrate in fish tissue in a dose and developmental stage dependent manner during PW exposure. However, juveniles appeared able to effectively metabolise the short chain APs. Importantly, PW exposure had no effect on embryo survival or hatching success. However, 1% PW clearly interfered with the development of normal larval pigmentation. After hatching most of the larvae exposed to 1% PW failed to begin feeding and died of starvation. This inability to feed may be linked to the increased incidence of jaw deformities seen in these larvae. In addition, cod exposed to 1% PW, had significantly higher levels of the biomarkers vitellogenin and CYP1A in plasma and liver, respectively. No similar effects were seen in cod exposed to either 0.1% or 0.01% PW.

Urdaibai was declared a Biosphere’s Reserve by UNESCO in 1984. Because we observed a high prevalence of hermaphroditism in mussels sampled in Urdaibai in March 2004, we started the present research work in order to determine the presence of endocrine disruptors (EDs) in sediments and to study possible EDs effects on mussels and oysters using gonad index and vitellogenin (VTG)-like protein levels as biomarkers. Samples were collected at five localities in April 2007 and 2008, and in October 2007. Estrogenic hormones were not detected in sediments and levels of bisphenol A and organotin compounds were very low. Alkylphenols were found at moderate levels and showed a time-dependent decrease. Phthalates were found at levels up to 8000 ng/g. High prevalence of oocyte atresia and necrosis occurred in mussels sampled in April. Retarded gametogenesis was observed in an oyster population from a shipyard. Hermaphrodites or alterations in VTG-like protein levels were not found but the high prevalence of histopathological alterations in oocytes is of concern., Work supported by Catedra UNESCO of the UPV/EHU through the project DERBiUr (UNESCO06/19) and by the Basque Government through project ETORTEK-IMPRES and a grant to consolidated research groups (GIC07/26-IT-393-07).

Background, aim and scope Ria de Aveiro (Portugal) is a shallow coastal lagoon of high economic and ecological importance. Hardly any data on its chemical pollution by polar organic pollutants are available in literature. This study focused on the presence and sources of a series of phenolic endocrine-disrupting compounds (EDCs) in this area, including parabens, alkylphenolic compounds and bisphenol-A (BPA). A number of possible sources of pollution are present in the area, including the large harbours present in the lagoon, the city of Aveiro and the rivers discharging into the area. A recently constructed submarine wastewater outfall, located a few kilometres from the lagoon inlet has also been suggested as a possible source of pollution to Ria de Aveiro in several publications. The aim of the current field study was to investigate the occurrence and main sources of phenolic endocrine disruptors in Ria de Aveiro. Materials and methods An extensive sampling campaign was performed, with surface water and wastewater grab samples taken at over 50 locations, in duplicate on different days. Samples were treated using solid phase extraction and analysed by liquid chromatography tandem mass spectrometry. Results and discussion Concentrations in lagoon water were generally low: not exceeding 20 ng/L for most analytes. Levels in river water exceeded those in the lagoon by a factor 3 to 500 (o-phenylphenol (PhP) and nonylphenoxy ethoxy acetic acids (A9PEC), respectively), with concentrations up to 700 ng/L for BPA and 7,300 ng/L for A9PEC. Samples from the harbours showed EDC levels similar to those in the rest of the lagoon, but in the city of Aveiro, elevated concentrations were observed for alkylphenol ethoxylates (A9PEO), A9PEC, PhP and BPA. Wastewater effluents showed low levels for parabens, whilst alkylphenolic compounds reached several micrograms per litre. The effluents are discharged into the ocean via a submarine outfall, but as marine water near the outfall showed slightly elevated concentrations only for A9PEO, it does not seem to be a significant source of these EDCs for the area. Conclusions All the studied phenolic EDCs were detected in the study area, with high levels found in some of the rivers discharging into the lagoon, and generally low concentrations in the lagoon itself. The main sources for all investigated EDCs were the rivers Caster and Antuã which discharge into the lagoon. The city of Aveiro was identified as a secondary source. As the tidal water exchange volume is much larger than the freshwater input from the rivers, concentrations of phenolic EDCs remained low in the lagoon. Electronic supplementary material The online version of this article (doi:10.1007/s11356-009-0275-5) contains supplementary material, which is available to authorized users.

The aim of this study was to determine the degradability of 26 Alkylphenols (APs) by Chemical Oxygen Demand (COD) and/or 5-day Biochemical Oxygen Demand (BOD(5)), and to describe these data from Quantitative Structure-activity Relationships (QSARs). Statistical analysis techniques, such as Multiple Linear Regression (MLR), Principal Component Regression (PCR), Partial Least-Squares (PLS) Regression and Neural Network (NN) were carried out to calibrate and validate four-descriptor QSAR models using two different types of descriptor sets. Stable MLR-QSAR models using Leave-One-Out (LOO) were obtained with high predictability performance: r(2) = 0.924, Q(2)(cv) =0.854 for log (1/BOD) model on 24 APs and r(2) = 0.888, Q(2)(cv) = 0.818 for log (1/COD) on all the studied APs. The MLR models, built with four Dragon descriptors selected by Genetic Algorithm (GA), presented the following performances on 24 APs: r(2) = 0.889, Q(2)(cv) = 0.848 for log (1/BOD(5)) and r(2) = 0.885, Q(2)(cv) = 0.834 for log (1/COD) on 26 compounds. From these results, it is expected that the QSAR models generated could be successfully expanded to predict the biological and chemical activities of structurally diverse AP compounds.

Three different sorbents (i.e. endcapped octadecylsilane, octasilane and styrene-N-vinylpiperidinone co-polymer) were investigated in order to develop an on-line solid phase extraction-liquid chromatographic tandem mass spectrometric method (on-line SPE-LC-MS/MS) for the simultaneous analysis of alkylphenols polyethoxylate (AP(n)EOs, n = 1-8) and corresponding monocarboxylate (AP1ECs) and phenolic (APs) metabolites. The endcapped octadecylsilane was selected due to its full compatibility with a chromatographic approach, which allowed the elution of positively and negatively ionisable compounds in two distinct retention time windows, using a water-acetonitrile-tetrahydrofuran ternary gradient and a pellicular pentafluorophenyl column. On this SPE sorbent, the composition of the loading/clean-up solution was then optimized in order to achieve the best recoveries of target analytes. Under the best experimental conditions, the total analysis time per sample was 25 min and method detection limits (MDLs) were in the sub-nanograms per litre to nanograms per litre range (0.0081-1.0 ng L(-1)) for AP(n)EOs with n = 2-8, AP1ECs and APs, whereas for AP1EOs, an MDL of about 50 ng L(-1) was found. Using the mass-labelled compound spiking technique, the method performance was tested on inlet and outlet wastewater samples from three activated sludge treatment plants managing domestic and industrial sewages of the urban areas and the textile district of Prato and Bisenzio valley (Tuscany, Italy); in most cases, apparent recovery percentages approximately in the ranges of 50-110% and 80-120% were found for inlet and outlet samples, respectively. The on-line SPE-LC-MS/MS analysis of wastewater samples highlighted the presence of target analytes at concentrations ranging from few nanograms per litre to thousands nanograms per litre, depending on the compound and matrix analysed. AP2ECs were also tentatively identified in outlet samples.

The occurrence and spatial distribution of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A were examined in five estuaries along the Northwest coastal area of Spain. As far as we know, no previous works about this topic could be found in the literature. A total of 98 seawater samples were collected during May 2011–July 2012 and analyzed by a highly sensitive DLLME–LC–MS/MS methodology recently developed. Results indicated nonylphenol was the most ubiquitous compound with maximal concentration of 0.337 μg L−1 (Ría de Vigo). The environmental quality standards (EQS) established in Directive 2013/39/EU for 4-tert-octylphenol were slightly exceeded in some sampling points. Fishing harbours, water treatment plant and industrial discharges were supposed as the main sources of contamination. Low and medium ecological risk was determined in all estuaries. Possible endocrine effects on biota and population were estimated in terms of estrogenic activity and daily intake respectively, and no risk was found in any case., SI

The occurrence, distribution and bioaccumulation of five endocrine disrupting compounds (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol and bisphenol A) in water, sediment and biota (Corbicula fluminea) collected along the Minho River estuary (NW Iberian Peninsula) were examined. Samples were collected in two campaigns(May andNovember, 2012) and analyzed by different extraction procedures followed by liquid chromatography tandem mass spectrometry determination. The presence of linear isomers (4-noctylphenol and 4-n-nonylphenol) was scarcely observed whereas branched isomers (4-tert-octylphenol and nonylphenol) were measured in almost all samples.Wastewater treatment plant effluents and nautical, fishing and agricultural activities are considered the primary source of pollution of the river by alkylphenols. The presence of bisphenol A in the river could be mainly associated to punctual sources of contamination from industrial discharges. A decrease in the total concentration of phenolic compounds in water was observed from spring to autumn (from 0.888 μg L−1 in May to 0.05 μg L−1 in November), while similar values were shown in C. fluminea samples from the two campaigns (1388 and 1228 ng g−1 dw in spring and autumn, respectively). In sediments, the total concentration of the target compounds varied between 13 and 4536 ng g−1 dw (average of 1041 ng g−1 dw). Sediment–water partition coefficient (Kd), bioaccumulation factor (BAF) and biota–sediment accumulation factor (BSAF) were estimated and highest values were obtained for nonylphenol. Calculated risk quotients showed low and moderate risk for the aquatic environment from the presence of the target compounds at all sampling points. The estimation of the daily intake of the studied compounds via water and biota ingestion indicated no risk for human health. Versión del editor 3,2580

A readily applicable method based on extraction by aqueous non-ionic surfactant solutions (Tween 80) and RP-HPLC coupled to fluorescence detection, has been developed for the simultaneous determination of the phenolic endocrine disrupting chemicals (EDCs) nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) and bisphenol A (BPA) in environmental solid matrices. Clean up of sample extracts was performed on Si-C18 solid phase extraction (SPE) cartridges. The overall Tween 80 extraction-SPE-RP-HPLC procedure was validated for accuracy and precision by analyzing sediment samples spiked with known amounts of EDCs. Recoveries for NP, NP1EO, NP2EO and BPA and limits of detection are in agreement with conventional extraction methods. The developed methodology was successfully applied to the analysis of target compounds in Italian river sediments, river suspended matter and benthonic macroinvertebrate organisms (oligochaetes Lumbriculus variegatus). Results confirmed that this relatively simple procedure performed satisfactorily in the determination of phenolic EDCs in environmental solid matrices of different complexity and that it can be a suitable alternative method to conventional systems even for routine analyses.

International audience; Endocrine disrupting compounds (EDCs) have been found in surface waters worldwide. They are known for exerting adverse effects on animals of many species, including humans. EDCs comprise compounds of anthropogenic origin. They can enter waterways via either discharges from wastewater treatment plant (WWTPs), combined sewer overflows (CSO) or atmospheric deposition. In this work, the fate and removal of four phthalates and two alkylphenols: Diethyl phthalate (DEP), Di-n-Butyl phthalate (DnBP), Butyl Benzyl phthalate (BBP), Di-(2-ethylhexyl) phthalate (DEHP), nonylphenol (NP) and octylphenol (OP) were investigated within a wastewater treatment plant (WWTP) using lamellar clarification and biofiltration. This plant receives about 240,000 m 3 d -1 of wastewater. The whole treatment process comprises: screening, grit removal, primary sedimentation using coagulant and flocculant, followed by biofiltration units. Phthalates and alkylphenols were monitored at three locations, including raw sewage, before primary treatment, decanted effluents, before biological treatment, and final effluents, just before discharge to receiving waters. Nine campaigns were performed in 2011 during different seasons. In raw wastewater, DEHP was the major compound (32.42 to 71.88, median 42.95 μg.l -1), followed by DEP (7.00 to 36.03, median 21.00 μg.l -1) and NP (4.08 to 10.63, median 5.95 μg.l -1). Other compounds averaged few μg.l -1. During the WWTP treatment, DEP becomes major contaminant (0.46 to 6.77, median 2.95 μg.l -1), followed by DEHP (0.95 to 6.43, median 2.30 μg.l -1) and NP (0.31 to 1.36, median 0.63 μg.l -1). Contaminant removal depends on the physicochemical characteristics of the compounds. For example, for lamellar clarification, removal efficiency was found to be strongly dependent to log Kow and, hence, to be highly correlated with their sorption coefficient (Kd). As a consequence, compounds with high log Kow (>3) were removed to a significant extent. DEHP was highly removed by lamellar clarification (68.8%), followed by BBP (61.5%) and NP (51.0%). Besides, DEP (log Kow < 3) was slightly removed (13.8%). During biofiltration, both hydrophilic and hydrophobic compounds were equally eliminated. Therefore, DEP (87.3%), OP (88.0%) and DEHP (81.9%) were mostly removed during biological treatment. © 201 WIT Press.

In spite of its outstanding ecological and touristic importance the Ria Formosa Lagoon shows signs of anthropogenic pollution. Nonetheless, until the present survey no studies had ever documented the measurement of natural and pharmaceutical estrogens (17β-estradiol, estrone, and 17α-ethynylestradiol), xenoestrogenic industrial pollutants (4-octylphenol, 4- nonylphenol, and their mono and diethoxylates and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, genistein), and sitosterol in this area. The 17 compounds measured herein are known as endocrine disrupters (EDCs) and act over the endocrine system even in few amounts (ng L−1–μg L−1). Thus to conclude about the influx of EDCs in the lagoon, water samples were taken every 2 months, during 1 year (2010), in low tide at nine sites distributed along the coastline. Water samples (1 L) were preconcentrated in the Oasis HLB cartridges and cleaned in silica cartridges before their analysis by GC-MS. Data showed the ubiquitous presence of potentially hazardous amounts of estrogens (particularly of ethynylestradiol, up to 24.3 ng L−1), nonylphenol (up to 547 ng L−1), and sitosterol (up to 12,300 ng L−1), mainly in summer, suggesting that the increase of the local number of inhabitants (tourists), the rise of the water temperature (up to 26 °C), and the blooming of local flora may interfere with the water quality parameters. This makes the lagoon a potential model to study. Taking into account the data, it was concluded that there are conditions for the occurrence of endocrine disruption in aquatic animals, even in areas included in the natural park of the Formosa. Besides, both the high amounts of un-ionized ammonia (up to 0.3 mg L−1) and phosphates (up to 1.6 mg L−1) my pose risks for local fauna and humans. This work was financially supported by FEDER funds through the Competitiveness and Trade Expansion Program—COMPETE and by National Funds provided by Fundação para a Ciência e a Tecnologia (FCT), via the project PTDC/MAR/70436/2006.

International audience; This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP(1)EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP(1)EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.

Denne screening prosjekt undersøkt forekomsten av nonylfenol og nonylfenol monoethoksylat, oktylfenol og oktylfenol monnoethoksylat, og bisfenol A i marin og ferskvanns akvatiske miljøer, bunnstoffet Zineb og dens nedbrytnings produkt ethylenethiourea i småbåthavner, det soppmiddel transformasjon produktet N,N-dimethylsulfamid, valgt annensgenerasjons antikoagulant rottegift i leveren hos utvalgte rovfugl, og nonylfenol og nonylfenol monoethoksylat, oktylfenol og oktylfenol monnoethoksylat og valgte nåværende bruk plantevernmidler i Arktis biota. Klif

The aquaculture industry is an expanding activity, mainly due to the world population demand of fish. However, intensive production and the use of chemicals have raised environmental concerns and have questioned the quality of cultured fish in comparison to wild fish. Up to date, there is little information regarding pollutant residues in cultured stocks and the risks associated to consumption. Here we summarize recent data on pollutants exposure, together with biochemical responses in both cultured and wild sea bass (Dicentrarchus labrax) from the Iberian Peninsula. The obtained data highlights the use of chemicals in current aquaculture practices as a significant source of pollution in cultured fish that poses a risk to exposed individuals and may negatively impact aquatic ecosystems. Nonetheless, a controlled use of those chemicals and a careful selection of the aquaculture location can ensure relatively low and homogeneous levels of pollutants in cultured fish in comparison to wild specimens. info:eu-repo/semantics/publishedVersion

International audience; The biotransformation of nonylphenol was investigated in an agricultural soil treated with a mixture of 14C-labelled and unlabelled surfactant. It was then studied in soil samples amended with sludges spiked with the mixture of chemicals. Nonylphenol amount in all samples of soil and soil/sludge mixtures was 40 mg kg−1. In the soil free of sludge, the half-life of nonylphenol was found to be 4 d. When the soil was amended with sludge from the city of Ambares, France, it was about 16 d. In the soil amended with sludge from Plaisir, a 8-day lag phase was observed before the transformation starts, and nonylphenol half-life exceeded 16 d. In each case, nonylphenol transformation resulted in mineralization as well as stabilization of the chemical as bound residues within the soil. Further, some strains of filamentous fungi were isolated from the soil/sludge mixtures and identified to belong to the Mucor and Fusarium species. Most of them were able to efficiently transform nonylphenol in liquid cultures. In addition, the ligninolytic basidiomycete Trametes versicolor was able to catalyze partly the conversion of nonylphenol into carbon dioxide. Laccases purified from T. versicolor cultures are enzymes involved in nonylphenol oxidative coupling leading to oligomerization.

9 pages, 4 figures, 4 tables., Red mullet (Mullus barbatus) were collected from different sampling sites (NW Mediterranean) in spring and autumn, with the aim of assessing potential alterations of the endocrine system. Alkylphenols were measured in fish bile as an indicator of estrogenic exposure. Key enzymatic activities involved in both synthesis (ovarian 17β-hydroxysteroid dehydrogenases and P450 aromatase) and metabolism of steroids were assessed together with histological alterations of the gonads. During the spring sampling, delayed gamete maturation, intersexuality, fibrosis, and depressed ovarian P450 aromatase activity were observed in organisms from the most polluted sites. During the autumn sampling, those effects were less evident, indicating that fish might be more susceptible to endocrine disrupting chemicals during the reproductive period. Nonetheless, enhanced glucuronidation of testosterone and estradiol was observed. Overall, this work provides first evidences of significant alterations in the endocrine system of red mullet from highly impacted areas in the NW Mediterranean., This work was partially supported by the EC Project ENVK3-CT-2000-00025. R.M.-S. acknowledges a predoctoral fellowship from the Spanish Government. Dr. Rémi Thibaut acknowledges a I3P contract from the Spanish Government.

7 pages, 3 figures, 3 tables.-- PMID: 15719999 [PubMed]. Available online Jul 21, 2004., Water samples (n = 183) from Portuguese rivers were tested for the presence of endocrine disruptors using the recombinant yeast assay (RYA) combined with chemical identification of compounds having endocrine-disruption properties by liquid chromatography coupled to mass spectrometry. Ten selected locations were sampled monthly for a period of 20 months, from April 2001 to December 2002. More than 90% of samples showed either no detectable or low levels of estrogenicity (, This work has been supported by the Ministerio do Ambiente of Portugal (Endocrine disruption in river waters from Portugal). We acknowledge additional funding from the Spanish Ministry for Science and Technology (CTM2006-0313E, BMC2001-0246 and SAF2002-00371) and the European Union (SWIFT-WFD, SSPI-CT-2003-502492 and EURO-LIMPACS, GOCE-CT-2003-505540).

13 pages, 4 schemes, 2 tables.-- PMID: 14564440 [PubMed].-- Available online Oct 16, 2003., This paper is a review with more than 100 references discussing the immunochemical methods reported in the literature for the most important man-made chemicals with suspected endocrine disrupting activity. Details regarding immunizing hapten design, antibody production, and the features (limit of detection, dynamic range, specificity) of the most important immunochemical methods developed (ELISA, FIIA, immunosorbents, immunosensors, etc.) are presented for important environmental pollutants such as bisphenol A, phthalates, alkylphenol polyethoxylates, alkylphenols, polychlorinated biphenyl compounds, and dioxins. Availability of commercial reagents and methods is reported., This work was supported by INIA (VIN00–053-C3–2), the EC Quality of Life Program (Contract QLRT-2000–01670), and by CICYT (BIO2000–0351-P4–05, AGL2001–5005-E and AGL2002–04635-C04–03).

POCIS (polar organic chemical integrative sampler) is one of the passive sampler the most frequently used for the monitoring of dissolved organic micropollutants in surface waters. The advantage of such a passive sampling is to decrease quantification limits and to obtain a time-averaged water concentration. POCIS is used for hydrophilic molecules (log KOW < 4). The aim of this paper is to review the advantages and drawbacks of this tool for the evaluation of the river water quality downstream wastewater treatment plants outflow (WWTP). As planned in the AMPERES project, POCIS were used during 5 in situ sampling campaigns from November 2007 to September 2008 : on the Saône, the Jalle d'Eysines, the Ardières, the Bourbre and the Seine rivers. They were set up in surface waters, upstream and downstream WWTP outfow, and also within the WWTP effluent. Several chemical classes of organic molecules were studied: industrial substances such as alkylphenols and bisphenol A; also 5 estrogenic hormones; and other pharmaceuticals from various therapeutic classes, such as 9 antidepressants, 6 anti-inflammatories, 10 betablockers, 1 lipopenic, 3 bronchodilators; as well as theophylline and caffeine. POCIS were exposed for up to 28 days to study the accumulation kinetics and the linearity of uptake rates. Sampling repeatability was verified by the exposure of triplicates. To better evaluate the performance of POCIS, grab sampling was also performed at regular intervals during POCIS exposure. For the estrogenic hormones and betablockers, accumulation kinetics and sampling rates were studied in situ. Concerning alkylphenols and other pharmaceuticals, calibration was performed in the laboratory. We also tried to identify a molecule that could be used as internal surrogate or PRC (performance reference compound). Finally, POCIS is well adapted for the sampling of pharmaceuticals and alkylphenols. Its efficiency was not proved in this study for bisphenol A and estrogenic hormones. The optimal exposure duration is about 15 days. Concentration factors and decrease of quantification limits are significant except for hormones, betablockers and bronchodilators. Promising preliminary results obtained on deuterated atenolol used as PRC need to be confirmed in laboratory. This work confirms that POCIS is useful for the monitoring of hydrophilic organic molecules in river and waste waters., Le POCIS (polar organic chemical integrative sampler) est l'un des échantillonneurs intégratifs les plus utilisés pour la surveillance des micropolluants organiques dissous dans l'eau. L'avantage de ce type d'échantillonnage est d'abaisser les seuils de quantification et d'obtenir une concentration moyennée sur la durée d'exposition. Le POCIS est employé pour le suivi des molécules hydrophiles (log KOW < 4). L'objectif de cet article est de faire le point sur les avantages et inconvénients de cet échantillonneur pour l'évaluation de la qualité des eaux de surface impactées par des effluents de station d'épuration (STEP). Des POCIS ont été mis en ½uvre dans le cadre du projet AMPERES, lors de 5 campagnes d'échantillonnage réalisées entre novembre 2007 et septembre 2008 : sur la Saône, la Jalle d'Eysines, l'Ardières, la Bourbre et la Seine. Ces POCIS ont été installés dans les rivières, en amont et en aval de STEP, ainsi que dans l'effluent traité de ces mêmes stations. Plusieurs familles de molécules organiques ont été étudiées : des substances d'origine plutôt industrielle telles que les alkylphénols et le bisphénol A ; et aussi 5 hormones oestrogéniques ; et d'autres molécules pharmaceutiques appartenant à plusieurs familles thérapeutiques, telles que 9 antidépresseurs, 6 anti-inflammatoires, 10 bêtabloquants, 1 hypolipémiant, 3 bronchodilatateurs ; et enfin la théophylline et la caféine. Les POCIS ont été exposés jusqu'à 28 jours afin d'étudier in situ les cinétiques et la linéarité de l'accumulation. La répétabilité de l'échantillonnage a été vérifiée par l'exposition de triplicats de POCIS. Pour évaluer la pertinence de l'outil, des échantillons ponctuels ont été prélevés périodiquement sur chaque site pendant la durée d'exposition des POCIS. Pour ce qui concerne les hormones oestrogéniques et les bêtabloquants, les cinétiques d'accumulation et les taux d'échantillonnage ont été étudiés in situ. Pour ce qui concerne les alkylphénols et certains médicaments, ces études ont été menées en laboratoire. Enfin, des essais ont été entrepris pour trouver une molécule pouvant jouer le rôle d'étalon interne ou de PRC (performance reference compound). Le POCIS se révèle adapté pour l'échantillonnage des micropolluants d'origine pharmaceutique et des alkylphénols. Son intérêt n'a pas été démontré ici pour les hormones et le bisphénol A. La durée optimale d'exposition est d'environ 15 jours. Les facteurs de concentration ou abaissements des seuils de quantification avec le POCIS sont significatifs sauf pour les hormones, bêtabloquants et bronchodilatateurs. Des premiers résultats prometteurs sur l'aténolol deutéré utilisé comme PRC restent à confirmer en laboratoire. Les travaux confirment que l'outil est pertinent pour la surveillance de molécules organiques hydrophiles dans les eaux résiduaires et de surface.

In this paper, we studied Fenton and photo-Fenton-advanced oxidation processes for degradation of alkylphenolic compounds under various experimental conditions. Bisphenol A (BPA) has been degraded more slowly than 3,5-dimethylphenol (3,5-DMP) and 2,5-dimethylphenol (2,5-DMP), but faster than 2,4,6-trimethylphenol (2,4,6-TMP) under the same experimental conditions (ratios of Fe2+/Organic Substrate-2, H2O2/Organic Substrate=14). Mineralization rate of BPA was increased by irradiation of Fenton reagent with UV light (photo-Fenton, 40 W UV lamp), and 89% of mineralization was achieved for 700 ml solutions, while only 63% mineralization was observed in absence of UV-light (Fenton) at 250 min reaction times. Considerable excess of H2O2 in reaction medium caused decreases in mineralization efficiency, due to scavenging the hydroxyl radicals generated in Fenton and photo-Fenton reactions. The efficiency of the degradation was improved by loading H2O2 into reaction medium in small amounts at various time intervals. © by PSP 2006.

L’étude ECUME était une opération destinée à tester localement dans les eaux côtières du littoral normand, des outils développés nationalement lors de nombreux travaux, et pressentis pour être utilisés lors des prochaines campagnes d’évaluation de la qualité chimique des masses d’eau littorales pour la DCE. Ceci afin de déterminer la méthode la plus adaptée et opérationnelle de les déployer, et comparer leurs résultats entre eux et par rapport aux connaissances actuelles des niveaux de contamination. Trois sites ont été choisis : Chausey, baie des Veys et estuaire de Seine. Les résultats des analyses chimiques dans l’eau de mer grâce aux DGT, POCIS, SBSE, et dans les moules ont permis de confirmer le contraste du niveau de contamination en éléments traces métalliques et en polluants organiques entre les trois sites de l’étude, avec une contamination croissante de Chausey, à la baie des Veys, à l’estuaire de Seine dans l’eau, les moules, et grâce aux biomarqueurs. Parmi les trois biomarqueurs testés, la stabilité lysosomale et le dénombrement des micronoyaux se sont avérés les plus intéressants. Enfin, un bilan opérationnel ainsi qu’une synthèse des travaux en cours à l’échelle nationale sont présentés. Ce premier reste mitigé avec la nécessité de revoir notamment la méthode de mouillage dans les eaux littorales normandes.