Screening of organic chemicals associated to virgin low-density polyethylene microplastic pellets exposed to the Mediterranean Sea environment by combining gas chromatography and liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry.

In this work, organic chemicals associated with microplastics (MPs) exposed to a coastal anthropogenized environment for up to eight weeks have been screened for, in order to discern the (de)sorption dynamics of chemicals in the marine ecosystem. Low-density polyethylene (LDPE) pellets were studied since they represent primary MPs used by the plastic industry and a relevant input of MPs into the oceans. To maximize the coverage of chemicals that could be detected, both liquid and gas chromatography coupled to quadrupole-time-of-flight (GC-QTOF and LC-QTOF, respectively) were used. In the case of LC-QTOF, an electrospray ionization source was employed, and the compounds were investigated by combining suspect and non-target screening workflows. The GC-QTOF was equipped with an electron ionization source and compounds were screened in raw and derivatized (silylated) extracts by deconvolution and contrast to high- and low-resolution libraries. A total of 50 compounds of multifarious classes were tentatively identified. Among them, melamine and 2-ethylhexyl salicylate (EHS) were detected in the original MPs but were rapidly desorbed. Melamine was completely released into the marine environment, while EHS was partly released but a portion remained bound to the MPs. On the other hand, many other chemicals of both anthropogenic (e.g. phenanthrene or benzophenone) and natural origin (e.g. betaine and several fatty acids) accumulated onto MPs over time. Quantification of 12 unequivocally identified chemicals resulted into a total concentration of 810 µg/kg after MPs exposure for 8 weeks.

Chlorhexidine residues in sludge from municipal wastewater treatment plants: analytical determination and toxicity evaluation.

In this work, a procedure for the sensitive and selective determination of chlorhexidine in sludge from municipal sewage treatment plants (STPs) based on matrix solid-phase dispersion (MSPD) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was optimized and validated. Analysis of sewage sludge samples, obtained from different STPs in Northwest Spain from 2018 to 2021, showed that chlorhexidine was ubiquitous in this environmental compartment with concentrations between 0.3 and 16 µg g-1. The toxicity of this pollutant was assessed in in vitro assays considering three different model organisms: Candida albicans, Escherichia coli, and Staphylococcus aureus. C. albicans was the most sensitive of the tested microorganisms to chlorhexidine with a lethal threshold concentration of 0.1 mg L-1. Thus, the lowest observed sludge residue was 3 times higher than the acute toxicity threshold measured for C. albicans. Moreover, E. coli and S. aureus were also affected at chlorhexidine concentrations around 1.8 mg L-1 and 0.5 mg L-1, respectively. So, chlorhexidine residues might affect the population of microorganisms existing in STPs. In addition, the potential phytotoxicity of the compound was evaluated with germination experiments using different model seeds. At the evaluated dose (10 µg g-1 dried soil), chlorhexidine did not affect the germination of Sorghum saccharatum, Lepidium sativum, or Sinapis alba seeds. Thus, amending agriculture soils with chlorhexidine containing sludge is unlikely to affect the germination of plants.

Use of illicit drugs, alcohol and tobacco in Spain and Portugal during the COVID-19 crisis in 2020 as measured by wastewater-based epidemiology.

The COVID-19 pandemic spread rapidly worldwide in the year 2020, which was initially restrained by drastic mobility restrictions. In this work, we investigated the use of illicit drugs (amphetamine, methamphetamine, ecstasy, cocaine and cannabis), and licit substances of abuse (alcohol and tobacco) during the earlier months (March-July 2020) of the pandemic restrictions in four Spanish (Bilbao and its metropolitan area, Vitoria-Gasteiz, Castellón and Santiago de Compostela) and two Portuguese (Porto and Vila do Conde) locations by wastewater-based epidemiology (WBE). The results show that no methamphetamine was detected in any of the locations monitored, while amphetamine use was only detectable in the two locations from the Basque Country (Bilbao and its metropolitan area and Vitoria-Gasteiz), with high estimated average usage rates (700-930 mg day-1 1000 inhabitant-1). The remaining substances were detected in all the investigated catchment areas. In general, no remarkable changes were found in population normalized loads compared to former years, except for cocaine (i.e. its main metabolite, benzoylecgonine). For this drug, a notable decrease in use was discernible in Castellón, while its usage in Porto and Santiago de Compostela seemed to continue in a rising trend, already initiated in former years. Furthermore, two events of ecstasy (3,4-methylenedioxymethamphetamine, MDMA) dumping in the sewage network were confirmed by enantiomeric analysis, one in Santiago de Compostela just prior the lockdown and the second one in the Bilbao and its metropolitan area in July after relieving the more stringent measures. The latter could also be associated with a police intervention. The comparison of WBE with (web) survey data, which do not provide information at a local level, points towards contradictory conclusions for some of the substances, thereby highlighting the need for stable WBE networks capable of near real-time monitoring drug use.

Mimicking human ingestion of microplastics: Oral bioaccessibility tests of bisphenol A and phthalate esters under fed and fasted states.

Notwithstanding the fact that microplastic fragments were encountered in the human stool, little effort has been geared towards elucidating the impact of chemical additives upon the human health. In this work, standardized bioaccessibility tests under both fasting and fed conditions are herein applied to the investigation of human oral bioaccessibility of plastic additives and monomers (i.e. eight phthalate esters (PAEs) and bisphenol A (BPA)) in low-density polyethylene (LDPE) and polyvinyl chloride (PVC) microplastics. The generation of phthalate monoesters is evaluated in the time course of the bioaccessibility tests. Maximum gastric and gastrointestinal bioaccessibility fractions are obtained for dimethyl phthalate, diethyl phthalate and BPA, within the range of 55-83%, 40-68% and 37-67%, respectively, increasing to 56-92% and 41-70% for dimethyl phthalate and diethyl phthalate, respectively, whenever their hydrolysis products are considered. Bioaccessibility fractions of polar PAEs are dependent upon the physicochemical characteristics of the microplastics, with greater bioaccessibility for the rubbery polymer (LDPE). With the method herein proposed, oral bioaccessible pools of moderately to non-polar PAEs can be also accurately assessed for risk-assessment explorations, with values ranging from 1.8% to 32.2%, with again significantly larger desorption percentages for LDPE. Our results suggested that the highest gastric/gastrointestinal bioaccessibility of the eight PAEs and BPA is reached under fed-state gastrointestinal extraction conditions because of the larger amounts of surface-active biomolecules. Even including the bioaccessibility factor within human risk assessment/exposure studies to microplastics, concentrations of dimethyl phthalate, di-n-butyl phthalate and BPA exceeding 0.3% (w/w) may pose severe risks after oral uptake in contrast to the more hydrophobic congeners for which concentrations above 3% (w/w), except for diethylhexyl phthalate, would be tolerated.

Development and application of an in-house library and workflow for gas chromatography-electron ionization-accurate-mass/high-resolution mass spectrometry screening of environmental samples.

This work presents an optimized gas chromatography-electron ionization-high-resolution mass spectrometry (GC-EI-HRMS) screening method. Different method parameters affecting data processing with the Agilent Unknowns Analysis SureMass deconvolution software were optimized in order to achieve the best compromise between false positives and false negatives. To this end, an accurate-mass library of 26 model compounds was created. Then, five replicates of mussel extracts were spiked with a mixture of these 26 compounds at two concentration levels (10 and 100 ng/g dry weight in mussel, 50 and 500 ng/mL in extract) and injected in the GC-EI-HRMS system. The results of these experiments showed that accurate mass tolerance and pure weight factor (combination of reverse-forward library search) are the most critical factors. The validation of the developed method afforded screening detection limits in the 2.5-5 ng range for passive sampler extracts and 1-2 ng/g for mussel sample extracts, and limits of quantification in the 0.6-3.2 ng and 0.1-1.8 ng/g range, for the same type of samples, respectively, for 17 model analytes. Once the method was optimized, an accurate-mass HRMS library, containing retention indexes, with ca. 355 spectra of derivatized and non-derivatized compounds was generated. This library (freely available at https://doi.org/10.5281/zenodo.5647960 ), together with a modified Agilent Pesticides Library of over 800 compounds, was applied to the screening of passive samplers, both of polydimethylsiloxane and polar chemical integrative samplers (POCIS), and mussel samples collected in Galicia (NW Spain), where a total of 75 chemicals could be identified.

Transformation products of the high-volume production chemicals 1-vinyl-2-pyrrolidinone and 2-piperazin-1-ylethanamine formed by UV photolysis.

This work investigates the reaction of 1-vinyl-2-pyrrolidinone (VP) and 2-piperazin-1-yletanamine (PPE) under UV radiation. Both substances are high-volume production chemicals (production >1000 tons/year) widely used in polymers, coatings and a wide array of applications, which have been classified as mobile chemicals and which can then lead to the formation of persistent and mobile transformation products (TPs). Thus, their reaction with UV light was studied by means of liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-QTOF-MS). Both compounds presented a high reactivity, the VP quantum yield was 0.28 mol/E; whereas, PPE had a quantum yield notably higher than 1 (16 mol/E). Five and 7 TPs were identified for VP and PPE, respectively. Some of them had been already reported in literature due to sunlight photodegradation or other oxidation processes, but most of them are reported here for the first time. Finally, the acute and chronical toxicity of precursors and TPs were estimated using two quantitative structure-activity relationship (QSAR) software tools which led to some discrepancies in the estimations, pointing to the need for experimental toxicity assays for these compounds.

Source identification of amphetamine-like stimulants in Spanish wastewater through enantiomeric profiling.

Amphetamine (AMP), methamphetamine (MAMP) and 3,4-methylenedioxymethamphetamine (MDMA) occur in wastewater not only as a result of illicit consumption, but also, in some cases, from prescription drug use or by direct drug disposal into the sewage system. Enantiomeric profiling of these chiral drugs could give more insight into the origin of their occurrence. In this manuscript, a new analytical methodology for the enantiomeric analysis of amphetamine-like substances in wastewater has been developed. The method consists of a solid-phase extraction (SPE) followed by liquid chromatography-triple quadrupole-tandem mass spectrometry (LC-MS/MS), which showed low quantification limits in the 2.4-5.5 ng L-1 range. The LC-MS/MS method was first applied to characterize a total of 38 solid street drug samples anonymously provided by consumers. The results of these analysis showed that AMP and MDMA trafficked into Spain are synthesized as racemate, while MAMP is exclusively produced as the S(+)-enantiomer. Then, the analytical method was employed to analyse urban wastewater samples collected from the wastewater treatment plants (WWTPs) of five different cities in 2018 and 2019. Consumption estimated through normalized population loads in wastewater showed an increased pattern of AMP use in the Basque Country. Furthermore, the enantiomeric profiling of wastewater samples was contrasted to lisdexamfetamine (LIS) and selegiline (SEL) prescription figures, two pharmaceuticals which metabolize to S(+)-AMP, and to R(-)-AMP and R(-)-MAMP, respectively. From this analysis, and considering uncertainties derived from metabolism and adherence to treatment, it was concluded that LIS is a relevant source of AMP in those cases with low wastewater loads, i.e. up to a maximum of 60% of AMP detected in wastewater in some samples could originate from LIS prescription, while SEL does not represent a significant source of AMP nor MAMP. Finally, removal efficiencies could be evaluated for the WWTP (serving ca. 860,000 inhabitants) with higher AMP influent concentrations. The removal of AMP was satisfactory with rates higher than 99%, whereas MDMA showed an average removal of approximately 60%, accompanied by an enrichment of R(-)-MDMA.

Combination of different chromatographic and sampling modes for high-resolution mass spectrometric screening of organic microcontaminants in water.

This study explores the combination of two sampling strategies (polar organic compounds integrative sampler (POCIS) vs. spot sampling) and four chromatographic retention modes (reversed-phase liquid chromatography (RPLC), hydrophilic interaction liquid chromatography (HILIC), mixed-mode liquid chromatography (MMLC) and supercritical fluid chromatography (SFC)) for high-resolution mass spectrometry (HRMS) screening of organic pollutants in water samples. To this end, a suspect screening approach, using iterative data-dependent tandem mass spectrometry (MS/MS) driven by a library of 3227 chemicals (including pharmaceuticals, pesticides, drugs of abuse, human metabolites, industrial chemicals and other pollutants), was employed. Results show that POCIS can afford a larger number of positive identifications as compared to spot sampling. On the other hand, the best suited retention mechanisms, in terms of identified analytes, are SFC, and followed by RPLC, MMLC and HILIC. However, the best combination (POCIS + SFC) would only allow the identification of 67% of the detected analytes. Thus, the combination of the two sampling strategies, spot and passive sampling, with two orthogonal retention mechanisms, RPLC and SFC, is proposed in order to maximize the number of analytes detected (89%). This strategy was applied to different surface water (river and estuary) samples from Galicia (NW Spain). A total of 155 compounds were detected at a confidence level 2a, from which the major class was pharmaceuticals (61%).

Comprehensive determination of phthalate, terephthalate and di-iso-nonyl cyclohexane-1,2-dicarboxylate metabolites in wastewater by solid-phase extraction and ultra(high)-performance liquid chromatography-tandem mass spectrometry.

Plasticizers are chemical compounds used in the production of flexible plastics for a large variety of applications. They are present in most of the environments and, hence, we are highly exposed to them via several routes (ingestion, inhalation, etc). Due to the endocrine disruption potential of some of these chemicals and the unknown toxicological effects of their alternatives, assessing human exposure to these contaminants is an issue of emerging concern. Herein we propose an analytical methodology for the determination of several plasticizer metabolites in wastewater as a non-invasive, cheap, and fast exposure monitoring tool complementary to the analysis of urine. A solid-phase extraction procedure followed by an ultra(high)-performance liquid chromatography-tandem mass spectrometry method was optimized and validated for 21 analytes among phthalate, terephthalate, and di-iso-nonyl cyclohexane-1,2-dicarboxylate metabolites. Method quantification limits ranged from 0.079 to 4.4 ng L-1. The method was applied to the analysis of seven daily composite wastewater samples collected in the NW of Spain. Metabolites of low molecular weight phthalates and of di-2-ethylhexyl phthalate were quantified in all samples, despite the existing regulations limiting the use of phthalates. Metabolites of terephthalates, introduced at the end of the 20th century as phthalate substituents, were also quantified in all samples, being the first time that they were detected in this matrix. Exposure back-calculation highlighted di-2-ethylhexyl terephthalate as the second most common plastic additive after diethyl phthalate in the population considered, reflecting the increasing substitution of di-2-ethylhexyl phthalate by its analogous terephthalate.

Reaction of phenazone-type drugs and metabolites with chlorine and monochloramine.

This work studies the chlorination and monochloramination reaction kinetics of two phenazone-type drugs (phenazone - Phe and propyphenazone - PrPhe) and three metabolites of phenazone-type drugs (4-formylaminoantipyrine - FAA, 4-aminoantipyrine - AA and 4-acetoamidoantipyrine - AAA). Kinetics were faster with chlorine (apparent second-order constants between 100 and 66,500 times higher) than with monochloramine. For FAA and AAA, no significant reaction was observed during monochloramination. Further, apparent rate constants decreased as the pH increased from pH 5.7 to 8.3, except during chlorination of AA. The transformation products (TPs) formed were also elucidated by liquid chromatography-high resolution mass spectrometry. The main transformation pathway for Phe and PrPhe consisted of halogenations, hydroxylations and dealkylations, while AAA and FAA were firstly transformed to AA, then followed by pyrazole ring opening and hydroxylations. The extend of the reaction was also tested in real water samples, where, in general, slower reaction kinetics were obtained during monochloramination, while the chlorination reaction showed similar half-lives to ultrapure water. Finally, acute and chronic toxicity of the TPs were estimated using two quantitative structure-activity relationship (QSAR) software (ECOSAR and TEST), showing that some TPs could be more toxic than their precursor compounds.

Assessing population exposure to phthalate plasticizers in thirteen Spanish cities through the analysis of wastewater.

Phthalates are widely used plasticizers that produce endocrine-disrupting disorders. Quantifying exposure is crucial to perform risk assessments and to develop proper health measures. Herein, a wastewater-based epidemiology approach has been applied to estimate human exposure to six of the mostly used phthalates within the Spanish population. Wastewater samples were collected over four weekdays from seventeen wastewater treatment plants serving thirteen cities and ca. 6 million people (12.8 % of the Spanish population). Phthalate metabolite loads in wastewater were transformed into metabolite concentrations in urine and into daily exposure levels to the parent phthalates. Considering all the sampled sites, population-weighted overall means of the estimated concentrations in urine varied between 0.7 ng/mL and 520 ng/mL. Very high levels, compared to human biomonitoring data, were estimated for monomethyl phthalate, metabolite of dimethyl phthalate. This, together with literature data pointing to other sources of this metabolite in sewage led to its exclusion for exposure assessments. For the remaining metabolites, estimated concentrations were closer to those found in urine. Their 4-days average exposure levels ranged from 2 to 1347 µg/(day∙inh), exceeding in some sites the daily exposure thresholds set for di-i-butyl phthalate and di-n-buthyl phthalate by the European Food Safety Authority.

First nation-wide estimation of tobacco consumption in Spain using wastewater-based epidemiology.

Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3'-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine consumption in the seven analyzed regions was 2.2 g/(day∙1000 inh.), without any daily pattern. This average estimated nicotine consumption value agreed with the value derived from official tobacco sales data. Differences in consumption among the seven studied regions were found, being Galicia, the region with the lowest rate, and the Basque Country and Catalonia those with the highest rates. However, no conclusive correlation was found between those values and the prevalence data taken from two different national surveys, nor sociodemographic and health data. This study demonstrates that this tool can complement other indicators in order to accurately assess tobacco consumption rates at regional and national levels and provides the most extensive application of the approach in the Spanish territory.

Applicability of mixed-mode chromatography for the simultaneous analysis of C1-C18 perfluoroalkylated substances.

A new analytical method for the determination of 22 perfluoroalkylated (carboxylic and sulfonic) acids in water samples is presented. The method's objective was to achieve the simultaneous quantification of compounds with different chain lengths (from C1 to C18). To this end, 500 mL of water were extracted with Oasis WAX solid-phase extraction cartridges and eluted with 3 mL of 5% ammonia in methanol. After evaporation to dryness, extracts were reconstituted in methanol:ultrapure water (1:1) and analyzed by mixed-mode liquid chromatography-tandem mass spectrometry (MMLC-MS/MS) using a weak anion exchange/reversed-phase column. The method provided good results, with limits of quantification lower than 1 ng/L in river water for most of compounds, except the two perfluorocarboxylic acids with the longest alkyl chain (>C14) and trifluoroacetic acid, for which a blank contamination problem was observed. The method proved good trueness and precision in both ultrapure and river water (R ≥ 81%, RSD ≤ 15%). After validation, the method was applied to the analysis of nine water samples where nine perfluoroalkylated acids were quantified. Seven of them were ultrashort- (C1-C4) and short-chain (C4-C8) perfluoroalkylated acids, pointing out the importance of developing methods capable to target such substances for further monitoring.

Determination of 18 organophosphorus flame retardants/plasticizers in mussel samples by matrix solid-phase dispersion combined to liquid chromatography-tandem mass spectrometry.

This study presents the development and validation of a new analytical method based on matrix solid-phase dispersion (MSPD), integrating sample extraction and clean-up in one single step, followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of 18 organophosphorus flame retardants and/or plasticizers (OPEs) in marine mussel (Mytilus edulis and Mytilus galloprovincialis) samples. Among these OPEs, 5 (tetraethyl 1,2-ethanediylbis(phosphonate), 6H-dibenzo[c,e] [1,2]oxaphosphinine 6-oxide, tris(2,3-dibromopropyl) phosphate, 2,2-propanediyldi-4,1-phenylene bis(phosphate) and resorcinol bis(diphenyl phosphate)) are considered here for the first time in marine samples. Different parameters affecting the MSPD (clean-up sorbent and elution solvent) were optimized to obtain a good compromise between analyte recoveries and extract clean-up. Also, particular attention was paid to tackle blank issues. The overall method was validated in terms of trueness, precision and detection and quantification limits. Percentages of recovery varied from 69% to 122% with relative standard deviations below 24%. Detection limits ranged from 0.06 to 5 ng g-1 and quantification limits from 0.19 to 17 ng g-1 dry weight. Finally, the method was applied to the analysis of 7 mussel samples collected in the coast of Galicia (Spain). 8 OPEs were detected in these samples at concentrations ranging from the LOQ to 291 ng g-1 dry weight.

Chlorination and bromination of 1,3-diphenylguanidine and 1,3-di-o-tolylguanidine: Kinetics, transformation products and toxicity assessment.

This works investigates the chlorination and bromination of two rubber and polymer related chemicals, which have emerged as relevant water contaminants, i.e. 1,3-di-o-tolylguanidine (DTG) and 1,3-diphenylguanidine (DPG). Kinetic constants at different pH values were obtained and modelled, taking into account the pKa values of DTG/DPG and HClO, showing that the maximum reaction rate (kapp > 104 M-1 s-1) is obtained at pH values 8.8 for DPG and 9.1 for DTG. Bromination is also very fast, although unlike chlorination, deviation from the model was observed at neutral pH, which was attributed to formation of metastable transformation product (TP). A total of 35 TPs, corresponding to halogenation, hydroxylation, formation of monophenylguanidine derivatives and cyclization reactions, were tentatively identified. Furthermore it was found that chloroform can be formed up to a 25% molar yield, while dichloroacetonitrile was formed into less than a 3% yield. Several ecotoxicological endpoints were predicted by quantitative structure-activity relationship models (QSAR) for the TPs, some of which were predicted to be more toxic than DPG/DTG. Also a chlorinated solution investigated by a Vibrio Fisheri acute toxicity test, confirmed that toxicity increases with chlorination.

Determination of human metabolites of chlorinated phosphorous flame retardants in wastewater by N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide-derivatization and gas chromatography-high resolution mass spectrometry.

The analysis of wastewater for the determination of human biomarkers of exposure (human metabolites) is a non-intrusive, economic and complementary alternative to the analysis of urine in the monitoring of human exposure to chemicals of concern. This study provides the first gas chromatography-based method for the determination of three metabolites of chlorinated organophosphorous flame retardants (OPFRs: bis(2-chloroethyl) phosphate, bis(chloropropyl) phosphate and bis(1,3-dichloro-2-propyl) phosphate) in wastewater. A solid-phase extraction procedure based on the use of mixed-mode reversed-phase weak anion exchange sorbents was optimized including a fractionated elution of OPFRs and their metabolites. Analytes derivatization was investigated by comparing two silylating reagents, N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide and N-methyl-N-(trimethylsilyl)trifluoroacetamide, the first one providing better results. Determination was performed by gas chromatography-high resolution mass spectrometry with a quadrupole-time-of-flight system (GC-QTOF) in order to improve selectivity. Furthermore, the use of GC-QTOF combined with the specific ion obtained from silylated metabolites (m/z 154.9924) can be exploited to screen for other phosphate ester metabolites. Under final conditions, the overall method performance was satisfactory, affording method detection limits ranging from 1.1 to 4.6 ng/L, percentages of recovery from 90% to 110%, and relative standard deviations below 13%. The analysis of composite raw wastewater samples collected over 24 h in the NW of Spain allowed to quantify, for the first time in this matrix, the metabolite bis(chloropropyl) phosphate at levels over 60 ng/L.

Legacy and emerging pollutants in marine bivalves from the Galician coast (NW Spain).

The presence of pollutants in estuary and oceanic systems is a global problem and a serious concern to human and environmental health. Usually, environmental monitoring studies consider classical persistent organic pollutants (POPs). However, the lists of POPs keep continuously growing and new POPs and other emerging pollutants should be considered in new monitoring programs. So, this study aimed to investigate the distribution and profile of classical POPs (polychlorinated biphenyl (PCBs), organochlorine pesticides (OCPs), and polycyclic aromatic hydrocarbons (PAHs)), new POPs and emerging pollutants (polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), novel halogenated flame retardants (NFRs) and UV filters) in bivalve mollusc samples (both raft-cultivated and wild mussel, Mytilus galloprovincialis; cockle, Cerestoderma edule; and clam, Ruditapes descussatus) collected in nine Galician Rias during the period February 2012 to February 2013. A predominance of PAHs (6.8-317 ng/g dry weight (dw)) followed by PCBs (0.47-261 ng/g dw), UV filters (1.4-157 ng/g dw), PFCs (0.53-62 ng/g dw), OCPs (0.07-29 ng/g dw), PBDEs (0.31-6.6 ng/g dw) and NFRs (0.07-3.2 ng/g dw) was found in the studied bivalves, being the UV filter octocrylene the compound found at the highest concentration (141 ng/g dw in a cockle sample), while the PAHs chrysene and benzo(b)fluoranthene were the compounds with the highest average concentration (20 and 14 ng/g dw, respectively). Inter-species, temporal and geographical variations on pollutants concentration were assessed by multifactorial analysis of variance. Statistically significant differences among the type of mollusc were observed for levels of organochlorinated and organobrominated pollutants considered (PCBs, OCPs and PBDEs), which were detected at higher concentrations in wild mussel. On the other hand, the main PFCs and UV filters showed a higher detection frequency in cockle samples. Location played significant role for PAHs, PCBs and the main PBDEs, being the most polluted rias those more industrialized and populated, i.e. A Coruña, Ferrol and/or Vigo. Finally, sampling timepoint was also a significant factor for most of the families considered but with different profiles. Thus, PAHs and PCBs showed higher concentrations in both February 2012 and 2013 and lower in August 2012, while the main PBDEs were measured at higher concentrations in November 2012 and lower in February 2012; and the main NFRs, PFCs and UV filters were present at lower levels in February 2013.

Profiling cocaine residues and pyrolytic products in wastewater by mixed-mode liquid chromatography-tandem mass spectrometry.

This work provides a new analytical method for the determination of cocaine, its metabolites benzoylecgonine and cocaethylene, the pyrolytic products anhydroecgonine and anhydroecgonine methyl ester, and the pharmaceutical levamisole in wastewater. Samples were solid-phase extracted and extracts analyzed by liquid chromatography-tandem mass spectrometry using, for the first time in the illicit drug field, a stationary phase that combines reversed-phase and weak cation-exchange functionalities. The overall method performance was satisfactory, with limits of detection below 1 ng/L, relative standard deviations below 21%, and percentages of recovery between 93% and 121%. Analysis of 24-hour composite raw wastewater samples collected in Santiago de Compostela (Spain) and Brasilia (Brazil) highlighted benzoylecgonine as the compound showing the highest population-normalized mass loads (300-1000 mg/day/1000 inhabitants). In Brasilia, cocaine and levamisole loads underwent an upsurge on Sunday, indicating a high consumption, and likely a direct disposal, of cocaine powder on this day. Conversely, the pyrolytic product resulting from the smoke of crack, anhydroecgonine methyl ester, and its metabolite anhydroecgonine were relatively stable over the four days, agreeing with a non-recreational-associated use of crack.

Determination of Persistent and Mobile Organic Contaminants (PMOCs) in Water by Mixed-Mode Liquid Chromatography-Tandem Mass Spectrometry.

The presence of persistent and mobile organic contaminants (PMOC) in aquatic environments has become a matter of concern due to their ability of breaking through natural and anthropogenic barriers, even reaching drinking water. The presence of many of these compounds in surface and drinking water has been reported in screening studies, but there is still a lack of analytical methods capable of quantifying them. Herein, we propose a method combining mixed-mode-solid-phase extraction (MM-SPE) as preconcentration technique and mixed-mode liquid chromatography (MMLC) coupled to tandem mass spectrometry as a determination technique for the quantitative determination of 23 target PMOCs in surface and drinking water samples. When compared to reversed-phase liquid chromatography, the MMLC protocol has proven to be superior in both retentive capabilities and peak shape for ionic compounds, while performing also well for neutrals. The overall method performance was satisfactory with limits of quantification under 50 ng L-1 for most of analytes in both surface and drinking water. The relative standard deviation was lower than 20%, and the average recovery was 78 and 80% in surface and drinking water, respectively. The method was applied to 15 water samples collected in Spain, where 17 out of the 23 target PMOCs were quantified in at least one sample. Among them, 6 chemicals (e.g., benzyltrimethylammonium) are reported and/or quantified here for the first time.

Multi-residue determination of psychoactive pharmaceuticals, illicit drugs and related metabolites in wastewater by ultra-high performance liquid chromatography-tandem mass spectrometry.

This study presents a new multi-residue analytical method for the simultaneous determination of 38 psychoactive drugs (including benzodiazepines, antidepressants and drugs of abuse) and related metabolites in raw wastewater. Potential analyte losses during sample filtration and stability in wastewater were evaluated. Analyte losses, especially for 12 compounds, were observed during filtration, indicating a strong sorption onto the filter material. In order to overcome this effect, filtered water samples were combined with methanolic washes of the corresponding filters and the resulting solutions were solid-phase extracted on mixed-mode (reverse-phase plus cation-exchange) sorbents. Extracts were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry. Quantification was performed by the internal standard method with isotopic labeled analogs. Recovery percentages varied between 65% and 137%; method quantification limits ranged between 0.2 and 22 ng/L in ultrapure water and between 0.3 and 30 ng/L in wastewater for all the analytes but three (for which they were ∼60-80 ng/L). The analysis of 24 h-composite samples collected during one week in the city of Santiago de Compostela demonstrated the ubiquity of 31 analytes, which were positively quantified in all samples. The highest concentrations were found for some of the antidepressants, with mean and maximum levels exceeding, in some cases, the levels previously reported in literature. This fact could be related to the additional washing step of the filters using methanol, which allowed to desorb retained analytes highlighting the importance of this step during the sample preparation protocol.