Assessing the estrogenic potency in a Portuguese wastewater treatment plant using an integrated approach.

The estrogenic potency of a wastewater treatment plant (WWTP) was evaluated using chemical and biological analyses, which showed that after the station treatment processes some of the selected endocrine disruptor compounds (EDCs) were still present in the treated effluent (e.g., bisphenol A, alkylphenols, estrone).

Analysis and occurrence of alkylphenolic compounds and estrogens in a European river basin and an evaluation of their importance as priority pollutants.

As a part of a project aiming to assess the potential toxicological effects of contaminants in aquatic ecosystems, the objective of this work was to determine the occurrence of several selected endocrine-disrupting compounds in water and sediment and to estimate the estrogenicity of the water. The study consisted of four sampling campaigns at seven sampling points in the lower Llobregat catchment area (NE Spain). Water and sediment samples underwent chemical target analysis for 19 steroid estrogens and alkylphenols, which are known to be endocrine-disrupting compounds.

Drugs of abuse and their metabolites in the Ebro River basin: occurrence in sewage and surface water, sewage treatment plants removal efficiency, and collective drug usage estimation.

Drugs of abuse and their metabolites have been recently recognized as environmental emerging organic contaminants. Assessment of their concentration in different environmental compartments is essential to evaluate their potential ecotoxicological effects. It also constitutes an indirect tool to estimate drug abuse by the population at the community level.

Determination of drugs of abuse in airborne particles by pressurized liquid extraction and liquid chromatography-electrospray-tandem mass spectrometry.

This work describes the first analytical method specifically developed for the multianalyte determination of several drugs of abuse and their metabolites in air. The methodology is based on pressurized liquid extraction (PLE) of atmospheric particles collected by means of high volume sampler equipped with quartz microfiber filters and subsequent analysis of the extracts by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Up to 17 different compounds belonging to five different chemical classes (cocainics, amphetamine-like compounds, opioids, cannabinoids, and lysergic compounds) are determined by means of this methodology.

Identification of disinfection by-products of selected triazines in drinking water by LC-Q-ToF-MS/MS and evaluation of their toxicity.

During the development of an on-line solid phase extraction-liquid chromatography-ultraviolet detection (SPE-LC-UV) analytical method for determination of eight selected triazines; ametryn, atrazine, cyanazine, metrybuzine, prometryn, propazin, simazine, and terbutryn, in drinking water, it was observed that the retention times of three of them (ametryn, prometryn, and terbutryn) in Milli-Q water were different from those in chlorinated Milli-Q water, indicating the formation of new products. The cause of this change was found in the oxidation of the molecules as a result of chlorination with sodium hypochlorite. Experiments performed at varying concentrations of triazines and hypochlorite showed that the extent of the reaction depended on their relative concentrations.

Fast and simultaneous monitoring of organic pollutants in a drinking water treatment plant by a multi-analyte biosensor followed by LC-MS validation.

This work describes the application of an optical biosensor (RIver ANALyser, RIANA) to the simultaneous analysis of three relevant environmental organic pollutants, namely, the pesticides atrazine and isoproturon and the estrogen estrone, in real water samples. This biosensor is based on an indirect inhibition immunoassay which takes place at a chemically modified optical transducer chip. The spatially resolved modification of the transducer surface allows the simultaneous determination of selected target analytes by means of "total internal reflection fluorescence" (TIRF).

Biosensors for environmental monitoring A global perspective.

The intention of this article is to reflect the advances and describe the trends on biosensors for environmental applications. Biosensors are useful analytical tools for environmental monitoring, capable of providing results in real time, simple to use, portable and cost-effective. Some examples of biosensors in advanced stage of development, which have been applied to real samples, as well as of commercial devices, are given.

Fully automated determination in the low nanogram per liter level of different classes of drugs of abuse in sewage water by on-line solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry.

The present work describes the first fully automated method, based on on-line solid-phase extraction (SPE)-liquid chromatography-electrospray-tandem mass spectrometry, developed for the determination of drugs of abuse (17 compounds and metabolites belonging to the classes of amphetaminics, cannabinoids, cocainics, opiates, and lysergics) in sewage waters. On-line SPE is performed by passing 5 mL of the water sample through a PLRP-s cartridge for analytes measured in positive ionization mode (all but cannabinoids) and through an Oasis HLB cartridge for analytes measured in negative ionization mode (cannabinoids). For unequivocal identification and confirmation two selected reaction monitoring transitions are registered per compound, thus achieving the four identification points requested by the European Union for banned substances.

Analysis of 17 polar to semi-polar pesticides in the Ebro river delta during the main growing season of rice by automated on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry.

This work describes the optimization of a fully automated method based on on-line solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (SPE-LC-ESI-MS/MS) for the simultaneous determination of 17 medium to polar pesticides in water. The list of target analytes included organophosphates, triazines, phenylureas, anilides, chloroacetanilides, acidic herbicides and thiocarbamates. Detection limits achieved were below 5 ng/L for all compounds except metolachlor (12 ng/L), alachlor (17 ng/L), malathion (36 ng/L) and fenitrothion (50 ng/L).

Comparative study of an estradiol enzyme-linked immunosorbent assay kit, liquid chromatography-tandem mass spectrometry, and ultra performance liquid chromatography-quadrupole time of flight mass spectrometry for part-per-trillion analysis of estrogens in water samples.

Estrogens have been often identified as the major contributors to the endocrine-disrupting activity observed in environmental waters. However, their analysis in these, sometimes very complex, matrices is still challenging due to the very low detection limits and the selectivity required for their reliable determination at the very low concentrations at which they are physiologically active. In this work, a polyclonal enzyme-linked immunosorbent assay (ELISA) kit for 17-beta-estradiol analysis, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) based on triple-quadrupole analyzer (QqQ), and a newly developed method based on ultra performance liquid chromatography-quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS) have been evaluated in terms of performance for the rapid screening, quantitative analysis, and unequivocal identification of some selected, environmentally relevant estrogens in different water matrices, including urban wastewater, river water, and ground water, after solid phase extraction.

Advantages and limitations of on-line solid phase extraction coupled to liquid chromatography-mass spectrometry technologies versus biosensors for monitoring of emerging contaminants in water.

On-line solid phase extraction (SPE) coupled to liquid chromatography-mass spectrometry (LC-MS) and biosensors are advanced technologies that have found increasing application in the analysis of environmental contaminants although their application to the determination of emerging contaminants (previously unknown or unrecognized pollutants) has been still limited. This review covers the most recent advances occurred in the areas of on-line SPE-LC-MS and biosensors, discusses and compares the main strengths and limitations of the two approaches, and examines their most relevant applications to the analysis of emerging contaminants in environmental waters. So far, the on-line configuration most frequently used has been SPE coupled to liquid chromatography-(tandem) mass spectrometry.

Determination of antimicrobials in sludge from infiltration basins at two artificial recharge plants by pressurized liquid extraction-liquid chromatography-tandem mass spectrometry.

This work describes the optimization of a multi-residue analytical approach for the simultaneous determination of 11 antimicrobials (9 sulphonamides and 2 penicillins) in sludge from infiltration basins. The method is based on pressurized liquid extraction (PLE) followed by solid-phase extraction (SPE) for pre-concentration and purification, and analysis by liquid chromatography-tandem mass spectrometry using electrospray in the positive ionization mode (LC-(ESI+)-MS/MS). Limits of detections (LODs) between 1 pg/g and 0.

Biosensors as useful tools for environmental analysis and monitoring.

Recent advances in the development and application of biosensors for environmental analysis and monitoring are reviewed in this article. Several examples of biosensors developed for relevant environmental pollutants and parameters are briefly overviewed. Special attention is paid to the application of biosensors to real environmental samples, taking into consideration aspects such as sample pretreatment, matrix effects and validation of biosensor measurements.

Evaluation of commercial immunoassays for the detection of estrogens in water by comparison with high-performance liquid chromatography tandem mass spectrometry HPLC-MS/MS (QqQ).

In this work four different commercially available enzyme-linked immunosorbent assays (ELISA) (from Japan EnviroChemicals, Ltd., Tokyo, Japan) were evaluated in terms of performance for the rapid screening of estrogens in different water matrices, including natural and spiked samples from urban wastewater, river water and ground water. All four test kits are based on monoclonal antibodies.

MODELKEY. Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity.

Background: Triggered by the requirement of Water Framework Directive for a good ecological status for European river systems till 2015 and by still existing lacks in tools for cause identification of insufficient ecological status MODELKEY (http:// www.modelkey.org), an Integrated Project with 26 partners from 14 European countries, was started in 2005.

Automated Water Analyser Computer Supported System (AWACSS) Part II: Intelligent, remote-controlled, cost-effective, on-line, water-monitoring measurement system.

A novel analytical system AWACSS (Automated Water Analyser Computer Supported System) based on immunochemical technology has been evaluated that can measure several organic pollutants at low nanogram per litre level in a single few-minutes analysis without any prior sample pre-concentration or pre-treatment steps. Having in mind actual needs of water-sector managers related to the implementation of the Drinking Water Directive (DWD) [98/83/EC, 1998. Council Directive (98/83/EC) of 3 November 1998 relating to the quality of water intended for human consumption.

Automated water analyser computer supported system (AWACSS) Part I: Project objectives, basic technology, immunoassay development, software design and networking.

A novel analytical system AWACSS (automated water analyser computer-supported system) based on immunochemical technology has been developed that can measure several organic pollutants at low nanogram per litre level in a single few-minutes analysis without any prior sample pre-concentration nor pre-treatment steps. Having in mind actual needs of water-sector managers related to the implementation of the Drinking Water Directive (DWD) (98/83/EC, 1998) and Water Framework Directive WFD (2000/60/EC, 2000), drinking, ground, surface, and waste waters were major media used for the evaluation of the system performance. The instrument was equipped with remote control and surveillance facilities.

Picogram per liter level determination of estrogens in natural waters and waterworks by a fully automated on-line solid-phase extraction-liquid chromatography-electrospray tandem mass spectrometry method.

The present work describes a novel, fully automated method, based on on-line solid-phase extraction-liquid chromatography-electrospray tandem mass spectrometry (SPE-LC-ESI-MS-MS), which allows the unequivocal identification and quantification of the most environmentally relevant estrogens (estradiol, estrone, estriol, estradiol-17-glucuronide, estradiol-17-acetate, estrone-3-sulfate, ethynyl estradiol, diethylstilbestrol) in natural and treated waters at levels well below those of concern (limits of quantification between 0.02 and 1.02 ng/L).

Monitoring of estrogens, pesticides and bisphenol A in natural waters and drinking water treatment plants by solid-phase extraction-liquid chromatography-mass spectrometry.

A multi-residue analytical method has been developed for the determination of various classes of selected endocrine disruptors. This method allows the simultaneous extraction and quantification of different estrogens (estradiol, estrone, estriol, estradiol-17-glucuronide, estradiol diacetate, estrone-3-sulfate, ethynyl estradiol and diethylstilbestrol), pesticides (atrazine, simazine, desethylatrazine, isoproturon and diuron), and bisphenol A in natural waters. In the method developed, 500 ml of water are preconcentrated on LiChrolut RP-18 cartridges.

Three new mussel tissue standard reference materials (SRMs) for the determination of organic contaminants.

Three new mussel tissue standard reference materials (SRMs) have been developed by the National Institute of Standards and Technology (NIST) for the determination of the concentrations of organic contaminants. The most recently prepared material, SRM 1974b, is a fresh frozen tissue homogenate prepared from mussels ( Mytilus edulis) collected in Boston Harbor, Massachusetts. The other two materials, SRMs 2977 and 2978, are freeze-dried tissue homogenates prepared from mussels collected in Guanabara Bay, Brazil and Raritan Bay, New Jersey, respectively.

Multianalyte determination of different classes of pesticides (acidic, triazines, phenyl ureas, anilines, organophosphates, molinate and propanil) by liquid chromatography-electrospray-tandem mass spectrometry.

This work describes the optimization of a liquid chromatography-electrospray-tandem mass spectrometry (LC-ESI-MS-MS) method for the multianalyte determination of twenty pesticides, selected based on current regulations and extent of use. Chromatographic separation was carried out on a Purospher STAR RP-18e column using gradient acetonitrile-water as mobile phase. Triazines, phenylureas, organophosphates, anilines, and molinate were determined in the positive ionization mode, and acidic pesticides and propanil in the negative ion mode.

Biosensors for environmental monitoring of endocrine disruptors: a review article.

This article provides an overview of the applications of biosensors in analysis and monitoring of endocrine-disrupting compounds (EDCs) in the environment. Special attention is devoted to the various types of physical-chemical signal transduction elements, biological mechanisms employed as sensing elements and techniques used for immobilisation of the bioreceptor molecules on the transducer surface. Two different classes of biosensors for EDCs are considered: biosensors that measure endocrine-disrupting effects, and biosensors that respond to the presence of a specific substance (or group of substances) based on the specific recognition of a biomolecule.

Determination of estrogens and progestogens by mass spectrometric techniques (GC/MS, LC/MS and LC/MS/MS).

Steroid sex hormones and related synthetic compounds have been shown to provoke alarming estrogenic effects in aquatic organisms, such as feminization, at very low concentrations (ng/L or pg/L). In this work, different chromatographic techniques, namely, gas chromatography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS), are discussed for the analysis of estrogens, both free and conjugated, and progestogens, and the sensitivities achieved with the various techniques are inter-compared. GC/MS analyses are usually carried out after derivatization of the analytes with bis(trimethylsilyl)trifluoroacetamide (BSTFA).

Liquid chromatography-(tandem) mass spectrometry of selected emerging pollutants (steroid sex hormones, drugs and alkylphenolic surfactants) in the aquatic environment.

Among the various compounds considered as emerging pollutants, alkylphenolic surfactants, steroid sex hormones, and pharmaceuticals are of particular concern, both because of the volume of these substances used and because of their activity as endocrine disruptors or as causative agents of bacterial resistance, as is the case of antibiotics. Today, the technique of choice for analysis of these groups of substances is liquid-chromatography coupled to mass spectrometry (LC-MS) and tandem mass spectrometry (LC-MS-MS). In the last decades, this technique has experienced an impressive progress that has made possible the analysis of many environmental pollutants in a faster, more convenient, and more sensitive way, and, in some cases, the analysis of compounds that could not be determined before.

Recent advances in the mass spectrometric analysis related to endocrine disrupting compounds in aquatic environmental samples.

An overview of mass spectrometric methods used for the determination of endocrine disrupting compounds (EDCs) in environmental samples is presented. Among the EDCs we have selected five groups of compounds that are of priority within European Union and US research activities: alkylphenols, polychlorinated compounds (dioxins, furans and biphenyls), polybrominated diphenyl ethers, phthalates and steroid sex hormones. Various aspects of current LC-MS and GC-MS methodology, including sample preparation, are discussed.