UV-filters and musk fragrances in seafood commercialized in Europe Union: Occurrence, risk and exposure assessment.

In the framework of the FP7 ECsafeSeafood project, 62 seafood samples commercialized in Europe Union from several representative species - mackerel, tuna, salmon, seabream, cod, monkfish, crab, shrimp, octopus, perch and plaice - were analysed for residues of 21 personal care products (PCPs), including 11 UV-filters (UV-Fs) and 10 musk fragrances (musks). PCPs analysis were performed by Quick, Easy, Cheap, Effective Rugged, Safe (QuEChERS), combined with liquid-liquid extraction (LLE) or dispersive solid-phase extraction (dSPE), followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The results showed the presence in a wide range of samples of nine out of eleven UV-Fs compounds analysed, namely 2-ethylhexyl salicylate (EHS), 2-ethylhexyl,4-methoxycinnamate (EHMC), 4-methylbenzylidenecamphor (4-MBC), benzophenone-1 (BP1), benzophenone-3 (BP3), isoamyl-4-methoxycinnamate (IMC), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (DHMB), homosalate (HS), and octocrylene (OC), whereas galaxolide (HHCB), galaxolide lactone (HHCB-lactone), and tonalide (AHTN) were the most found musks. The potential risks to human health associated with the exposure to eight of the more prevalent PCPs - EHS, EHMC, 4-MBC, BP1, BP3, IMC, HHCB, and AHTN - through seafood consumption were assessed for consumers from five European countries (Belgium, Ireland, Italy, Portugal and Spain). Results showed that the human exposure to UV-Fs and musks estimated from the concentration values found in seafood and the daily consumption of concerned seafood species, were far below toxicological reference values.

Co-occurrence of musk fragrances and UV-filters in seafood and macroalgae collected in European hotspots.

In the last decades, awareness regarding personal care products (PCP), i.e. synthetic organic chemicals frequently used in cosmetic and hygienic products, has become a forward-looking issue, due to their persistency in the environment and their potential multi-organ toxicity in both human and wildlife. Seafood is one of the most significant food commodities in the world and, certainly, one of the most prone to bioaccumulation of PCP, what can consequently lead to human exposure, especially for coastal population, where its consumption is more marked. The aim of this work was to evaluate the co-occurrence of musk fragrances and UV-filters in both seafood and macroalgae collected in different European hotspots (areas with high levels of pollution, highly populated and near wastewater treatment plants). Despite the fact that UV-filters were detected in three different kind of samples (mussel, mullet, and clam), in all cases they were below the limit of quantification. Galaxolide (HHCB) and tonalide (AHTN) were the musk fragrances most frequently detected and quantified in samples from the European hotspots. Cashmeran (DPMI) was also detected in most samples but only quantified in two of them (flounder/herring and mullet). The highest levels of HHCB and AHTN were found in mussels from Po estuary.

Characterization of organic fouling in reverse osmosis membranes by headspace solid phase microextraction and gas chromatography-mass spectrometry.

Adsorption of organic substances on reverse osmosis (RO) membrane surfaces may form an organic film on the membrane, known as organic fouling, and cause flow-rate loss. This problem is mostly unavoidable as no pretreatment method exists for perfect removal of possible foulants, including organic compounds resulting from undesirable bioactivity. Understanding the characteristics of fouling layers is an essential step towards overall improvement of RO membrane operations. In this study, the organic fouling in RO membranes treating the effluent of a secondary treatment from an urban wastewater treatment plant was characterized. Headspace solid phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry has been used for the first time, to provide valuable information of organic fouling. Different polarity SPME fibers were tested for this purpose. In addition, the characterization of the organic fouling obtained by HS-SPME was compared with the results obtained by extraction using several organic solvents. The results indicated that more compound families can be identified by HS-SPME than by organic solvent extraction. Moreover, complementary organic analyses were done for better understanding of the organic fouling in RO membranes, such as total organic carbon and loss on ignition.

Pressurized liquid extraction and liquid chromatography-tandem mass spectrometry applied to determine iodinated X-ray contrast media in sewage sludge.

Pressurized liquid extraction (PLE) has been successfully applied for the first time to the extraction of five iodinated X-ray contrast media from sludge. Once optimized all PLE parameters, the extract has been analyzed by liquid chromatography-tandem mass spectrometry, being the method developed sensible enough to reach limit of quantifications (LOQs) of 25 µg kg(-1) (d.w.). The developed method has been applied to the analysis of sludge from urban sewage treatment plants and although some compounds such as iopromide, diatrizoic acid and iopamidol have been identified, their concentrations have been lower than their LOQs.

Comparison of triple quadrupole mass spectrometry and Orbitrap high-resolution mass spectrometry in ultrahigh performance liquid chromatography for the determination of veterinary drugs in sewage: benefits and drawbacks.

This paper presents a comparison of triple quadrupole tandem mass spectrometry (MS/MS) and Orbitrap high-resolution mass spectrometry (HRMS) combined to ultrahigh performance liquid chromatography for the determination of glucocorticoids and polyether ionophores in sewage, in order to show the major benefits and drawbacks for each mass spectrometry analyser. Overall, HRMS measurements have enhanced performance in terms of confirmatory capabilities than MS/MS measurements. Moreover, similar limits of quantification, limits of detection, linear range and repeatability for glucocorticoids with both the MS/MS and HRMS methods were compared, but in the case of polyether ionophores, slightly better limits of detection and limits of quantification were obtained with the HRMS method because of the high sensitivity obtained when diagnostic ions are used for quantification instead of selected reaction monitoring transitions for these compounds. The two methods have been applied to the analysis of several influent and effluent sewage samples from sewage treatment plants located in the Tarragona region (Catalonia, Spain), showing an excellent correlation between the two methods.

A pressurised hot water extraction and liquid chromatography-high resolution mass spectrometry method to determine polar benzotriazole, benzothiazole and benzenesulfonamide derivates in sewage sludge.

Benzothiazole, benzotriazole and benzenesulfonamide derivates are well-known aquatic contaminants, although very few studies have been published about their occurrence in sewage sludge samples. In this paper, a pressurised hot water extraction (PHWE) method has been developed for the simultaneous determination of these families of compounds. The compounds were determined by LC-Orbitrap-HRMS and several clean-up strategies such as in-cell PHWE and solid-phase extraction (SPE) were tested to reduce the high matrix effect that occurs when sludge samples are analysed. Absolute recoveries using the whole method were above 80% and the matrix effect was under -20% for most of the compounds studied. Repeatability and reproducibility were usually under 10% (%RSD, 50 and 250ngg(-1) (d.w.), n=5), while LODs and LOQs were between 0.25 and 25ngg(-1) (d.w.) and 0.5 and 50ngg(-1) (d.w.), respectively. The PHWE/SPE/LC-HRMS method developed was used to analyse several sludge samples collected from five sewage treatment plants (STPs) in Catalonia that use different sewage treatments. The most frequently determined compounds were benzotriazole derivates and the most abundant compound found was 2-hydroxybenzothiazole.

Asymmetrical flow field-flow fractionation hyphenated to Orbitrap high resolution mass spectrometry for the determination of (functionalised) aqueous fullerene aggregates.

In this short communication we report on the technical implementations of coupling an asymmetric flow field-flow fractionation (AF4) instrument to a high resolution mass spectrometer (Orbitrap) using an atmospheric photoionisation interface. This will allow for the first time online identification of different fullerenes in aqueous samples after their aggregates have been fractionated in the FFF channel. Quality parameters such as limits of detection (LODs), limits of quantification (LOQs) or linear range were evaluated and they were in the range of hundreds ng/L for LODs and LOQs and the detector response was linear in the range tested (up to ∼20 µg/L). The low detection and quantification limits make this technique useful for future environmental or ecotoxicology studies in which low concentration levels are expected for fullerenes and common on-line detectors such as UV or MALS do not have enough sensitivity and selectivity.

Determination of iodinated X-ray contrast media in sewage by solid-phase extraction and liquid chromatography tandem mass spectrometry.

A method for the quantitative determination of five iodinated X-ray contrast media (ICMs) in sewage was developed by solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry. A fused-core analytical column was successfully applied for the first time for the separation of ICMs. Oasis HLB was selected from the sorbents tested because of its higher recoveries. The optimized method allowed the determination of the ICMs at low ng/L levels in both influent and effluent sewage, with detection limits of 40 ng/L and 10 ng/L for most compounds in influent and effluent sewage, respectively. The five ICMs studied were determined in all samples analysed, with iopromide being the analyte found at the highest concentration (8.9 µg/L), while iopamidol was the analyte found at lowest concentration (1.3 µg/L) in influent sewage. Effluent sewage did not show a significant decrease in ICM concentrations.

Simultaneous determination of 76 micropollutants in water samples by headspace solid phase microextraction and gas chromatography-mass spectrometry.

This study focuses on the development of an analytical method based on headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 76 micropollutants in water samples. The selected micropollutants include volatile organic compounds (VOCs) (e.g. chlorobenzenes, chloroalkanes), endocrine disrupting compounds (EDCs) (e.g. bisphenol A and tributyl phosphate), odour compounds (e.g. limonene, phenol), fragrance allergens (e.g. geraniol, eugenol) and some pesticides (e.g. heptachlor, terbutryn). The experimental conditions affecting their extraction, such as the type of fibre, temperature and time of extraction, sample volume and ionic strength of the samples were optimized using HS-SPME. The method showed good linear range, reproducibility between days, repeatability and low detection limits (at ng L(-1) levels). The validated method has been applied to determine the target organic micropollutants in aqueous samples from different experimental research units of surface water, sea water, waste water and those effluents of advance membrane treatments. The optimized method showed good performance in the different types of samples studied. The analysis revealed the presence of several micropollutants at concentrations between 20 and 5000 µg L(-1), such as ethylbenzene, o-xylene, p-isopropilbenzene, D-limonene, citral and isoeugenol, due to the fact that these species are commonly used in domestic and industrial applications.

Efficient tandem solid-phase extraction and liquid chromatography-triple quadrupole mass spectrometry method to determine polar benzotriazole, benzothiazole and benzenesulfonamide contaminants in environmental water samples.

An analytical method has been developed that allows the simultaneous determination of five benzotriazole (BTRs), four benzothiazole (BTs) and five benzenesulfonamide (BSAs) derivates. The method is based on tandem solid-phase extraction (SPE) with Oasis HLB followed by a clean-up step with Florisil. The chromatographic analysis was performed in less than 15min and detection was carried out with a triple quadrupole mass analyser operating in multiple reaction monitoring (MRM) mode. A comparison was performed between Oasis HLB and Oasis MAX sorbents for the solid-phase extraction, with Oasis HLB being the sorbent that gave the highest recoveries, ranging between 75% and 106%, depending on the compound and the matrix analysed. The proposed clean-up with Florisil sorbent reduced the matrix effect to below 20%. The repeatability (%RSD, 50-3000ng/L, n=3) of the method was less than 15% for all of the compounds in all of the matrices. The limits of detection (LODs) achieved ranged from 1ng/L for BTR in river water up to 100ng/L for BT in influent sewage. All of the compounds were determined in environmental waters such as river water and sewage. The highest concentrations determined corresponded to influent sewage samples in which the sum of concentrations for all compounds were between 4.6µg/L and 8.0µg/L. These concentrations were slightly reduced in secondary effluent and tertiary effluent sewage. Moreover, samples from tertiary effluent sewage based on ultra-filtration membrane treatments were also analysed and preliminary results seem to indicate that these treatments may be most effective for removing BTR, BT and BSA derivates.

Determination of polyether ionophores in urban sewage sludge by pressurised liquid extraction and liquid chromatography-tandem mass spectrometry: study of different clean-up strategies.

A method for the determination of five polyether ionophores in urban sewage sludge has been developed. The extraction of compounds was performed by pressurised liquid extraction using acetone, while florisil was used for in-cell clean-up to minimise the matrix effect in the sludge extracts. An amide polar-embedded reversed-phase column was used for the chromatographic separation with a rapid-resolution liquid chromatograph coupled to a tandem mass spectrometer. Moreover, several clean-up strategies such as in-cell and on-cell clean-up and solid-phase extraction clean-up, among others, were tested and their results are discussed in the present paper. Recoveries (10 and 250 µg/kg in dry weight (d.w.), n=6) were close to 90%, repeatability and reproducibility (%RSD, 10 and 250 µg/kg (d.w.), n=6) were less than 10% and 12%, respectively. Limits of detection (LODs) and limits of quantification (LOQs) ranged between 0.5 and 1 µg/kg (d.w.) and between 1 and 5 µg/kg (d.w.), respectively. The method was applied to samples collected in five sewage treatment plants in Catalonia. Monensin and narasin were determined in some sludge samples at concentrations from

Pressurised liquid extraction and ultra-high performance liquid chromatography-tandem mass spectrometry to determine endogenous and synthetic glucocorticoids in sewage sludge.

Glucocorticoids are a type of steroid hormones classified as endocrine disrupting chemicals (EDCs) and they are widely used by human and animal medicine. In this paper, we describe the development and validation of an analytical method for the determination of 9 selected glucocorticoids (betamethasone, cortisol (hydrocortisone), cortisone, dexamethasone, flumethasone, methylprednisolone, prednisolone, prednisone and triamcinolone acetonide) in sewage sludge by pressurised liquid extraction (PLE) and ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). PLE with on-cell clean-up followed by solid-phase extraction (SPE) clean-up (Oasis HLB) has been applied to extract the analytes and clean up the matrix. Recoveries of the method were from 8% for prednisone and cortisone to 73% for triamcinolone acetonide. The developed method achieves limits of detection (LODs) between 1 and 5 µg/Kg dry weight (d.w.) in sludge and the repeatability expressed as relative standard deviation (%RSD, 50 µg/Kg (d.w.), n=3) is less than 8%. The PLE/SPE/UHPLC-MS/MS method was successfully applied to determine these pollutants in sludge samples from two sewage treatment plants located in the Tarragona area. Cortisone was found at levels below LOQ, cortisol between 5.2 and 6.1 µg/Kg (d.w.) and prednisolone between

Novel amide polar-embedded reversed-phase column for the fast liquid chromatography-tandem mass spectrometry method to determine polyether ionophores in environmental waters.

A fast chromatographic method has been developed that takes less than 5 min per run to determine five polyether ionophores with a novel amide polar-embedded reversed-phase column coupled to a triple quadrupole mass spectrometer. A comparison between Oasis HLB and Oasis MAX sorbents for the solid-phase extraction was done. Oasis HLB sorbent gave recoveries close to 90% and the repeatability (%RSD, 25-100 ng/L, n=3) of the method was less than 7% for all compounds in all matrices. The presence of polyether ionophores in environmental waters such as river water and sewage was investigated. Monensin and narasin were frequently determined in influent and effluent sewage at concentrations from 10 ng/L to 47 ng/L in influents and from 6 ng/L to 34 ng/L in effluents. In river waters, polyether ionophores were not detected in any sample.

Determination of glucocorticoids in sewage and river waters by ultra-high performance liquid chromatography-tandem mass spectrometry.

In this paper we present a method based on ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) combined with a solid-phase extraction to determine nine glucocorticoids in river waters and sewage. In addition, we attempt the chromatographic separation of two glucocorticoid epimers (betamethasone and dexamethasone) which until now had not been determined simultaneously in environmental matrices. For SPE, we have tested three commercial polymeric polar/non-polar balanced sorbents. The recoveries were close to or above 90% in rivers and sewage influents and effluents. The repeatability expressed as relative standard deviation (%RSD, n=3, 10 ng/L) was less than 8% in all cases. The method obtains LODs for glucocorticoids at low ng/L levels in aqueous environmental matrices (0.5-20 ng/L depending on the matrix and the analyte). The method was applied to determine these compounds in three Catalan rivers (Ebre, Ter and LLobregat) and two sewage treatment plants in the Tarragona area. Cortisone, cortisol, prednisone and prednisolone were frequently determined in influent sewage samples between 21 and 285 ng/L. Moreover, the two epimers were successfully determined below LOQs in some influent sewage samples.

Comparison of the removal of phthalates and other organic pollutants from industrial wastewaters in membrane bioreactor and conventional activated sludge treatment plants.

In recent years greater attention has been paid to the presence of pollutants in wastewater treatment plants, mainly because of strict environmental regulations and the possibility of reusing treated water in industrial processes. Since some organic pollutant compounds are not sufficiently removed in conventional activated sludge treatment (CAST) plants, new treatment processes have been developed, such as membrane bioreactors (MBRs). In this study a submerged membrane bioreactor (MBR) was used to treat mixed industrial wastewaters in parallel with a CAST plant. Two hydraulic retention times (HRT) of wastewater were tested as one of the operational conditions of MBR and the quality of effluents of the two processes were studied and compared. Several general quality parameters were analysed in wastewaters: chemical oxygen demand (COD), pH, conductivity, nitrogen, phosphate, suspended solids (SS) and turbidity. The two systems reduced COD by around 90%. SS was reduced by around 81% in the CAST plant and around 90% in the MBR plant. The results for the other general parameters were similar or better in the MBR process, which worked at a lower HRT. We also studied the removal of a group of six phthalates and bis(2-ethylhexyl)adipate ester by SPME/GC-MS in the two treatment plants. Most of these compounds were not completely removed in the two treatment plants and were identified at low microg l(-1) levels. We also tentatively identify some organic compounds in the wastewaters. Most of the compounds we found in the influent, MBR effluent and CAST effluent were benzene derivates, styrene, naphthalene and naphthalene derivates, and phenol derivates.

Stir bar sorptive extraction and large volume injection gas chromatography to determine a group of endocrine disrupters in water samples.

Stir bar sorptive extraction (SBSE) combined with gas chromatography (GC) with mass spectrometric detection (MS) has been applied to determine a group of suspected endocrine disrupters in water samples. One centimeter stir bars coated with PDMS were used to extract the analytes and then solvent desorption was carried out. The absorption and desorption parameters in SBSE were optimized and large volume injection was used with a programmed temperature vaporizer injector (PTV) in GC to enhance the sensitivity of the method. The linear range of some endocrine disrupters was between 0.05 and 5 microg l(-1) and limits of detection were 0.01-0.24 microg l(-1) under full scan acquisition mode. The repeatability and reproducibility of the method (n = 5) for Ebro river water samples spiked at a level of 0.5 microg l(-1) was below 13 and 23%, respectively. Recoveries between 42 and 96% were obtained with the exception of atrazine. The method was applied to analyze real water samples from the Ebro River and irrigation streams of Ebro Delta and some of the compounds studied (aldrin, dieldrin, 4,4'-DDE and 4,4'-DDT) were found in some of them between detection and quantification limits.

Determination of endocrine-disrupting compounds in water samples by on-line solid-phase extraction-programmed-temperature vaporisation-gas chromatography-mass spectrometry.

We developed an automated on-line solid-phase extraction (SPE)-gas chromatography-mass spectrometry method to determine a group of endocrine disruptors in water samples. The interface device used for connecting SPE with GC was a programmed-temperature vaporiser (PTV) whose liner was packed with Tenax. We optimized the parameters that affected both SPE and PTV working in solvent vent mode. The performance of the method was tested with several environmental water samples. The limits of detection of the method were between 0.001 and 0.036 microg l(-1) under full-scan acquisition mode. We determined phthalates and adipate in all real samples at concentrations between 0.11 and 8.10 microg l(-1). Atrazine and p,p'-DDE were also found in an irrigation stream water sample at 0.16 and 0.04 microg l(-1), respectively.

Method based on solid-phase microextraction--high-performance liquid chromatography with UV and electrochemical detection to determine estrogenic compounds in water samples.

We determined a group of estrogenic compounds by solid-phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC) with both ultraviolet (UV) and electrochemical detection (ED). A modified liquid chromatograph was used. Polyacrylate fibers (85 microns) were used to extract the analytes from the aqueous samples. Dynamic and static modes of desorption were compared and the variables affecting both absorption and desorption processes in SPME-HPLC were optimized. Static desorption gave the best recoveries and peak shapes. The performance of the SPME-HPLC-UV-ED method was checked with river water and wastewater. The method enabled estrogenic compounds to be determined at low-microgram l-1 levels in real water samples. Limits of detection were between 0.3 and 1.1 micrograms l-1 using UV detection and between 0.06 and 0.08 microgram l-1 using ED. beta-Estradiol was found in samples from a wastewater treatment plant at concentrations between 1.9 and 2.2 micrograms l-1.

Application of on-line solid-phase extraction-gas chromatography-mass spectrometry to the determination of endocrine disruptors in water samples.

We have applied a method based on solid-phase extraction (SPE), on-line coupled to gas chromatography-mass spectrometry through an on-column interface, to determine a group of endocrine-disrupting compounds in water samples. We have optimised the parameters affecting the SPE process and transfer step and used the method to analyse river, coastal and tap waters. In the full-scan acquisition mode, all the compounds were determined by preconcentrating only 15 ml of water sample. Di-n-butyl phthalate, benzylbutyl phthalate, bis(2-ethylhexyl) phthalate and bis(2-ethylhexyl) adipate at concentrations between 0.02 and 0.5 microg l(-1) were determined in some real samples.

Solid-phase microextraction coupled to high-performance liquid chromatography to determine phenolic compounds in water samples.

Solid-phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC) with ultraviolet (UV) and electrochemical detection (ED) has been applied to determine 11 phenolic compounds considered priority pollutants by the US Environmental Protection Agency. 85 microm polyacrylate fibers were used to extract the analytes from the aqueous samples. Two different designs of the liquid chromatograph were compared in combination with SPME. Dynamic and static modes of desorption in both HPLC designs were compared and the variables affecting both absorption and desorption processes in SPME-HPLC were optimized. Static desorption in both HPLC systems showed better recoveries for the phenolic compounds. The performance of the SPME-HPLC-UV-ED method was evaluated with river water and wastewater samples. The method enabled the determination of phenolic compounds at low levels in these water samples.