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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.

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, the effect of the addition of waste on the emissions from coal co-combustion was investigated. Coal was co-combusted with different additions of medium-density fiberboard and polyethylene terephthalate plastic (10 and 50%), in a low-power boiler (18 W). Polycyclic aromatic hydrocarbons, phenols, alkylphenols, phthalates, and biomass burning markers emissions were determined. Gas chromatography, coupled with a mass spectrometry detector, was used to analyze these compounds in particulate matter and gas phase, after extraction and derivatization. The emissions of polycyclic aromatic hydrocarbons were the highest among all the compounds determined. The total emission of these compounds was 215.1 mg/kg for coal, and 637.7 and 948.3 mg/kg for a 10 and 50% additive of polyethylene terephthalate plastic, respectively. For the 10 and 50% additive of medium-density fiberboard, the total emission was 474.2 and 464.0 mg/kg, respectively. The 50% addition of PET also had the highest emissions of phenols (638.5 mg/kg), alkylphenols (246.5 mg/kg), and phthalates (18.1 mg/kg), except for biomass burning markers, where the emissions were the highest for the 50% addition of medium-density fiberboard (541.3 mg/kg). In our opinion, the obtained results are insufficient for the identification of source apportionment from household heating.

The Transient Receptor Potential Ankyrin 1 cation channel (TRPA1) is a broadly-tuned chemosensor expressed in nociceptive neurons. Multiple TRPA1 agonists are chemically unrelated non-electrophilic compounds, for which the mechanisms of channel activation remain unknown. Here, we assess the hypothesis that such chemicals activate TRPA1 by inducing mechanical perturbations in the plasma membrane. We characterized the activation of mouse TRPA1 by non-electrophilic alkylphenols (APs) of different carbon chain lengths in the para position of the aromatic ring. Having discarded oxidative stress and the action of electrophilic mediators as activation mechanisms, we determined whether APs induce mechanical perturbations in the plasma membrane using dyes whose fluorescence properties change upon alteration of the lipid environment. APs activated TRPA1, with potency increasing with their lipophilicity. APs increased the generalized polarization of Laurdan fluorescence and the anisotropy of the fluorescence of 1,6-diphenyl-1,3,5-hexatriene (DPH), also according to their lipophilicity. Thus, the potency of APs for TRPA1 activation is an increasing function of their ability to induce lipid order and membrane rigidity. These results support the hypothesis that TRPA1 senses non-electrophilic compounds by detecting the mechanical alterations they produce in the plasma membrane. This may explain how structurally unrelated non-reactive compounds induce TRPA1 activation and support the role of TRPA1 as an unspecific sensor of potentially noxious compounds. This work was funded by grants of the Research Council of the KU Leuven (C14/18/086) and the Fund for Scientific Research Flanders (FWO: G0D0417N and G0B2219N). J.B.S. has a Postdoctoral Mandate of the Research Council of the KU Leuven. R.N. is funded by a PhD Fellowship of the FWO. Y.A.A. has a Postdoctoral Fellowship of the FWO. Talavera, K (corresponding author), Katholieke Univ Leuven, Dept Cellular & Mol Med, Lab Ion Channel Res, B-3000 Leuven, Belgium ; VIB Ctr Brain & Dis Res, B-3000 Leuven, Belgium. justyna.startek@kuleuven.be; milicialina13@gmail.com; robbe.naert@kuleuven.be; andrei.segal@kuleuven.be; yeranddy.aguiaralpizar@uhasselt.be; thomas.voets@kuleuven.be; karel.talavera@kuleuven.be

The results of the study of removal of nonylphenol, octylphenol and their ethoxylates from real industrial and municipal wastewater are presented. Industrial wastewater was pre-treated by coagulation with FeCl3 and adsorption on zeolite, before discharging into municipal sewer system. Their removal efficiencies in primary sedimentation tank of municipal WWTP were very low. From the practical point of view, the highest and the most significant removal efficiencies within the whole WWTP were observed for nonylphenol and nonylphenol ethoxylates. Dominancy of abiotic mechanisms of alkylphenols removal follows from adsorption measurements. Activated sludge cultivated in lab-scale extended aeration tank accounted for relatively high adsorption affinity to these substances. Activated sludge sampled from municipal wastewater treatment plant (MWWTP) receiving industrial wastewater containing alkylphenols accounted for very low adsorption affinity to these pollutants. Significantly higher removal efficiency of octylphenol ethoxylates was observed with the O3/granular active carbon (GAC) process compared to the ozonation process alone. Lower toxicity impact of intermediates and products of ozonation treatment on Vibrio fischeri was measured in comparison to the O3/GAC process. Actually, the municipal WWTP effluent discharge concentration values complies with EQS values, including nonylphenols. This work is licensed under a Creative Commons Attribution 4.0 International License.

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.

The spatial and temporal distribution of selected endocrine disrupting compounds (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol, and bisphenol A) in two coastal areas of the Iberian Peninsula (Ria de Vigo and Mar Menor lagoon) were evaluated for the first time. Seawater and sediment samples collected during spring and autumn of 2015 were analysed using greener extraction techniques and liquid chromatography-tandem mass spectrometry. The presence of branched isomers (4-tert-octylphenol and nonylphenol) and bisphenol A in almost all seawater and sediment samples demonstrated their importance as pollutants in the frame of water policy, while no concentrations of linear isomers (4-n-octylphenol and 4-n-nonylphenol) were found. Higher seawater levels were observed in Mar Menor lagoon, especially in spring, associated with wastewater treatment plant effluents and nautical, agricultural and industrial activities. Similar sediment concentrations were measured in both studied areas, being nonylphenol levels five times higher than those measured for the other EDCs. Experimental sediment–water partition coefficients showed a moderate sorption of target compounds to sediments. Risk quotients for water compartment evidenced a moderate risk posed by nonylphenol, considering the worst-case scenario. For sediments, moderate risk related to 4-tert-octylphenol and high risk to nonylphenol were estimated., Sí

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

In this study, a polymer, prepared by crosslinking cyclodextrin (CD) by means of a polycarboxylic acid, was used for the removal of pollutants from spiked solutions and discharge waters from the surface treatment industry. In spiked solutions containing five metals, sixteen polycyclic aromatic hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic groups and CD cavities, the adsorption mechanism involves four main interactions: ion exchange, electrostatic interactions and precipitation for metal removal, and inclusion complexes for organics removal. In industrial discharge waters, competition effects appeared, especially because of the presence of calcium at high concentrations, which competed with other pollutants for the adsorption sites of the adsorbent.

This paper reports the reconstruction of the pollution history of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in the Baltic Sea. Alkylphenols are endocrine-disrupting compound and therefore toxic to aquatic organisms. Sediment cores were collected from regions with relatively stable sedimentation conditions. The cores were dated by the 210Pb method. The OP and NP were determined using HPLC-FL. The highest inventory of these compounds was observed in the Gotland Deep (610 μg m2 of NP and 47 μg m2 of OP) and the lowest—on the slope of the Gdansk Deep (24 μg m2 of NP and 16 μg m2 of OP). Such spatial distribution was probably, among other factors, the result of the uplift of the sea floor. The pollution trends of OP and NP in sediments coincided with the following: (1) the beginnings of eutrophication (1960s/1970s of the twentieth century) and (2) strong increase in the areal extent and volume of hypoxia and anoxia in the Baltic (present century). Electronic supplementary material The online version of this article (doi:10.1007/s11356-016-6262-8) contains supplementary material, which is available to authorized users.

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).

The enantioselective oxyfunctionalisation of C−H bonds is a highly interesting reaction, as it provides access to chiral alcohols that are important pharmaceutical building blocks. However, it is hard to achieve using traditional methods. One way in which it can be achieved is through the action of oxidative enzymes. Although many reports of the oxyfunctionalisation capabilities of enzymes at an analytical scale have been published, reports on the use of enzymes to achieve oxyfunctionalisation on a synthetically relevant scale are fewer. Here, we describe the scale-up of the conversion of 4-ethylphenol to (R)-1-(4′-hydroxyphenyl)ethanol using the flavin-dependent enzyme vanillyl alcohol oxidase. The process was optimised by testing different reaction media and substrate and enzyme concentrations and by performing it under an oxygen atmosphere. Under optimised reaction conditions, 4.10 g (R)-1-(4′-hydroxyphenyl)ethanol at 97% ee was obtained from 10 g 4-ethylphenol (isolated yield 36%). These results highlight some of the challenges that can be encountered during scale-up of an enzymatic oxyfunctionalisation process to a synthetically relevant scale and will be of use for the development of enzymatic processes for the synthesis of industrially relevant compounds. (Figure presented.).

Alkylphenol (AP) and bisphenol A (BPA) contamination of urban runoff has already been established. Potential sources of these contaminants in runoff are endogenous to the urban watershed and are mainly related to traffic and leaching from construction materials. This article summarizes the results of experimental work carried out on a selection of building materials, automotive materials, and consumables, which can be in contact with rain, to assess their potential emission of alkylphenols, alkylphenol ethoxylates, and bisphenol A into runoff. 36 samples of materials, new and used, across 7 major families of building materials (PVC, concrete, polycarbonate, SBS-modified bitumen, drainage materials) and automotive materials (body, tires) were subjected to leaching tests with methanol and then, for a selection of them, with water. Automotive fluids were also directly analyzed. The results demonstrate the ubiquitous presence of APs and BPA in urban materials and their extractable character with water. The compounds with the strongest emission rates were bisphenol A and nonylphenol. The most important BPA emissions into water (10 to 300 ng/g) were measured for polycarbonate, tires, some car bodies, and PVC. Nonylphenol was leached in large quantities (1 to 10 ng/g) from PVC, some concretes, SBS-modified bitumen, and body samples. The tires were the only materials having a strong emission in octylphenol (1 to 10 ng/g). The analysis of automotive fluids confirmed the presence of BPA (0.3 to 5.5 g/L) and nonylphenol (2.3 to 2.9 mg/L) in brake fluids, while APs and BPA were found at trace levels in coolants and windscreen washer. Graphical abstract ᅟ.

Operational planned discharges of produced water (PW) to the marine environment from offshore oil production installations, contain low concentrations of dispersed oil compounds, like polycyclic aromatic hydrocarbons (PAH) and alkylated phenols (APs). Biotransformation in natural seawater (SW) of naphthalene/PAH and phenol/AP in field-collected PW from a North Sea platform was investigated in this biodegradation study. The PW was diluted in SW from a Norwegian fjord, and the biodegradation study was performed in slowly rotating carousels at environmental conditions (13⁰C) over a period of 62 days. Naphthalene/PAH and phenol/AP biotransformation was determined by first-order rate kinetics, after normalization against the recalcitrant biomarker 17α(H),21β(H)-Hopane. The results from this study showed total biotransformation half-lives ranging from 10 to 19 days for groups of naphthalenes and PAH, while half-lives for APs (C0- to C9-alkylated) were 10 to 14 days. Biotransformation half-lives of single components ranged from 8 to >100 days for naphthalenes and PAHs (median 16 days), and from 6 to 72 days (median 15 days) for phenols and AP. Four of the tested PAHs (chrysene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(g,h,i,)perylene) and one AP (4-tert-butylphenol) showed biotransformation half-lives >50 days. This is one of a few studies that has investigated the potential for biodegradation of PW in natural SW. Methods and data from this study may be used as a part of Risk Based Approaches (RBA) for assessments of environmental fate of PW released to the marine environment and as part of the persistence related to risk.

In the present study five different types of alkylphenols, each of the two different types of mono and poly-aromatic hydrocarbons were selected for degradation, and conversion into poly-3-hydroxybutyrate (PHB) using the Bacillus sp. CYR1. Strain CYR1 showed growth with various toxic organic compounds. Degradation pattern of all the organic compounds at 100 mg/l concentration with or without addition of tween-80 were analyzed using high pressure liquid chromatography (HPLC). Strain CYR1 showed good removal of compounds in the presence of tween-80 within 3 days, but it took 6 days without addition of tween-80. Strain CYR1 showed highest PHB production with phenol (51 ± 5%), naphthalene (42 ± 4%), 4-chlorophenol (32 ± 3%) and 4-nonylphenol (29 ± 3%). The functional groups, structure, and thermal properties of the produced PHB were analyzed. These results denoted that the strain Bacillus sp. CYR1 can be used for conversion of different toxic compounds persistent in wastewaters into useable biological polyesters.

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.

This study assessed the environmental risk on coastal ecosystems posed by three phenolic compounds of special environmental and human health concern used in plastics and household products: bisphenol A (BPA), triclosan (TCS) and 4-nonylphenol (4-NP). These three chemicals are among the organic contaminants most frequently detected in wastewater. The most toxic compound tested was 4-NP, with 10% effective concentration at 11.1 μg L−1 for Isochrysis galbana, 110.5 μg L−1 for Mytilus galloprovincialis, 53.8 μg L−1 for Paracentrotus lividus, and 29.0 μg L−1 for Acartia clausi, followed by TCS (14.6 μg L−1 for I. galbana, 149.8 μg L−1 for M. galloprovincialis, 129.9 μg L−1 for P. lividus, and 64.8 μg L−1 for A. clausi). For all species tested, BPA was the less toxic chemical, with toxicity thresholds ranging between 400 and 1200 μg L−1 except for A. clausi nauplii (186 μg L−1). The relatively narrow range of variation in toxicity considering the broad physiological differences among the biological models used point at non-selective mechanisms of toxicity for these aromatic organics. Microalgae, the main primary producers in pelagic ecosystems, showed particularly high susceptibility to the chemicals tested. When the toxicity thresholds experimentally obtained were compared to the maximum environmental concentrations reported in coastal waters, the risk quotients obtained correspond to very low or low risk for BPA and TCS, and from low to high for 4-NP., SI

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.

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.

Background: Laboratory and human studies raise concerns about endocrine disruption and asthma resulting from exposure to chemicals in consumer products. Limited labeling or testing information is available to evaluate products as exposure sources. Objectives: We analytically quantified endocrine disruptors and asthma-related chemicals in a range of cosmetics, personal care products, cleaners, sunscreens, and vinyl products. We also evaluated whether product labels provide information that can be used to select products without these chemicals. Methods: We selected 213 commercial products representing 50 product types. We tested 42 composited samples of high-market-share products, and we tested 43 alternative products identified using criteria expected to minimize target compounds. Analytes included parabens, phthalates, bisphenol A (BPA), triclosan, ethanolamines, alkylphenols, fragrances, glycol ethers, cyclosiloxanes, and ultraviolet (UV) filters. Results: We detected 55 compounds, indicating a wide range of exposures from common products. Vinyl products contained > 10% bis(2-ethylhexyl) phthalate (DEHP) and could be an important source of DEHP in homes. In other products, the highest concentrations and numbers of detects were in the fragranced products (e.g., perfume, air fresheners, and dryer sheets) and in sunscreens. Some products that did not contain the well-known endocrine-disrupting phthalates contained other less-studied phthalates (dicyclohexyl phthalate, diisononyl phthalate, and di-n-propyl phthalate; also endocrine-disrupting compounds), suggesting a substitution. Many detected chemicals were not listed on product labels. Conclusions: Common products contain complex mixtures of EDCs and asthma-related compounds. Toxicological studies of these mixtures are needed to understand their biological activity. Regarding epidemiology, our findings raise concern about potential confounding from co-occurring chemicals and misclassification due to variability in product composition. Consumers should be able to avoid some target chemicals—synthetic fragrances, BPA, and regulated active ingredients—using purchasing criteria. More complete product labeling would enable consumers to avoid the rest of the target chemicals.

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 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.

Comprehensive two-dimensional gas chromatography has been successfully applied to the analysis of various organic contaminants; however, few studies report its use in the analysis of endocrine disrupting compounds. These compounds are suspected to cause dysfunction of the endocrine system in humans and animals. This work describes the development of a method to analyse dibutylphthalate, benzylbutylphthalate, nonylphenol and octylphenol in water using solid-phase microextraction (SPME) and comprehensive two-dimensional gas chromatography with a flame ionisation detector. The merit parameters of the comprehensive two-dimensional gas chromatography with flame ionisation detector method were weighed against a gas chromatography/mass spectrometry-single ion monitoring method of endocrine disrupting compounds analysis. The compounds were evaluated over a concentration range of 0.2 to 6.0 mu g L-1. The use of a two-dimensional chromatography method proved to be advantageous in analysing endocrine disrupting compounds, according to the observed increase of the signal relative to the noise and peak resolution. publishersversion published

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

Two oriental lacquers from Rhus succedanea and Melanorrhoea usitata were characterised by Py-GC–MS with in situ silylation using HMDS. Pyrolytic markers, which were helpful in differentiating between the lacquers, were identified in their silylated forms, and the mass spectra are presented and discussed. Aliphatic and aromatic hydrocarbons were formed as well as TMS derivatives of alkylcatechols and alkylphenols, and relative characteristic pyrolytic profiles were compared for the two lacquers. The method, here applied for the first time to the characterisation of the Vietnamese and Burmese lacquers, proved successful not only in distinguishing between the two lacquers, but also in highlighting the polymerisation processes undergone by the saps in the formation of the lacquer layers. The results obtained demonstrated that in situ Py/silylation-GC–MS with using HMDS is a suitable tool for the analysis of all oriental lacquers with possible application to diagnose their presence in samples of unknown composition.

A solid phase derivative extraction method using acetic anhydride was developed for the determination of chlorophenols and alkylphenols in water and fruit juice by gas chromatography–mass spectrometry (GC–MS). The quantitative extraction was performed by passing 100 mL of sample prepared in 0.1 mol L−1sodium hydroxide through a column packed with 500 mg of a strong anion-exchange resin at a flow rate of 0.75 mL min−1. The retained phenols were quantitatively derivatized in the column by the introduction of 0.25 mL of acetic anhydride. The derivatized phenols were eluted with 3.0 mL of hexane and the effluent was dried under nitrogen. The final volume was diluted to fifty microliters with hexane and analyzed by GC–MS. Under the optimum conditions, preconcentration factors of 2000, limits of detection between 0.005 and 1.796 µg L−1, and relative standard deviations of 2.1% to 6.7% were obtained. The method was successfully applied to wastewater and fruit juice and the recoveries of phenols were between 76% and 111%. © 2015, Taylor & Francis Group, LLC.

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; During the last 10 years, the appearance of emerging organic compounds described as endocrine disrupters in wastewaters and water resources has become a major concern for both society and public health authorities, the whole industrial world and the agricultural sector. Endocrine disrupting compounds are found in various environmental compartments such as water, sediments, soils and atmosphere, as a result of their wide usage. Numerous products are concerned including surfactants, industrial additives and formulations, pharmaceuticals, and also personal care products. However, the existing conventional water treatment plants were not designed for these new contaminants. In the present study, an overview of the literature on methods for the elimination (removal and/or degradation) of emerging trace organic contaminants is presented. This review is limited to details of the treatment of one class of endocrine disrupters, namely alkylphenols and their polyethoxylate derivatives, which are suspected to interfere with the hormonal system of wildlife. The technologies proposed for alkylphenol treatment include membrane treatment using biological (membrane bioreactors) or physical processes (membrane filtration such as nanofiltration), biotechnological-based methods (biofilms, immobilized enzymes, etc.), adsorption-oriented processes using conventional (activated carbons) or nonconventional adsorbents (clays, cyclodextrin, etc.), and advanced oxidation processes (photocatalysis, photolysis, and sonochemistry). Examples are taken from the literature to illustrate various features of the technologies used in decontamination methods. Among them, photocatalytic oxidation is an interesting tool for alkylphenol treatment due to its potential to reach complete mineralization.

A chromatographic procedure for the preparative isolation of six different 6-alkylsalicylic acids (syn. ginkgolic acids) with as alkyl substituents C13:0, C15:0, C15:1, C17:1, C17:2 and, tentatively C17:3 from Ginkgo biloba leaves was developed. The procedure consisted of a combination of normal-phase, reversed-phase and argentation chromatography. The compounds were characterised by means of UV, 1H-NMR and 13C-NMR spectroscopy, and mass spectrometry after silylation. A 15 cm C18 RP-HPLC column connected in series with a 20 cm silver(I) loaded cation exchanger HPLC column in combination with the solvent methanol-water (93:7) acidified with 0.1% formic acid was capable of separating the ginkgolic acids C13:0, C15:1, C17:2, C15:0 and C17:1 within 21 min on an analytical scale. The separation is based on a combination of reversed-phase mechanisms and double bond complexation. Detection took place by UV at 311 nm. The separation is a good starting point for the development of a quantitative procedure for the five major ginkgolic acids in Ginkgo leaves and standardised extracts.

This paper was presented at the Symposium on Estrogens in the Environment, III: Global Health Implications held 9-11 January 1994 in Washington, DC., Estrogens are defined by their ability to induce the proliferation of cells of the female genital tract. The wide chemical diversity of estrogenic compounds precludes an accurate prediction of estrogenic activity on the basis of chemical structure. Rodent bioassays are not suited for the large-scale screening of chemicals before their release into the environment because of their cost, complexity, and ethical concerns. The E-SCREEN assay was developed to assess the estrogenicity of environmental chemicals using the proliferative effect of estrogens on their target cells as an end point. This quantitative assay compares the cell number achieved by similar inocula of MCF-7 cells in the absence of estrogens (negative control) and in the presence of 17 beta-estradiol (positive control) and a range of concentrations of chemicals suspected to be estrogenic. Among the compounds tested, several "new" estrogens were found; alkylphenols, phthalates, some PCB congeners and hydroxylated PCBs, and the insecticides dieldrin, endosulfan, and toxaphene were estrogenic by the E-SCREEN assay. In addition, these compounds competed with estradiol for binding to the estrogen receptor and increased the levels of progesterone receptor and pS2 in MCF-7 cells, as expected from estrogen mimics. Recombinant human growth factors (bFGF, EGF, IGF-1) and insulin did not increase in cell yields. The aims of the work summarized in this paper were a) to validate the E-SCREEN assay; b) to screen a variety of chemicals present in the environment to identify those that may be causing reproductive effects in wildlife and humans; c) to assess whether environmental estrogens may act cumulatively; and finally d) to discuss the reliability of this and other assays to screen chemicals for their estrogenicity before they are released into the environment., This work was partially supported by grants from the W. Alton Jones Foundation, EPA-CR 820301, NIH-CA-13410, and NSF-DCB-9105594. The assistance of The Center for Reproductive Research at Tufts University (P30 HD 28897) is gratefully acknowledged.

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.

Two rapid methods were evaluated for the simultaneous extraction of seven parabens and two alkylphenols from soil based on matrix solid-phase dispersion (MSPD) and microwave-assisted extraction (MAE). Soil extracts were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide and analyzed by gas chromatography with mass spectrometry. Extraction and clean-up of samples were carried out by both methods in a single step. A glass sample holder, inside the microwave cell, was used in MAE to allow the simultaneous extraction and clean-up of samples and shorten the MAE procedure. The detection limits achieved by MSPD were lower than those obtained by MAE because the presence of matrix interferences increased with this extraction method. The extraction yields obtained by MSPD and MAE for three different types of soils were compared. Both procedures showed good recoveries and sensitivity for the determination of parabens and alkylphenols in two of the soils assayed, however, only MSPD yielded good recoveries with the other soil. Finally, MSPD was applied to the analysis of soils collected in different sites of Spain. In most of the samples analyzed, methylparaben and butylparaben were detected at levels ranging from 1.21 to 8.04 ng g -1 dry weight and 0.48 to 1.02 ng g -1 dry weight, respectively. © 2011 Springer-Verlag.

In this study, a methodology for pressurized solvent extraction of alkylphenols (APs) and alkylphenol ethoxylates (APEOs) from biosolids was optimized by utilizing a biosolid natively containing these compounds at a high concentration level. Optimization of the extraction was carried out through a multivariate analysis experimental design with a central composite design (CCD) producing the following optimum values for the variables: temperature of 129 ºC, extraction time per cycle of 34 min in two cycles and acetone as extraction solvent. Upon comparison with Soxhlet extraction, this methodology turned out to be more efficient for the extraction of APEOs and of similar efficiency for APs. On the other hand, the methodology is considerably faster than Soxhlet and uses a smaller amount of extraction solvent. Concentrations of 204 ± 20 and 1053 ± 23 mg kg-1 for nonylphenol and nonylphenol-ethoxylate, respectively, were determined in the biosolid sample assayed. Neste estudo, uma metodologia de extração em solvente pressurizado de alquilfenóis (APs) e alquilfenóis etoxilados (APEOs) a partir de biosólidos foi otimizada utilizando-se um biosólido contendo nativamente estes compostos em um nível de concentração elevada. A otimização da extração foi realizada através de um planejamento experimental de análise multivariada com um planejamento composto central (CCD) produzindo os seguintes valores otimizados: temperatura de 129 ºC, tempo de extração por ciclo de 34 min em dois ciclos e acetona como solvente de extração. Em comparação com a extração Soxhlet, esta metodologia acabou por ser mais eficiente para a extração de APEOs e de eficiência semelhante para a extração de APs. Por outro lado, a metodologia é consideravelmente mais rápida do que a de Soxhlet e usa uma pequena quantidade de solvente de extração. As concentrações de 204 ± 20 e 1053 ± 23 mg kg-1 de nonilfenol e nonilfenol-etoxilato, respectivamente, foram determinadas na amostras de biosólido.

Purpose: Sediments can function as secondary source for water pollution of aerobically biodegradable non-halogenated organic compounds, which are persistent in anaerobic sediments. The mass transfer of compounds from sediment to bulk water depends on hydraulic conditions. In this study, desorption, mass transfer and biodegradation are investigated under settled and resuspended sediment conditions for branched nonylphenol (NP), which was used as model compound for aerobically biodegradable and anaerobic persistent compounds. Materials and methods: Continuous flow through reactor experiments were performed in duplicate with aged NP polluted sediment under sterile and non-sterile conditions to investigate the mass transfer and combined mass transfer and biodegradation. Results and discussion: The mass transfer of NP from the sediment bed to the bulk water decreased from 5.1 ± 0.6 μg d-1 to a stable value of 0.3±0.02 μg d-1. The desorbed NP in the non-sterile reactors was biodegraded in the first 20 days of the experiment. At the end of the settled sediment conditions, the biodegradation became very limited, and the mass transfer was comparable to the mass transfer under sterile conditions. Upon resuspension, the NP concentration in the bulk water increased instantaneously in all reactors with a factor of 100. This immediate, increased mass transfer of NP from the sediment was larger than the amount that can be biodegraded under optimal conditions. Under non-sterile conditions, a second increase in the mass transfer was observed. However, the amount of desorbing NP during this second increase in mass transfer can be biodegraded under optimal environmental conditions. Conclusions: NP desorbs continuously at low concentrations from the sediment bed into the bulk water, which can almost be completely biodegraded. Resuspension of NP-polluted sediment initially led to an increase in the desorbing NP concentrations and can be followed by a subsequent reduction of the concentrations due to biodegradation under environmental conditions where biodegradation of NP can occur. © The Author(s) 2009.

International audience; The study proposes an analytical method to quantify 10 alkylphenols and 12 pesticides at ultra-trace levels by liquid chromatography in reverse mode coupled to positive electrospray ionisation-tandem mass spectrometry. The extraction procedure from environmental solids was optimised by pressurised liquid extraction using acetonitrile:isopropanol (1:1, v/v). The influence of several extraction experimental factors, temperature, pressure, duration and number of cycles, related to the PLE was investigated by an original and efficient chemometric approach. The optimised extraction method (80 degrees C, 40 bar, 10 min, 1 cycle) exhibited recoveries between 67 and 127% with RSD mostly under 13%. The whole method was applied to real samples: sludge, suspended materials, atmospheric fallouts and roof deposit. Pollutant levels were between 1 microg kg(-1) and 5.9 mg kg(-1).

The chemical analysis and quality control of Ginkgo leaves, extracts, phytopharmaceuticals and some herbal supplements is comprehensively reviewed. The review is an update of a similar, earlier review in this journal [T.A. van Beek, J. Chromatogr. A 967 (2002) 21-55]. Since 2001 over 3000 papers on Ginkgo biloba have appeared, and about 400 of them pertain to chemical analysis in a broad sense and are cited herein. The more important ones are discussed and, where relevant, compared with the best methods published prior to 2002. In the same period over 2500 patents were filed on Ginkgo and the very few related to analysis are mentioned as well. Important constituents include terpene trilactones, i.e. ginkgolide A, B, C, J and bilobalide, flavonol glycosides, biflavones, proanthocyanidins, alkylphenols, simple phenolic acids, 6-hydroxykynurenic acid, 4-O-methylpyridoxine and polyprenols. In the most common so-called "standardised" Ginkgo extracts and phytopharmaceuticals several of these classes are no longer present. About 130 new papers deal with the analysis of the terpene trilactones. They are mostly extracted with methanol or water or mixtures thereof. Supercritical fluid extraction and pressurised water extraction are also possible. Sample clean-up is mostly by liquid-liquid extraction with ethyl acetate although no sample clean-up at all in combination with LC/MS/MS is gaining in importance. Separation and detection can be routinely carried out by RP-HPLC with ELSD, RI or MS, or by GC/FID or GC/MS after silylation. Hydrolysis followed by LC/MS allows the simultaneous analysis of terpene trilactones and flavonol aglycones. No quantitative procedure for all major flavonol glycosides has yet been published because they are not commercially available. The quantitation of a few available glycosides has been carried out but does not serve a real purpose. After acidic hydrolysis to the aglycones quercetin, kaempferol and isorhamnetin and separation by HPLC, quantitation is straightforward and yields by recalculation an estimation of the original total flavonol glycoside content. A profile of the genuine flavonol glycosides can detect poor storage or adulteration. Although the toxicity of Ginkgo alkylphenols upon oral administration has never been undoubtedly proven, most suppliers limit their content in extracts to 5 ppm and dozens of papers on their analysis were published. One procedure in which a methanolic extract is directly injected on a C8 HPLC column appears superior in terms of sensitivity (5 ppm), separation, simplicity and validation and will be incorporated in the European Pharmacopoeia. Alternatively GC/MS and ELISA methods can be used. A sharp contrast to the plethora of papers on terpene trilactones, flavonol glycosides, and ginkgolic acids forms the low number of papers on biflavones, proanthocyanidins, simple phenolics, simple acids, and other constituents that make up the remaining 70% of Ginkgo standardised extracts. More research in this direction is clearly needed. For the analysis of Ginkgo proanthocyanidins (7%) for instance, no reliable assays are yet existing. Finally the growing literature on pharmacokinetic and fingerprinting studies of Ginkgo is briefly summarised.

International audience; Innovative and simultaneous multiresidue analytical methods of 33 multi-class pollutants in wastewaters, surface and ground waters, using solid phase extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) are presented. Target compounds include several groups of emerging and persistent contaminants derived from the European priority list of the registration evaluation and authorisation of chemicals system (REACH): organochlorine (8) and organophosphorus (2) pesticides, carbamates (2), fungicides (8), phthalates (2), alkylphenols (10) and bisphenol A. The recovery rates of the SPE gave levels ranged from 84 to 118% with exception of some compounds that yielded lower (methamidophos (50%), p,p'-DDT (60%) and o,p'-DDT (72%)) but all recoveries were acceptable. Low limits of detection (LOD) varied between 0.2 and 88.9 ngL(-1) (except for HPTE and 4n-octylphenol giving 161 and 220 ngL(-1), respectively). A study of matrix effects was performed in order to evaluate the best and reliable calibration approach. The developed analytical method was successfully applied to the analysis of the 33 substances in wastewater effluents as well as surface and ground waters. The most frequently detected families were alkylphenols and industrial endocrine disrupting compounds (phthalates and bisphenol A).

This thesis has been designed to improve the understanding of the distribution pattern and transport mechanisms of alkylphenols and the phthalates in the coastal margins, especially the roles of the air-sea exchanges in these processes. Henry’s Law Constants (HLC) were determined for the diastereomeric mixture of NP and t- OP in artificial seawater over given temperature range using a dynamic equilibrium system. An analytical method has been developed for the simultaneous extraction and determination of trace tertiary octylphenol (t-OP), technical nonylphenol isomers (NP), nonylphenol monoethoxylate isomers (NP1EO) and the phthalates in the atmosphere and sea water using gas chromatography-mass spectrometry (GC-MS). The method was successfully applied to the determination of APs and the phthalates in the atmosphere and sea water samples collected from the North Sea. A decreasing concentration profile of NP, t-OP, NP1EO and the phthalates appeared as the distance from the coast increased to the central part of the North Sea. Air-sea exchanges of t-OP, NP, DBP, BBP, and DEHP were estimated using the two-film resistance model based upon relative air-water concentrations. The average of air-sea exchange fluxes indicates a net deposition is occurring. These results suggest that the air–sea vapour exchange is an important process that intervenes in the mass balance of alkylphenols and the phthalates in the North Sea. Das primäre Ziel dieser Arbeit bestand darin, das Wissen über Verteilung und Transport von Alkylphenolen und Phthalaten in der Küstenzone, unter besonderer Berücksichtigung des Austausches zwischen Meer und Atmosphäre, zu vertiefen. Hierzu wurde eine spurenanalytische Methode zur gleichzeitigen Extraktion und Messung, von tertiärem- Oktylphenol, technischem Nonylphenol- Isomeren (NP), Nonylphenol- Monoethoxylat Isomeren (NP1EO) und Phthalaten im Meer und der Atmosphäre mittels Gaschromatographie-Massenspektrometrie (GC-MS) entwickelt. Die Methode wurde erfolgreich für die Bestimmung dieser Verbindungen in Luft und Wasserproben aus der Nordsee angewendet. Die Ergebnisse dieser Messungen zeigen sowohl für die Wasserphase wie auch für die Luft einen abnehmenden Konzentrationsgradienten mit zunehmender Entfernung von den Küsten. Für diastereomere Gemische von Nonylphenol und Oktylphenol in künstlichem Meereswasser wurden die Henry-Konstanten über einen Temperaturbereich von 278 K bis 298 K ermittelt. Der Phasentransfer von t-OP, NP, DBP, BBP und DEHP, zwischen Gas- und Wasserphase wurde mit einem “two-film resistance model“, über die Luft- und Wasserkonzentrationen ermittelt. Die gemittelten Phasenflüsse weisen für diese Verbindungen auf eine Nettodeposition hin. Diese Ergebnisse legen nahe, dass der Gasaustausch zwischen der Meeresoberfläche und der Luft entscheidenden Einfluss auf die Massenbilanz der Alkylphenole und der Phthalate in der Deutschen Bucht hat.

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.

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).