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Endocrine disrupting compounds (EDCs) are a wide group of contaminants of emerging concern known to be harmful for organisms. The aim of the study was to assess the occurrence and distribution of six EDCs (estrone-E1, ß-estradiol-E2, 17α-ethinylestradiol-EE2, bisphenol A-BPA, perfluooctanoic acid-PFOA, perfluorooctane sulfonate-PFOS) in the Apenninic rivers and groundwaters of the Romagna area (North of Italy). Groundwaters were unaffected by EDC contamination, while all classes of compounds were detected at concentrations above the method quantification limit (MQL) in the majority of the river bodies. In detail, PFOA and PFOS concentrations varied between

Abstract: Several groups of organic compounds have emerged as particularly relevant as environmental pollutants. These compounds, including new brominated flame retardants, disinfection by-products, drugs of abuse and their metabolites, hormones and other endocrine disrupting compounds, nanomaterials, perfluoroalkyl substances, pharmaceuticals and siloxanes among others, constitute new risks for environmental and human health. In order to face up to these new risk challenges there is an increasing need to assess their occurrence and behaviour in the environment, as well as, that of their degradation products. Therefore, during recent years an important part of research has been focused on to the improvement of analytical schemes for complex matrices, in which the new tendencies in sample preparation (e.g. online clean up systems), the development of new materials and new mass spectrometry analysers have played an important role. This paper presents a general overview of new analytical trends and potentials in trace analysis of emerging pollutants in the environment, including chromatographic techniques coupled to mass spectrometry, and bio analytical approaches (biosensors). [Copyright &y& Elsevier]

In this study, the presence of 18 perfluorinated compounds was investigated in biota and environmental samples from the Antarctica and Tierra de Fuego, which were collected during a sampling campaign carried out along February and March 2010. 61 samples were analysed including fish, superficial soils, guano, algae, dung and tissues of Papua penguin by liquid chromatography coupled to tandem mass spectrometry. The concentrations of PFCs were ranging from 0.10 to 240 ng/g for most of the samples except for penguin dung, which presented levels between 95 and 603 ng/g for perfluorooctane sulfonate, and guano samples from Ushuaia, with concentration levels of 1190–2480 ng/g of perfluorohexanoic acid. PFCs acids presented, in general, the highest levels of concentration and perfluorooctanesulfonate was the most frequently found compound. The present study provides a significant amount of results, which globally supports the previous studies, related to the transport, deposition, biodegradation and bioaccumulation patterns of PFCs. [Copyright &y& Elsevier]

Abstract: Perfluorinated compounds (PFCs) are widely used in everyday life and one of the main recipients of these compounds is waste water treatment plants (WWTPs). Due to the structure and physicochemical properties of PFCs, these compounds could be redistributed from influent water to sludge. This work reports a new validated protocol for the analysis of 13 perfluorinated acids, 4 perfluorosulfonates and the perfluorooctanesulfonamide. The present work has been focused to develop a sensitive and robust method for the analysis of 18 PFCs in sewage sludge, based on pressurized solvent extraction (PSE) followed by solid phase extraction (SPE) clean-up, analytes separation by liquid chromatography and analysis in a hybrid quadrupole-linear ion trap mass spectrometer (LC–QLiT-MS/MS) working in single reaction monitoring (SRM) mode. The final methodology was validated using a blank sewage sludge fortified at different concentration levels. The method limits of detection were ranging in general from 15 to 79ng/kg. These values were comparable to the decision limit (CCα) and the detection capability (CCβ), which were 17–1134ng/kg and 18–1347ng/kg, respectively. The percentage of recovery was from 79 to 111% in the most cases at different spiked levels. Finally, the repeatability of the method was in the range 4% (PFOS and PFOA) to 25% (RSD %). In order to evaluate the applicability of the method, 5 sludge samples were analyzed. The results showed that the 18 PFCs were present in all samples. However, the concentrations for most of them were below the limits of quantification. The compound present at higher concentrations was perfluorooctanesulfonate (PFOS), which was in concentrations from 53.0 to 121.1μg/kg. The other PFCs were at concentrations between 0.3 and 30.3μg/kg. [Copyright &y& Elsevier]

Summary: The increasing use and production of carbon-based nanoparticles demands for new analytical approaches able to achieve sensitivities in the low ng/L range in order to assess their presence in environmental samples. This paper describes development, optimization and validation of a novel method for the analysis of C60 and, C70 fullerenes and N-methylfulleropyrrolidine C60 in the environment. The method relies on ultrasonication extraction from suspended solids in wastewater, followed by liquid chromatography (LC) coupled to a hybrid triple quadrupole linear ion trap mass spectrometry (QqLIT-MS) for trace quantification. Recoveries obtained were generally higher than 60% for both surface water and wastewaters. The overall variability of the method was below 15%, for the three fullerenes and all tested matrices: ultra-pure water, surface water and wastewater. For the effluents of wastewater treatment plants the method quantification limits (MQL) ranged from 0.2 to 1ng/L. The precision of the method, calculated as relative standard deviation (RSD), ranged from 1% to 2% and from 5% to 9% for intra and inter-day analysis, respectively. The developed analytical method was applied to the analysis of fullerenes in the effluents of 22 wastewater treatment plants in Catalonia (NE of Spain). 50% of the analyzed samples contained fullerenes, nine of them in the μg/L concentration range. This work constitutes the first report on the occurrence of fullerenes in suspended solids of wastewater effluents highlighting the need of nanotechnologies residues assessment for risk evaluation of nanoparticles in the environment. [Copyright &y& Elsevier]

Abstract: This paper describes the development and validation of an analytical methodology to determine eight perfluorinated compounds (PFCs) in edible fish using pressurized liquid extraction (PLE) with water and solid-phase extraction (SPE) with an ion-exchanger as extraction and pre-concentration procedures, followed by liquid chromatography–quadrupole-linear ion trap mass spectrometry (LC–QqLIT–MS). The rapidity and effectiveness of the proposed extraction procedure were compared with those most commonly used to isolate PFCs from fish (ion-pairing and alkaline digestion). The average recoveries of the different fish samples, spiked with the eight PFCs at three levels (the LOQ, 10 and 100μgkg−1 of each PFC), were always higher than 85% with relative standard deviation (RSD) lower than 17%. A good linearity was established for the eight PFCs in the range from 0.003–0.05 to 100μgkg−1, with r >0.9994. The limits of quantification (LOQs) were between 0.003 and 0.05μgkg−1, which are well below those previously reported for this type of samples. Compared with previous methods, sample preparation time and/or LOQs are reduced. The method demonstrated its successful application for the analysis of different parts of several fish species. Most of the samples tested positive, mainly for perfluoropentanoic acid (PFPA), perfluorobutane sulfonate (PFBS) and perfluorooctanoic acid (PFOA) but other of the eight studied PFCs were also present. [Copyright &y& Elsevier]

Abstract: 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-β-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. Compounds quantified and/or identified included the estrogens 17-β-estradiol, estrone, 17-α-ethynyl estradiol and estriol, and the isoflavones daidzein, genistein, and biochanin A. Except for a moderate overestimation using the ELISA kit, especially in the analysis of complex wastewater samples, results obtained by all the investigated techniques were in very good, general agreement. The instrumental sensitivity achieved increased in the order: UPLC–Q-TOF-MS

Abstract Pollution has been less investigated in marine and coastal environments than in inland waters. The low levels at which pollutants are expected to be present in seawater calls for the use of reliable and high sensitivity analytical methodologies. In this context, this work presents the optimization and validation of an analytical method to determine 26 medium to highly polar pesticides in seawater based on solid phase extraction and liquid chromatography-tandem mass spectrometry detection. The developed methodology was linear, accurate (relative recoveries within 80–120% for most analytes), repeatable (relative standard deviations <18% for most analytes), and sensitive (limits of determination <1 ng/L for 89% of the compounds). The use of isotopically labeled compounds as surrogate standards compensated for low analyte recoveries and matrix effects. The method was applied to the analysis of seawater samples collected along the coastline of Catalonia (NE Spain). Overall, total pesticide loads were higher inside the marinas than outside. The booster biocides diuron and irgarol used in antifouling paintings and different triazine pesticides were the most abundant compounds. Irgarol was present above the maximum allowable concentration set in European regulations in 70% of the samples collected inside the marinas. A different pesticide pollution pattern, with MCPA and bentazone presenting the highest concentrations, was observed at the Ebro Delta area due to the impact of the agricultural activities carried out there. To the authors' knowledge, 4 out of the 26 target pesticides, namely, chlorfenvinphos, fenthion oxon, fenthion sulfone, and fenthion sulfoxide, have not been previously investigated in seawater. Graphical abstract Image 1 Highlights • Reliable and sensitive method optimized for analysis of 26 pesticides in seawater. • Reliability of results ensured by quantification with an isotope dilution approach. • Pesticide occurrence was evaluated in coastal and offshore water of Catalonia. • Total levels were higher inside the marinas than outside. • Irgarol, diuron and triazine pesticides were the most abundant compounds. [ABSTRACT FROM AUTHOR]

The main objective of this study was to assess the concentration levels and the seasonal variations of 13 poly- and perfluoroalkyl substances (PFASs) in different compartments (water, sediments and fish) of the Ebro Delta (NE Spain) and surrounding coastal areas. Perfluorooctanoic acid (PFOA) was the most frequently detected compound in waters and sediments. Perfluorocarboxylic acids (PFCAs) were the compounds found at the highest concentrations in water samples. On the other hand, sediments were more enriched in perfluorooctanesulfonate (PFOS) (range < 1.02–22.6 ng/g dw). Waters and sediments showed a different seasonal trend. While waters were characterised by a substantial constant level of PFASs over the year, sediments showed a progressive decrease from autumn to summer, revealing the great influence that environmental conditions exert on PFAS distribution in sediments. As regards fish samples, in spite of the ban of its production, PFOS was the most frequently detected compound in seawater fishes, in agreement with its high persistency, bioaccumulation and biomagnification. Moreover, PFASs showed to be more distributed in the skin rather than in muscle tissues. In addition, river fishes were characterised by very high PFAS levels (∑ PFAS range from 63.8 ng/g ww to 938 ng/g ww), with perfluoroalkyl carboxylic acids being more concentrated than sulfonates. The PFASs concentrations in water, sediment, and biota revealed that one of the studied sites, Isla de Buda was the most contaminated site of the Ebro Delta. These results are consistent with its location at the final part of the estuary, where many irrigation channels are collected together. [ABSTRACT FROM AUTHOR]

Abstract: The concentrations of 21 perfluoroalkyl substances (PFASs: C4–C14, C16, C18 carboxylates, C4, C6–C8 and C10 sulfonates and C8 sulfonamide) were determined in influent, effluent and sludge from 16 different sewage treatment plants (STPs) located in the Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (3) Rivers, in two consecutive years (2010 and 2011). The analytes were extracted by solid phase extraction (SPE) and determined by Liquid Chromatography triple Quadrupole Mass Spectrometer (LC-QqQ-MS). All samples, except two sludges from Guadalquivir River STPs, were contaminated with at least one PFAS. Perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (L-PFOS) were the most frequently detected. The highest concentration in water was determined in 2010 in a Guadalquivir River STP (perfluorohexanoate, PFHxA: 5.60μgL−1) and, in 2011, in an Ebro River STP (perfluorobutane sulfonate, L-PFBS: 0.31μgL−1). In sludge samples, the maximum concentration in 2010 was 1.79μgg−1 dry weight (dw) (L-PFOS, in a Llobregat River STP), and in 2011, 1.88μgg−1 dw (PFBA, in one Guadalquivir River STP). High PFAS values in sludge could be related to positive removal efficiencies, and can be attributed to their adsorption. Distribution coefficients (Kd) were determined ranging between 0.32Lkg−1 (perfluorohexane sulfonate, L-PFHxS) and 36.6 103 Lkg−1 (PFBA). The total PFAS loads discharged into the basins showed high values for the Ebro River STPs (66.9gday−1) while in the others, the loads were between 3.97gday−1, in the Jucar STPs, and 32.2gday−1, in the Guadalquivir STPs. [Copyright &y& Elsevier]