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Wastewater-based epidemiology (WBE) is a well-established approach that can provide objective and real-time data on the consumption of substances such as pharmaceuticals. However, most of the studies reported so far compares consumption data obtained using WBE with those derived from prescription data from public health systems, which is often incomplete and might represent a source of uncertainty. This study aims to compare the measured pharmaceutical consumption back calculated with the WBE approach with consumption derived from dispensed pharmaceuticals in two regions of Spain, managed by two different Health Systems. To do so, a group of 17 pharmaceuticals, including the most representative ones of every therapeutic family, were monitored in influent wastewater (IWW) samples collected over a week campaign in spring 2022 at four different wastewater treatment plants (WWTPs) in Spain: two WWTPs in Madrid city (center of Spain) and two WWTPs in Catalonia (Northeast of Spain). Population-normalized daily loads (PNDL) revealed that the patterns of pharmaceutical occurrence in the different WWTPs are very similar, being acetaminophen, 4-acetamidoantipyrine and valsartan the pharmaceuticals with the highest PNDL values: 17162 ± 1457 mg day -1 1000 inh -1 for acetaminophen, 2365 ± 696 and 2429 ± 263 mg day -1 1000 inh -1 for 4-acetamidoantipyrine, 2006 ± 541 and 2041 ± 352 mg day -1 1000 inh -1 for valsartan. Pharmaceutical PNLDs were then transformed into measured pharmaceutical consumption (MC) and compared with dispensed consumption (DC) data obtained from the pharmacies in the catchment area where the WWTPs are located. A ratio MC/DC within 0.8 to 1.2 was obtained for 11 out of the 17 studied pharmaceuticals. Highlighting a match in all the cardiovascular system pharmaceuticals, with the exception of losartan (1.29-1.39 ratio) and valsartan (1.35-1.43) in all WWTPs. In summary, the degree of correlation between MC/DC is higher than those previously reported comparing with the prescribed pharmaceutical consumption., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The decline in fish populations and the depletion of marine resources have sparked concerns about sustainable fish production, driving the innovation of new aquaculture methods. While some argue that wild fish are healthier than farmed fish due to less exposure to contaminants and pathogens, wild fish can accumulate contaminants from more contaminated water sources. The slower growth of wild fish and their longer exposure to the environment may contribute to higher pollutant levels in fish tissues. In this study, we focus on 25 contaminants considered as high production volume chemicals (HPVCs), such as organophosphate esters (OPEs), benzothiazoles (BTs), benzosulfonamides (BSAs) and phthalates (PAEs). The compounds were extracted from the edible part of the fish using the QuEChERS method and analysed by gas chromatography-tandem mass spectrometry. A total of 74 samples were analysed from three of the most commonly consumed species in Catalonia, Spain (turbot, sea bass and sea bream). Two samples of each species were collected each month, one form farmed and one from wild origin. In general, the compounds were found in all the samples in a wide concentrations range, although no significant differences were observed between the mean concentration of wild and farmed samples. Although similar mean concentrations for the OPEs, BTs and BSAs were found between farmed and wild origin samples, PAEs were more frequently detected in farmed samples. Di-n-octyl phthalate and diethyl phthalate showed the highest concentrations in all fish samples, with values up to 19505 and 17605 ng g -1 (d.w.), in sea bass and sea bream, respectively. Di-(2-ethylexyl)-adipate proved to be the most relevant carcinogenic compound, with no associated health risk. Despite the detection of the studied HPVCs, no health risk was associated with the consumption of these three fish species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This paper investigates the occurrence and removal of 60 organic micropollutants (OMPs) including pharmaceuticals, personal care products, pesticides and per- and polyfluoroalkyl substances in a drinking water treatment plant (DWTP) treating raw water from the Ebro River (NE Spain). The behaviour of the OMPs was evaluated in each treatment: pre-ozonation, flocculation-coagulation-decantation-sand filtration, post-ozonation and granular activated carbon filtration. Thirty-one of the sixty OMPs studied were detected in source water with individual median concentrations below 10 ng L -1 for all the compounds except for caffeine (64.1 ng L -1 ). The highest concentration peaks in the source water were found for caffeine (124.5 ng L -1 ), terbuthylazine (52.0 ng L -1 ), imidacloprid (30.2 ng L -1 ) and paracetamol (25.6 ng L -1 ). Of the 31 compounds detected in the source water, 17 were also detected in the finished drinking water. Of these 17 compounds, 10 were PFASs, which indicated that this group of compounds had not been effectively removed throughout the drinking water treatments. The overall removal efficiencies of OMPs in the DWTP ranged from -50.9% to 100%. The most efficient removal technologies were ozonation and granular activated carbon., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Data obtained from wastewater analysis can provide rapid and complementary insights in illicit drug consumption at community level. Within Europe, Spain is an important country of transit of both cocaine and cannabis. The quantity of seized drugs and prevalence of their use rank Spain at the top of Europe. Hence, the implementation of a wastewater monitoring program at national level would help to get better understanding of spatial differences and trends in use of illicit drugs. In this study, a national wastewater campaign was performed for the first time to get more insight on the consumption of illicit drugs within Spain. The 13 Spanish cities monitored cover approximately 6 million inhabitants (12.8% of the Spanish population). Untreated wastewater samples were analyzed for urinary biomarkers of amphetamine, methamphetamine, MDMA, cocaine, and cannabis. In addition, weekend samples were monitored for 17 new psychoactive substances. Cannabis and cocaine are the most consumed drugs in Spain, but geographical variations showed, for instance, comparatively higher levels of methamphetamine in Barcelona and amphetamine in Bilbao, with about 1-fold higher consumption of these two substances in such metropolitan areas. For amphetamine, an enantiomeric profiling was performed in order to assure the results were due to consumption and not to illegal dumping of production residues. Furthermore, different correction factors for the excretion of cannabis were used to compare consumption estimations. All wastewater results were compared with previously reported data, national seizure data and general population survey data, were a reasonable agreement was found. Daily and yearly drug consumption were extrapolated to the entire Spanish population with due precautions because of the uncertainty associated. These data was further used to estimate the retail drug market, where for instance cocaine illicit consumption alone was calculated to contribute to 0.2-0.5% of the Spanish gross domestic product (ca. 3000-6000 million Euro/year)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This study evaluates the applicability of a method based on the direct injection of a large volume of water samples to identify and quantify 34 priority and emerging substances, most of them discussed in Directive 2013/39/EU on priority substances in the field of water policy, and Decision 2018/840/EU (Watch List). The method directly injects 500 µL of filtered water sample and so does not use a pre-concentration step. The method was satisfactorily validated for influent and effluent water from a drinking water treatment plant, at three concentrations (1, 10 and 100 ng L -1 ) with precision and accuracies in the range 1-17% and 71-122% respectively. Sensitivity was good with detection limits in the range 0.15-10 ng L -1 and complied with EU limits in all cases except for estrone, 17-β-estradiol and 17-α-ethinylestradiol. For these hormones, an on-line solid phase extraction was developed and evaluated. The methods were applied to the analysis of water collected at the influent and effluent of a drinking water treatment plant and revealed the presence of 18 of the target compounds in the influent water and 8 in the effluent water. This showed that most the compounds had been efficiently removed by the processes of the drinking water treatment plant., Competing Interests: Declaration of Competing Interest The authors declare that they have no conflict of interest., (Copyright © 2020. Published by Elsevier B.V.)

Generally, dietary intake assessment and risk characterization are evaluated using contaminant concentration in raw fish while it is usually ingested cooked, which can cause an overestimation because one of the essential issues for risk-benefit analysis is to determine the maximum amount of a contaminant that can be released from the food matrix and be absorbed by the human body, called bioaccessibility. Moreover, despite most seafood products are cooked before consumption, risk assessment is still evaluated in raw products, strongly affecting public health guidelines. In the present study, an in vitro bioaccessibility assay was performed for Galaxolide (HHCB) in fish samples. Raw spiked hake samples were in vitro digested and aliquots of each fraction of the digestion process were analysed. HHCB was quantitatively present in the bioaccessibility fraction. The effect of fish cooking on HHCB was also evaluated in cod and mackerel samples. Results demonstrate that steaming and grilling processes lead to a loss of 50-70% HHCB in fish., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Iodinated X-ray contrast media (ICM-XR) are a group of pharmaceuticals widely used in medicine. Due to their low biodegradation rate, which makes their removal at wastewater treatment plants difficult, and the high doses at which they are administered, they have been detected in aquatic environments. In the present paper, a method for the quantitative determination of a group of ICM-XR in different fish species was developed and validated for the first time. Two extraction techniques were compared: pressurised liquid extraction (PLE) and QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe), with PLE being selected, followed by liquid chromatography-high resolution mass spectrometry. In addition, several clean-up strategies were evaluated. The optimised method provided PLE recoveries ranging from 60% to 88% and limits of detection ranging from 5ng/g to 25ng/g (dry weight). The method was applied in order to evaluate the presence of the selected ICM-XR in different fish species., (Copyright © 2016 Elsevier B.V. All rights reserved.)

An analytical method based on pressurised liquid extraction (PLE) followed by liquid chromatography-high resolution mass spectrometry (Orbitrap) was developed for the simultaneous determination of ten high-intensity sweeteners in fish samples. As the method was developed, the different PLE parameters were optimised and different clean-up strategies were evaluated, of which in-cell clean-up using alumina and on-cell clean-up with hexane were the most effective. PLE recoveries were between 43% and 94%. The method quantification limits were between 12.5ngg -1 dry weight (d.w.) and 250ngg -1 (d.w.) and the method detection limits between 2.5ngg -1 (d.w.) and 125ngg -1 (d.w.). Intra-day precision and inter-day precision were below 16% and 25%, respectively. Fish samples from different species were analysed and, saccharin was found below its method quantification limit in the species Scomber scombrus (Atlantic mackerel)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

An analytical method based on pressurized liquid extraction and solid-phase extraction with a mixed-mode Oasis(®) MAX sorbent as cleanup, followed by liquid chromatography with electrospray ionization and tandem mass spectrometry was developed and validated for the determination of seven widely used pharmaceuticals in mussel species. The optimization of the pressurized liquid extraction and the solid-phase extraction parameters is described. The method provided extraction recoveries ranging from 61 to 90%, and limits of detection ranging from 2 to 50 ng/g (dry weight). The repeatability and reproducibility of the method, expressed as relative standard deviation, were lower than 15 and 19%, respectively. The method was successfully applied to the analysis of mussel samples from different locations. The analyses showed that salicylic acid was present in mussels at concentrations up to 177 ng/g (dry weight)., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The occurrence of ten synthetic musks in samples of 10 widely consumed fish and shellfish species from Tarragona (Catalonia, Spain) was determined. The most used nitro and polycyclic musks, as well as a well-known transformation product in tissues, were analyzed. Furthermore, the human health risks derived from the musk exposure through seafood consumption were characterized. None of the nitro musks were detected in any of the analyzed samples. In contrast, most of the polycyclic musks were found, being galaxolide (HHCB) and tonalide (AHTN) present in all the samples. HHCB was the greatest contributor, with maximum levels in sardine and mackerel (367 and 304 ng g(-1) (d.w.) (dry weight), respectively). The highest exposure to individual musks was estimated for HHCB and HHCB-Lactone, with average values of 19.7 and 6.8 ng kg(-1)bw day(-1), respectively, in adults. A notably lower mean exposure was calculated for AHTN, cashmeran (DPMI) and traseolide (ATII), being ranged between 1.1 and 3.7 ng kg(-1)bw day(-1). The current concentrations of musks in fish and shellfish should not mean human health risks for the adult population living in Tarragona. However, a continuous monitoring would be desirable to assure that the exposure does not follow increasing temporal trends., (Copyright © 2015 Elsevier Inc. All rights reserved.)

A method for the quantitative determination of seven pharmaceuticals in bivalves was developed by QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction, followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with electrospray ionization. Both the European Standard Method EN 15662 and the AOAC Official Method 2007.01 for QuEChERS were tested. In addition, several clean-up strategies were evaluated in order to clean the matrix previous to the LC-MS/MS analyses. Dispersive solid-phase extraction with silica gel and modification of the chromatographic separation were the clean-up strategies that gave the best results. The optimized method was validated in mussels (Mytilus galloprovincialis) and allowed the determination of pharmaceuticals at nanograms per gram levels (dry weight (d.w.)). Limits of quantification ranged from 5 to 100 ng/g. Apparent recoveries ranged from 35 to 77%. The application of this method to bivalves revealed the presence of salicylic acid at concentrations up to 103 ng/g (d.w.).

Musk compounds are widely used as fragrances in personal care products. On account of their widespread use and their low biodegradation, they can be found in environmental samples. In our study two extraction methodologies were compared and different clean-up strategies were also studied in order to develop a reliable analytical method, with minimum matrix effect and good detection limits, to determine synthetic musk fragrances- six polycyclic musks, three nitro musks and the degradation product of one polycyclic musk- in fish and mussel samples. The first extraction technique involves a QuEChERS extraction, a consolidate extraction methodology in the field of food analysis of growing interest over recent years, followed by a dispersive solid-phase extraction (dSPE) as clean-up strategy. The second extraction technique consists of a conventional pressurised liquid extraction (PLE) with dichloromethane and an in-cell clean-up to decrease the matrix effect and remove the undesired components(⁎)present in PLE extracts. Large volume injection (LVI) followed by gas chromatography-ion trap-tandem mass spectrometry (GC-IT-MS/MS) was chosen as the separation and detection technique. Validation parameters, such as method detection limits and method quantification limits were found at ng g(-1) levels for both fish and mussel matrices. Good levels of intra-day and inter-day repeatabilities were obtained analysing fish and mussel samples spiked at 50 ng g(-1) (d.w.) (n=5, RSDs<17%). The developed PLE/GC-IT-MS/MS method was successfully applied to determine the target musk fragrances present in fish and mussel samples from the local market in Tarragona and fish samples from the Ebro River. The results showed the presence of galaxolide (2.97-18.04 ng g(-1) (d.w.)) and tonalide (1.17-8.42 ng g(-1) (d.w.)) in all the samples analysed, while the remaining polycyclic musks such as cashmeran, celestolide and phantolide, were only detected in some of the fish samples analysed. None of the samples analysed contained detectable traces of the nitro musks studied., (Copyright © 2014 Elsevier B.V. All rights reserved.)

An on-line coupling solid-phase extraction (SPE) has been developed for the first time to preconcentrate trace amounts of 17 musk fragrances extensively used in personal care products (6 polycyclic musks, 3 nitro musks, 7 macrocyclic musks and 1 polycyclic musk degradation product) from wastewater samples, prior to analysis by gas chromatography and mass spectrometry through an on-column interface. A 10 mm × 2 mm I.D. precolumn packed with Oasis HLB (60 μm) or C18 (60 μm) was compared for the optimization of the solid-phase extraction process. The parameters affecting the transfer of the analytes from the precolumn to the GC system (e.g. flow-rate, temperature and solvent vapor exit time) as well as SPE parameters (e.g. sample flow, sample volume, elution solvent, etc.) were optimized. An organic modifier such as methanol was added to the sample before the extraction process to avoid adsorption problems. The use of the MS detector under selected ion monitoring acquisition enabled the analytes to be quantified at low ng L(-1) levels, preconcentrating only 10 mL of sample, and the limits of detection were between 1 and 30 ng L(-1). The method was applied for the determination of musk fragrances in wastewater samples from three urban wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed that galaxolide, tonalide and ambrettolide were the most abundant musk compounds with concentrations ranging between 18 ng L(-1) and 45,091 ng L(-1), 852 ng L(-1) and 49,904 ng L(-1) and 507 ng L(-1) and 21,528 ng L(-1) respectively. The remaining musks were present at lower concentrations and two of the macrocyclic musk studied (musk MC4 and civetone) were not detected. The analysis of effluent wastewater showed a decrease in the concentrations of all of the compounds present in influent samples, with the decrease being more significantly in the case of polycyclic and nitro musks than for macrocyclic musks. Only HHCB-lactone remained constant or increased its concentration., (Copyright © 2014 Elsevier B.V. All rights reserved.)

An analytical method based on pressurized liquid extraction (PLE) and liquid chromatography-(electrospray)-tandem mass spectrometry was developed for the simultaneous determination of nicotine, four drugs of abuse (opiates and alkaloids) and four of their main metabolites in sewage sludge. The optimum PLE conditions were: cell volume 11 mL, dichloromethane as extraction solvent, 5 min preheating time, 100 °C temperature, 1500 psi pressure, 60% flush volume, 1 cycle, 15 min static extraction time, 120 s purge time and sample weight 1g. Absolute recoveries for all compounds were between 25% and 65%. Data acquisition was done by selective reaction monitoring and the two most abundant product ions were used for confirmation. Limits of detection were lower than 10 μg/kg dry weight (d.w.) and limits of quantification were between 2.5 and 25 μg/kg (d.w.). The highest concentrations found in sludge samples from two sewage treatment plants were for nicotine and cocaine in the range of 23-173 μg/kg (d.w.) and 9-232 μg/kg (d.w.) respectively., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction method followed by liquid chromatography-(Orbitrap) high resolution mass spectrometry was developed for the simultaneous determination of five benzotriazole, four benzothiazole and five benzenesulfonamide derivates in sewage sludge. While the method was being developed, several buffers and dispersive solid-phase extraction clean-up (dSPE) sorbents were tested. Citrate buffer and Z-sep+ (zirconium-based sorbent) were the most effective extraction buffer and dSPE clean-up material. The absolute recoveries were higher than 80% for all compounds (100ng/g (d.w.)) and the matrix effect was less than -20% for most compounds. The limits of detection were between 0.5 and 10ng/g (d.w.) and the limits of quantification (LOQ) were between 1 and 25ng/g (d.w.). Repeatability and reproducibility were lower than 15% (%RSD, n=5). Several sludge samples from five sewage treatment plants in Catalonia were analysed and the most abundant compounds were 2-hydroxybenzothiazole (

A method for the quantitative determination of ten musk fragrances extensively used in personal care products from sewage sludge was developed by using a pressurized liquid extraction (PLE) followed by an automated ionic liquid-based headspace single-drop microextraction and gas chromatography-tandem mass spectrometry. The influence of main factors on the efficiency of PLE was studied. For all musks, the highest recovery values were achieved using 1 g of pretreated sewage sludge, H(2) O/methanol (1:1) as an extraction solvent, a temperature of 80°C, a pressure of 1500 psi, an extraction time of 5 min, 2 cycles, a 100% flush volume, a purge time of 120 s, and 1 g Florisil as in-cell clean-up extraction sorbent. The use and optimization of an in-cell clean-up sorbent was necessary to remove fatty interferents of the PLE extract that make the subsequent ionic liquid-based headspace single-drop microextraction difficult. Validation parameters, namely LODs and LOQs, ranged from 0.5-1.5 to 2.5-5 ng/g, respectively. Good levels of intra- and interday repeatabilities were obtained analyzing sewage sludge samples spiked at 10 ng/g (n = 3, RSDs < 10%). The method applicability was tested with sewage sludge from different wastewater treatment plants. The analysis revealed the presence of all the polycyclic musks studied at concentrations higher than the LOQs, ranging from 6 to 530 ng/g. However, the nitro musk concentrations were below the LOQs or, in the case of musk xylene, was not detected., (© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A method for the quantitative determination of the nine EPA N-nitrosamines in sewage sludge was developed by using pressurised hot water extraction (PHWE) followed by headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to chemical ionization ion trap tandem mass spectrometry (GC-CI-MS-MS). The pressurised hot water extraction was optimized using a central composite design with regard to operational parameters such as temperature, extraction time and pH of water as extracting solvent. The optimum conditions were: water at pH 7.5 as extracting solvent, temperature of 125°C and extraction time of 5 min. The sewage sludge extract was automatically analyzed by HS-SPME using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber and GC-CI-MS-MS. The limits of detection of all compounds were lower than 0.15 μg/kg of dry weight (d.w.) of sewage sludge. The repeatability and reproducibility between days (10μg/kg d.w.) expressed as relative standard deviation were lower than 16 and 19%, respectively. The method was applied to determine the N-nitrosamines in sewage sludge from urban and industrial sewage treatment plants (STPs) and from a potable water treatment plant. Some N-nitrosamines were determined in the samples and N-nitrosodiethylamine (NDEA) and N-nitrosodi-n-butylamine (NDBA) showed the highest values (371 and 305 μg/kg (d.w.), respectively) in sewage from industrial STPs., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The growing demand on water resources has increased the interest in wastewater reclamation for multiple end-use applications such as indirect and direct potable reuse. In these applications, the removal of organic micropollutants is of a greater concern than in conventional wastewater treatment. This article presents a collection of data of trace organic micropollutants in an urban wastewater treatment plant (WWTP) in North East Spain using reverse osmosis (RO) membrane treatment. The RO rejection values of the organic molecules studied with a wide range of solute size and hydrophobicity were determined. Several chromatographic methods monitoring different endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs) were used. Results indicated that secondary effluents from this Spanish WWTP contained most of the studied organic compounds indicating incomplete removal of organics in the conventional treatment of the plant. However, the rejection of most micropollutants was high for all three RO membrane types (low energy, high rejection, fouling resistant) tested. It was observed that some selected micropollutants were less efficiently removed (e.g. the small and polar and the more hydrophobic) and the molecular weight and membrane material influenced removal efficiencies.

An automated, environmentally friendly, simple, selective, and sensitive method was developed for the determination of ten primary aliphatic amines in sewage sludge at μg/kg dry weight (d.w.). The procedure involves a pressurized hot water extraction (PHWE) of the analytes from the solid matrix, followed by a fully automated on-fiber derivatization with 2,3,4,5-pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) and subsequent gas chromatography ion-trap tandem mass spectrometry (GC-IT-MS-MS) analysis. The limits of detection (LODs) of the method were between 0.5 and 45 μg/kg (d.w.) for all compounds except for ethyl-, isopropyl-, and amylamine, whose LODs were 70, 109, and 116 μg/kg (d.w.), respectively. The limits of quantification (LOQs) were between 10 and 350 μg/kg (d.w.). Repeatability and intermediate precision, expressed as RSD(%) (n=3), were lower than 18 and 21%, respectively. The method developed enabled to determine primary aliphatic amines in sludge from various urban and industrial sewage treatment plants as well as from a potable treatment plant. Most of the primary aliphatic amines were found in the sewage sludge samples analyzed corresponding to the maximum concentrations to the samples from the urban plant: for instance, isobutylamine and methylamine were found at 7728 and 12 536 μg/kg (d.w.), respectively. Amylamine was detected only in few samples but always at concentrations lower than its LOQ., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A solid-phase extraction and liquid chromatography-tandem mass spectrometry (SPE/LC-MS-MS) method was developed and validated for the simultaneous determination of nicotine, five drugs of abuse (morphine, cocaine, codeine, methadone, and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine) and four metabolites (dihydrocodeine, 6-acetylmorphine, 11-nor-carboxy-Δ(9)-tetrahydrocannabinol, and benzoylecgonine) in water samples. A Fused-Core™ particle column was used as an alternative to sub-2-μm particles in chromatographic separations to work with low backpressures and high efficiencies in short analysis times. Drugs were extracted from waste and surface water with SPE using Oasis MCX cartridges. Electrospray (ESI) in positive and negative mode and tandem MS selected reaction monitoring mode were used for identification and quantification. Calibration by linear regression analysis with deuterated internal standards was used to compensate the matrix effects. Limits of detection were found as low as 0.5-1 ng/L (surface water) and 1-50 ng/L (wastewater). The method was applied to the analysis of different kinds of samples. Wastewater from a sewage treatment plant was collected from three sampling points (after primary, secondary, and tertiary treatments) for a week. The analysis of the samples revealed a significant presence of these drugs in samples from primary treatments, where maximum concentrations of nicotine (1105 ng/L) and benzoylecgonine (3336 ng/L) were found. Most of the compounds showed values between

A fully automated method for determining nine Environmental Protection Agency N-nitrosamines in several types of environmental waters at ng/L levels is presented. The method is based on a headspace solid-phase microextraction followed by GC-MS-MS using chemical ionization. Three different fibers (carboxen/PDMS, divinylbenzene/carboxen/PDMS, and PEG) were tested. Solid-phase microextraction conditions were best when a divinylbenzene/carboxen/PDMS fiber was exposed for 60 min in the headspace of 10 mL water samples at pH 7 containing 360 g/L of NaCl, at 45°C. All compounds were analyzed by GC-MS-MS within 18 min. The method was validated using effluent from an urban wastewater treatment plant and the LODs ranged from 1 to 5 ng/L. The method was then applied to determine the N-nitrosamines in samples of different complexities, such as tap water and several influent and effluent wastewater samples from urban and industrial wastewater treatment plants and a potable water treatment plant. Although the analysis of influent industrial wastewater revealed high concentrations of some compounds (N-nitrosomorpholine and N-nitrosodimethylamine at μg/L levels), in industrial effluents and other samples, the concentrations were substantially lower (ng/L levels). The new method is suitable for the simple and reliable determination of N-nitrosamines in highly complex water samples in a completely automated procedure.

Stir-bar-sorptive extraction (SBSE) with liquid desorption (LD) and ultra-high-performance liquid chromatography-electrospray ionization triple-quadrupole tandem mass spectrometry (UHPLC-(ESI)MS-MS) were used for analysis of six personal care products in environmental water: four UV filters (2,2-dihydroxy-4-methoxybenzophenone, benzophenone-3, octocrylene, and octyldimethyl-p-aminobenzoic acid) and two antimicrobial agents (triclocarban and triclosan). Experimental conditions that affect SBSE-LD sorption efficiency (extraction time and temperature, sample pH, and ionic strength) and desorption efficiency (solvent, temperature, and time) were optimized. The method proved to be sensitive--a 50-mL sample was used to determine these compounds in environmental waters at trace levels. The detection limits of the analytical method were 2.5 ng L(-1) for river water and 5-10 ng L(-1) for effluent and influent sewage water. In river waters, benzophenone-3 was found at levels from 6 ng L(-1) to 28 ng L(-1) and triclosan at levels

The contamination of wastewater and sewage sludge has been examined for three phosphodiesterase type V inhibitors sildenafil, vardenafil and tadalafil, active agents of Viagra, Levitra and Cialis, respectively. Sensitive quantification methods based on solid-phase extraction (SPE) and pressurized liquid extraction (PLE) followed by high performance liquid chromatography - tandem mass spectrometry (HPLC-MS/MS) have been developed to analyse these compounds in wastewater and sewage sludge. Effluent water of nine sewage treatment plants (STPs) has been analysed to assess the impact of the phosphodiesterase type V inhibitors on the environment. One municipal STP (Tarragona, Spain) has been thoroughly studied over the year 2008 (i) with respect to the distribution of these compounds among influent and sewage sludge and (ii) the elimination efficiency. The developed methods allowed quantification at trace concentrations. Sildenafil was present in all investigated samples at the low ng/L and ng/g range, respectively. Tadalafil was not detected or below the limit of detection (LOQ) in effluent water taken in Spain but in sewage sludge (12 ng/g - < LOQ). Vardenafil was present only in one sludge sample and between 5 ng/g and < LOQ in effluent water. The overall removal efficiency of the STP in Tarragona (Spain) is 68%, 69% and 80% for sildenafil, tadalafil and vardenafil, respectively. This study shows for the first time the determination of these compounds in wastewater and sewage sludge., (Copyright 2009 Elsevier Ltd. All rights reserved.)

This paper presents a fully automated method for determining ten primary amines in wastewater at ng/L levels. The method is based on simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to ion trap tandem mass spectrometry (GC-IT-MS-MS). The influence of main factors on the efficiency of derivatization and of HS-SPME is described in detail and optimized by a central composite design. For all species, the highest enrichment factors were achieved using a 85 microm polyacrylate (PA) fiber exposed in the headspace of stirred water samples (750 rpm) at pH 12, containing 360 g/L of NaCl, at 40 degrees C for 15 min. Under optimized conditions, the proposed method achieved detection limits ranging from 10 to 100 ng/L (except for cyclohexylamine). The optimized method was then used to determine the presence of primary amines in various types of wastewater samples, such as influent and effluent wastewater from municipal and industrial wastewater treatment plants (WWTPs) and a potable water treatment plant. Although the analysis of these samples revealed the presence of up to 1500 microg/L of certain primary amines in influent industrial wastewater, the concentration of these compounds in the effluent and in municipal and potable water was substantially lower, at low microg/L levels. The new derivatization-HS-SPME-GC-IT-MS-MS method is suitable for the fast, reliable and inexpensive determination of primary amines in wastewater in an automated procedure., (Copyright 2009 Elsevier B.V. All rights reserved.)

Personal care products (PCPs) are widely used emerging contaminants which can cause adverse environmental effects. This paper reports the development and validation of a method based on solid-phase extraction (SPE) and ultra-high-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry (UHPLC-(ESI)MS-MS) for simultaneously determining eleven PCPs: 4 preservatives (methylparaben; ethylparaben; benzylparaben; propylparaben); 2 antimicrobial agents (triclocarban and triclosan) and 5 UV filters (2,4-dihydroxybenzophenone; 2,2-dihydroxy-4-methoxybenzophenone; benzophenone-3; octocrylene and octyldimethyl-p-aminobenzoic acid) in environmental waters in only 9 run minutes of chromatographic separation. The SPE was carried out with two polymeric cartridges (Oasis HLB and Bond Elut Plexa). The recoveries obtained with Bond Elut Plexa were between 69% and 101% for 500 mL of river waters, with the exception of octyldimethyl-p-aminobenzoic acid (46%). Limits of detection for 500 mL of river water were in the range of 1-5 ng/L. Oasis HLB was chosen for wastewater samples with recoveries between 38% and 92% (250 mL of effluents) and 36-89% (100mL of influents). In both wastewater samples, octyldimethyl-p-aminobenzoic acid and methylparaben showed the lowest recoveries (20% and 27%). The method revealed benzophenone-3 as having the highest concentration levels ( 7 ng/L) in river waters. Most of PCPs determined were found in influent waters being methylparaben and propylparaben the ones found at highest concentration with values of 5613 and 1945 ng/L, respectively. In effluent waters, significant lower levels of some PCPs were found, being benzophenone-3 the one found at the highest concentration (100 ng/L).

A sensitive method for simultaneously determining eleven free and conjugated steroid estrogens has been developed using liquid chromatography-(electrospray)triple quadrupole-mass spectrometry (LC-(ESI)MS-MS) in negative mode with application to environmental aqueous matrices. Two selected reaction monitoring (SRM) transitions per compound were used, one of which was used for quantification and the second one for confirmation. The procedure includes a solid-phase extraction with an Oasis HLB solid-phase cartridge. Recoveries in 500 mL of river water spiked at 50 ng/L for sulfate estrogens and 100 ng/L for the rest of the compounds were 46-87%, except for E2, which had lower values (32%). Recoveries in wastewater were higher than 49% and 30% for all the compounds, except E2-17A and E2-17G (lower than 26% and 28%, respectively), in effluent (250 mL) and influent (100 mL), respectively. Ion suppression is a well-known phenomenon when using ESI; thus its impact on method recovery made us consider this effect when quantifying our samples. Limits of detection varied from 2 to 30 ng/L in river water and 10 to 100 ng/L in sewage water. The method was used to determine the target compounds in the Ebro river water where none of the analytes were found. In effluent and influent water samples, EE2, E1-3S and E2-3S were determined at concentration levels ranging from 35 to 160 ng/L.

In this study we present a pressurized liquid extraction/liquid chromatography-tandem mass spectrometry (PLE/LC-MS-MS) method to determine a group of estrogens and conjugated estrogens in sewage sludge. Parameters that affect the extraction step such as extraction solvent, temperature, pressure, static extraction time, number of cycles, purge time and flush volume have been optimized. In the LC-MS-MS system, electrospray ionization and a triple quadrupole analyzer have been used, and the multiple reaction monitoring mode has enabled low levels of target analytes to be detected. All recoveries were higher than 81% except for estrone 3-glucoronide and estradiol 17-glucoronide which were not extracted and consequently, they were not considered in the present study. The repeatability and reproducibility between days expressed as %RSD (n=3), were lower than 6% and 9%, respectively. The method developed allowed the target analytes to be quantified at low levels of microg/kg. The limits of detection were lower than 26 microg/kg of dry weight (d.w.) of sewage sludge, except for 17 alpha-estradiol, 17beta-estradiol, 17 alpha-ethinylestradiol and estradiol 17-acetate whose values were between 150 and 175 microg/kg (d.w.). The method was applied to determine these compounds in sewage sludge from two domestic sewage treatment plants. Estrone 3-sulfate, estradiol 3-sulfate, diethylstilbestrol, estrone and estriol were determined in some samples and estriol showed the highest value (406 microg/kg d.w.).

This paper describes a method for determining 11 pharmaceuticals in various water sources by SPE followed by LC-(ESI) MS. SPE was carried out with Oasis HLB and the recoveries were 33-67% for 250 and 100 mL sewage water, 55-77% for 500 mL river water and 72-98% for 1 L tap water, with the exception of sulfamethoxazole and omeprazole which showed lower recoveries in all kinds of sample. The LODs in river water were of 5 ng/L for sulfadiazine, trimethoprim, sulfamethazine, sulfamethoxazole, and ranitidine and 10 ng/L for the other compounds. The highest concentrations found in river waters were for sulfamethoxazole (50 ng/L). In influent sewage waters, ranitidine was the most commonly detected compound with a maximum value of 0.24 microg/L.

A method was developed to determine 11 pharmaceutical compounds in water samples. The method uses SPE and HPLC coupled to MS (LC/MS) using ESI in both positive and negative modes. Three different sorbents were compared for the extraction of analytes from river and sewage treatment plant (STP) waters and OASIS HLB provided the best results. For the solid-phase extraction of 500 mL of river water samples, the recoveries were between 41 and 101% with the exception of acetaminophen, salicylic acid and naproxen. The LODs were between 3 and 5 ng/L for all the compounds, except naproxen which had an LOD of 15 ng/L. Acetaminophen, caffeine, carbamazepine, bezafibrate and ibuprofen were found in three of the tested river samples at ng/L levels and among them, the highest values were for caffeine and bezafibrate with 305 and 363 ng/L, respectively. For the influent and effluent water samples of the STP, volumes of 100 and 250 mL were used, respectively, to obtain acceptable recoveries. All the compounds showed recoveries between 33 and 91% for effluent samples and 33-72% for influent samples, with the exception of acetaminophen, salicylic acid and bezafibrate, which had lower recoveries. The method developed enabled pharmaceuticals in the influent and effluent sewage waters to be determined in five campaigns carried out between February 2004 and June 2005. Several pharmaceuticals were found in the influent samples: for instance, maximum concentrations of ibuprofen and caffeine were 6 and 40 microg/L, respectively.

We monitored 26 compounds known or suspected to be endocrine disruptors in several environmental water samples from a river, the sea, and an irrigation canal. Because of the various chemical properties of the compounds monitored, analyses were carried out by using two different methods. One method is based on solid-phase extraction (SPE) on-line coupled to gas chromatography-mass spectrometry through an on-column interface. Another is based on high-performance liquid chromatography-(electrospray) mass spectrometry working in negative ionization mode and using off-line SPE. The limits of detection for the two methods were at levels of low microg/L. Phthalates and bis-(2-ethylhexyl) adipate were found at levels between 0.05 and 13 microg/L in all of the water samples analyzed. Some pesticides, alkylphenols, and estrogens were determined in a few samples at levels below 0.1 microg/L.

Spain is one of the European countries that still discharges untreated wastewaters and sewage sludge into the sea. Aromatic monosulfonated compounds were detected in 36 seawater samples collected bimonthly on the Catalonian coast (Spain) over a period of 18 months. These compounds are of environmental concern because of their limited biodegradability and high mobility within the aquatic system. A method based on a sequential solid-phase extraction procedure (SSPE) followed by ion-pair liquid chromatography coupled to electrospray ionization-mass spectrometry (IPC-ESI-MS) in negative ionization mode was used to monitor aromatic monosulfonated compounds in the Catalonian coastal waters. Triethylamine (TEA) and acetic acid (HOAc) were used as volatile mobile-phase additives. A comparison of two polymeric solid-phase extraction (SPE) materials for the extraction of 15 aromatic monosulfonated compounds of environmental concern was performed. The investigated adsorbents were the polystyrene-divinylbenzene materials Lichrolut EN, from Merck, and Isolute ENV+, from International Sorbent Technology (IST). The influence of the matrix on the analysis of seawater samples was also studied. Applications of the developed analytical procedure to seawater samples gave limits of detection (n = 3) ranging from 0.6 to 45 pg on column for the target analytes. Barcelona and Tarragona locations were chosen along the Catalonian coast as sampling sites because of their large sewage discharges and intensive industrial activities. Samples were acquired from submarine outfalls of two rivers, Besos and Llobregat, located in the north and south of Barcelona city, respectively. Samples from petrochemical industry submarine outfalls located near the commercial port of Tarragona were also studied. Concentrations of benzenesulfonates (BS) and naphthalenesulfonates (NS) were of the order of ng/ml. Most of the collected samples were found to contain both isomers of mononaphthalenesulfonate. The study showed that these compounds can contaminate marine coastal waters.