Evaluation of chemical contamination of crops produced in greenhouse by irrigation with reclaimed water.

Using reclaimed water for agricultural irrigation is increasing worldwide to compensate for water scarcity. The aim of this work was to evaluate the uptake of some of the most commonly detected organic contaminants of emerging concern (CECs) and pesticides in regenerated water in a field study. Furthermore, it was studied their distribution and accumulation in the different parts of a crop (soil, plant and fruit). Three crops (cucumber, pepper and melon) were grown under controlled agronomic conditions in a greenhouse. In order to make an accurate evaluation of the process, "regenerated blank water" was spiked with 70 chemicals (including antibiotics, anti-inflammatories, analgesics, anaesthetics, anxiolytics, anticonvulsants, pesticides) at environmental concentrations (∼1 µg/L) and used for continuous crop irrigation. After crop season, the average total concentration of contaminants detected in the soil samples ranged from 132 to 232 µg/kg d.w depending of the crops type. Between 7 and 10 different contaminants were found in the harvested fruits, up to levels of 27.8 µg/kg f.w. cucumber, 12.4 µg/kg f.w. melon and 7.8 µg/kg f.w pepper. In general, cucumber fruit showed higher accumulation levels of contaminants than pepper and melon for most target analytes. The accumulation rates followed the order: root (0.2 %) < stem/leaf (1-4 %) < fruit (1-6 %) < soil (17-30 %). The experimental data obtained in this study were also used to assess the risk associated with the reuse of reclaimed water for crop irrigation as well to identify those contaminants that, due to their physicochemical properties, show higher accumulation rates and environmental impact.

Long-term effects on the agroecosystem of using reclaimed water on commercial crops.

The use of reclaimed water for crop irrigation has been proposed as a suitable alternative for farmers in the coastal areas of Mediterranean countries, which suffer from greater water scarcity. In this work we study the impact on the water-soil-plant continuum of using reclaimed water for commercial crops irrigated over a long period, as well as the human risks associated with consuming the vegetables produced. Forty-four CECs were identified in the reclaimed water used for crop irrigation. Of these, twenty-four CECs were identified in the irrigated soil samples analysed. Tramadol, ofloxacin, tonalide, gemfibrozil, atenolol, caffeine, and cetirizine were the pharmaceuticals detected at the highest levels in the water samples (between 11 and 44 µg/L). The CECs with the highest average soil concentrations were tramadol (14.6 µg/kg), followed by cetirizine (13.2 µg/kg) and clarithromycin (12.7 µg/kg). In the irrigated vegetable samples analysed over the study period, carbamazepine, lidocaine, and caffeine were only detected at levels from 0.1 to 1.7 µg/kg. The CEC accumulation rate detected in the edible parts of the vegetables permanently irrigated with reclaimed water was very low (~1 %), whereas it was 33 % in the soils. The results revealed that consuming fruits harvested from plants irrigated for a long period with reclaimed water does not represent a risk to human health, opening the door to a circular economy of water. Nevertheless, for crop irrigation, future studies need to be conducted over longer periods and in other matrices to provide more scientific data on the safety of using reclaimed water.

Phosphoproteomic analysis of neoadjuvant breast cancer suggests that increased sensitivity to paclitaxel is driven by CDK4 and filamin A.

Precision oncology research is challenging outside the contexts of oncogenic addiction and/or targeted therapies. We previously showed that phosphoproteomics is a powerful approach to reveal patient subsets of interest characterized by the activity of a few kinases where the underlying genomics is complex. Here, we conduct a phosphoproteomic screening of samples from HER2-negative female breast cancer receiving neoadjuvant paclitaxel (N = 130), aiming to find candidate biomarkers of paclitaxel sensitivity. Filtering 11 candidate biomarkers through 2 independent patient sets (N = 218) allowed the identification of a subgroup of patients characterized by high levels of CDK4 and filamin-A who had a 90% chance of achieving a pCR in response to paclitaxel. Mechanistically, CDK4 regulates filamin-A transcription, which in turn forms a complex with tubulin and CLIP-170, which elicits increased binding of paclitaxel to microtubules, microtubule acetylation and stabilization, and mitotic catastrophe. Thus, phosphoproteomics allows the identification of explainable factors for predicting response to paclitaxel.

Fate, modeling, and human health risk of organic contaminants present in tomato plants irrigated with reclaimed water under real-world field conditions.

Using reclaimed water to irrigate crops can be an important route for organic contaminants of emerging concern (CECs) to be introduced into agricultural production and thus find their way into the food chain. This work aims to establish accumulation models for the different parts of a crop (fruit/leaves/roots) and the soil of some of the most commonly detected CECs in reclaimed water, through field trials in greenhouses. For this, tomato plants were permanently irrigated under realistic agricultural conditions with a mixture of the selected compounds at approx. 1 µg/L. A total of 30 contaminants were analyzed belonging to different compound categories. A modified QuEChERS extraction method followed by liquid chromatography coupled to tandem mass spectrometry was the procedure used. The study revealed the presence of 21 target contaminants in the tomatoes, and 18 CECs in the leaves, roots, and soil. The average total concentration of pesticides detected in the tomatoes was 3 µg/kg f.w., whereas the average total load of pharmaceuticals was 5.8 µg/kg f.w. after three months, at the time of crop harvesting. The levels of pharmaceutical products and pesticides in the non-edible tissues were up to 3.5 and 2.1 µg/kg f.w., respectively, in the leaves and up to 89.3 and 31.3 µg/kg f.w., respectively, in the roots. In the case of the soil samples, the pesticide concentration found after crop harvesting was below 11.4 µg/kg d.w., and less than 3.0 µg/kg d.w. for pharmaceuticals. Overall, the concentration levels of CECs detected in the tomatoes, which were permanently irrigated with contaminated reclaimed water, do not pose a risk to human health via dietary intake.

Monitoring of pesticide residues in crops irrigated with reclaimed water by a multiresidue method based on modified QuEChERS.

In this study, we aimed to validate and apply a quick and easy extraction method for the simultaneous determination of 27 pesticide residues at trace levels in agricultural samples (soil, fruit, and leaf) to monitor the presence of these contaminants released from reclaimed water. The procedure was based on a salting-out extraction method with acidified acetonitrile, followed by a dispersive solid-phase extraction (d-SPE) clean-up step applying the C18 sorbent. Ultra-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC-MS/MS) was used for identification and quantification of the target analytes. This methodology provided recovery values higher than 70%, for all pesticides and matrices evaluated in the study, except for propamocarb in soil samples (35%). Repeatability and reproducibility results, calculated as relative standard deviations (RSD, %), ranged between 1% and 18% in both cases. No remarkable matrix effects were observed for vegetable samples, except for thiamethoxam in red cabbage, and hexythiazox in carrot and leaves (between 30 and 40%). Soil samples showed a moderate matrix effect (between 21 and 35%) for more than 80% of the compounds. Monitoring pesticide residues found in agricultural samples irrigated with contaminated reclaimed water under controlled conditions revealed the efficacy of the proposed method. Three common vegetables were grown to evaluate the different migration and distribution rates in crops and soil. Pesticide accumulation in the different parts of the crop (soil, fruit, and leaves) and the potential human exposure to pesticides through daily intake were also discussed.

Determination study of contaminants of emerging concern at trace levels in agricultural soil. A pilot study.

In this study, we aimed to develop and validate a quick, easy, and robust extraction method for the simultaneous determination of 30 organic contaminants of emerging concern (CECs) including some transformation products in soil samples. Three different extraction methods based on an ultrasonic cylindrical probe (UAE), a pressurized liquid extraction (PLE), and a QuEChERS method were compared. Ultra-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC-MS/MS) was used for identification and quantification of the target analytes. A modified QuEChERS method showed the best results in terms of extractability and accuracy. The extraction procedure developed provided adequate extraction performances (70% of the target analytes were recovered within a 70-99% range), with good repeatability and reproducibility (variations below 20%) and great sensitivity (LOQ < 0.1 ng/g in most cases). No matrix effects were observed for 70% of the compounds. Finally, the analytical methodology was applied in a pilot study where agricultural soil was irrigated with reclaimed water spiked with the contaminants under study. Of the 25 CECs added in irrigation water, a total of 13 pesticides and 5 pharmaceutical products were detected at concentration ranges from 0.1 to 1.2 ng/g (d.w) and from 0.1 to 2.0 ng/g (d.w), respectively.

Unlocking the potential of big data to support tactical performance analysis in professional soccer: A systematic review.

In professional soccer, increasing amounts of data are collected that harness great potential when it comes to analysing tactical behaviour. Unlocking this potential is difficult as big data challenges the data management and analytics methods commonly employed in sports. By joining forces with computer science, solutions to these challenges could be achieved, helping sports science to find new insights, as is happening in other scientific domains. We aim to bring multiple domains together in the context of analysing tactical behaviour in soccer using position tracking data. A systematic literature search for studies employing position tracking data to study tactical behaviour in soccer was conducted in seven electronic databases, resulting in 2338 identified studies and finally the inclusion of 73 papers. Each domain clearly contributes to the analysis of tactical behaviour, albeit in - sometimes radically - different ways. Accordingly, we present a multidisciplinary framework where each domain's contributions to feature construction, modelling and interpretation can be situated. We discuss a set of key challenges concerning the data analytics process, specifically feature construction, spatial and temporal aggregation. Moreover, we discuss how these challenges could be resolved through multidisciplinary collaboration, which is pivotal in unlocking the potential of position tracking data in sports analytics.

Identification of non-intentionally added substances in food packaging nano films by gas and liquid chromatography coupled to orbitrap mass spectrometry.

The control of chemical migration from new functionalized food contact materials (FCMs) is a challenge for meeting food safety requirements. The non-intentionally added substances (NIAS) constitute a group of chemicals that are not applied, but may be introduced or formed during the production process of FCMs. This study describes a multi-analytical approach for the evaluation of unknown substances that migrate from FCMs. A case study is presented using a developed polymer consisting of a monolayer film with polylactic acid (PLA), polylimonene (PL) and zinc oxide nanoparticles (ZnO NPs). This approach incorporates the platforms of ICP-MS (inductively coupled plasma mass spectrometry), to determine whether there is transference of ZnO NPs used as antimicrobial agent and, the systems GC-MS and LC-MS (gas / liquid chromatography coupled to a quadrupole orbitrap mass spectrometer) for the characterization of the chemical structure of NIAS using the molecular mass and specific features of mass fragmentation. The screening of unknown compounds comprised retrospective analysis and data processing using both, a mass spectral library and databases, for GC and LC data, respectively. This approach has provided the tentative identification and quantification of seven NIAS, 3 by GC (Tripropylene glycol diacrylate, 10-Heneicosene and α-Tocopherol acetate) and 4 by LC (N,N-Diethyldodecanamide, N-[(9Z)-9-Octadecen-1-yl]acetamide, 1-Palmitoylglycerol and Glycerol stearate). This migration study was carried out according to the standard protocols established by EU regulation for FCMs.

Shifting the paradigm in gas chromatography mass spectrometry pesticide analysis using high resolution accurate mass spectrometry.

In the last 10 years, the majority of the pesticide food control laboratories moved from GC-MS to GC-MS/MS as the preferred analytical technique to address GC amenable compounds. The main reason for this change was the negative impact on the single stage GC-MS analysis caused by the interference from coeluting matrix compounds. The new development of gas chromatography coupled to high resolution accurate mass spectrometry (GC-HRAMS) provides opportunities to overcome such matrix interferences as a result of its much higher selectivity; allowing laboratories to carry out full-scan analysis covering the most exigent analytical performance criteria. The aim of this work is the evaluation of the main analytical performance parameters for the multiresidue screening of pesticide residues by a gas chromatography-Orbitrap™ mass spectrometer in fruits and vegetables. Electron ionization and full-scan high resolution mass spectrometry was selected for this evaluation. Mass resolving power, selectivity, sensitivity, analyte identification and database generation are discussed in light of the analysis of various commodities and a large scope of pesticides. The selected operational conditions provided optimal mass accuracy, within ±1mDa and achieved LOQs of 10µg/kg or lower for practically all the selected pesticides and commodities. Applicability for quantitative residue analysis was verified by the validation of the 210 pesticides in four matrices (tomato, apple, leek and orange). The performance of the GC-EI-full scan Orbitrap HRAMS developed method was confirmed with the analysis of 102 real samples providing good results.

POCIS passive samplers as a monitoring tool for pharmaceutical residues and their transformation products in marine environment.

In the last years, several scientific studies have shown that carbamazepine (CBZ) is one of the most frequently detected pharmaceutical in aquatic environment. However, little data is available on its detection and its transformation products (TPs) in marine water. The use of polar organic chemical integrative sampling (POCIS) passive samplers as a semi-quantitative and qualitative tool for screening of pharmaceuticals and TPs in seawater has been studied. Furthermore, the uptake rates of the target compounds were also determined under laboratory experiments to characterize the levels accumulated in devices. The results confirmed the presence of residues of anticonvulsant CBZ as well as some of its main metabolites, over a 1-year monitoring campaign carried out in French coast on the Mediterranean Sea. The work reports for the first time the presence of two TPs (10,11-dihydro-10,11-trans-dihydroxycarbamazepine (TRANS) and 10-hydroxy-10,11-dihydrocarbamazepine (10OH)) in marine water. The results contribute in assessing the environmental and human health risk of pharmaceuticals on coastal areas.

In vivo exposure of marine mussels to carbamazepine and 10-hydroxy-10,11-dihydro-carbamazepine: Bioconcentration and metabolization.

Aquatic organisms are exposed to pharmaceuticals present in natural waters, but few data are available on the accumulation of these substances in such organisms. The present study evaluated the in vivo bioconcentration of two anticonvulsants--carbamazepine (CBZ) and 10-hydroxy-10,11-dihydro-carbamazepine (10 OH)--in marine mussels (Mytilus galloprovincialis) exposed to nominal 10 µg L(-1) concentrations for one week. The bioconcentration factors (BCFs) were 3.9 and 4.5 L kg(-1) dry weight (dw) for CBZ and 10 OH, respectively. CBZ accumulation reached an average tissue concentration of 29.3 ± 4.8 ng g(-1) dw, and 10 OH accumulated up to 40.9 ± 4.6 ng g(-1) dw in tissues within one week, showing first-order kinetics. BCF obtained with linear QSAR models correctly estimated the CBZ bioconcentration and overestimated the 10 OH bioconcentration to some extent. The detection of two metabolites (carbamazepine-10,11-epoxide and acridine) among the five sought suggested an active metabolism for CBZ. In contrast, none of the 10 OH metabolites were detected in mussels exposed to 10 OH. CBZ showed higher accumulation in the digestive gland, where some relevant metabolites were detected, than in other studied tissues. The implication of those findings on field biomonitoring is discussed.

Effect of preoperative oral pravastatin reload in systemic inflammatory response and myocardial damage after coronary artery bypass grafting. A pilot double-blind placebo-controlled study.

AIM: Statins exert pleiotropic effects that result in cardioprotective and antiinflammatory properties. There is a lack of information about the effect of preoperative reloading statin administration in surgical coronary patients regarding myocardial protection, systemic inflammatory response (SIR) attenuation and nitric oxide (NO) metabolism. METHODS: Thirty consecutive dyslipidemic patients under chronic treatment with statins were randomized to orally receive pravastatin 80 mg (N.=10), 40 mg (N.=10) or placebo (N.=10) two hours before anesthetic induction for non-emergent on-pump coronary artery bypass grafting (CABG) procedures. Perioperative peripheral venous and intraoperative CS blood samples were collected for determination of drug-related adverse effects, NO metabolism and both myocardial damage and SIR biomarkers. RESULTS: Pravastatin reloading resulted in a significant and dose-related intense attenuation of SIR, but no differences in cardiac damage biomarker levels were demonstrated. NO release and inducible nitric oxide synthase expression was significantly reduced in both treatment groups. Highest pravastatin doses significantly increased systemic creatine phosphokinase (CPK) concentration compared with intermediate doses but no other adverse effects were observed. CONCLUSION: Oral pravastatin reloading before non-emergent CABG significantly attenuates postoperative SIR and systemic NO/iNOS concentrations with no effect in perioperative myocardial damage. Highest pravastatin doses increase CPK levels and must be avoided in susceptible patients.

Detection of emerging contaminants (UV filters, UV stabilizers and musks) in marine mussels from Portuguese coast by QuEChERS extraction and GC-MS/MS.

The UV filters and musk fragrances have come into focus because these compounds are contained and increasingly used not only in sunscreen products but also in many products of daily use, such as cosmetics, skin creams, plastics or varnish. In view of this, the main objective of the present work was to develop and validate a method for the determination of three UV filters, two UV stabilizers and four musks in mussel samples (Mytilus galloprovincialis). The procedure combined a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method with an analysis by gas chromatography-tandem mass spectrometry (GC-MS/MS). The methodology allowed the determination of target analytes at trace concentration levels (ng/g), with mean recoveries ranging from 91 to 112%. A monitoring study was conducted in four beaches in the Portuguese coast which are impacted by recreational activities and outflow of treated waste water effluents in rivers. The results are used to assess the occurrence of UV filters in comparison with UV stabilizers and musk fragrances which indicate other activities than bathing.

Post-acquisition data processing for the screening of transformation products of different organic contaminants. Two-year monitoring of river water using LC-ESI-QTOF-MS and GCxGC-EI-TOF-MS.

This study describes a comprehensive strategy for detecting and elucidating the chemical structures of expected and unexpected transformation products (TPs) from chemicals found in river water and effluent wastewater samples, using liquid chromatography coupled to electrospray ionization quadrupole-time-of-flight mass spectrometer (LC-ESI-QTOF-MS), with post-acquisition data processing and an automated search using an in-house database. The efficacy of the mass defect filtering (MDF) approach to screen metabolites from common biotransformation pathways was tested, and it was shown to be sufficiently sensitive and applicable for detecting metabolites in environmental samples. Four omeprazole metabolites and two venlafaxine metabolites were identified in river water samples. This paper reports the analytical results obtained during 2 years of monitoring, carried out at eight sampling points along the Henares River (Spain). Multiresidue monitoring, for targeted analysis, includes a group of 122 chemicals, amongst which are pharmaceuticals, personal care products, pesticides and PAHs. For this purpose, two analytical methods were used based on direct injection with a LC-ESI-QTOF-MS system and stir bar sorptive extraction (SBSE) with bi-dimensional gas chromatography coupled with a time-of-flight spectrometer (GCxGC-EI-TOF-MS).

Occurrence of venlafaxine residues and its metabolites in marine mussels at trace levels: development of analytical method and a monitoring program.

Coastal areas are subject to growing pressures and impacts because of the increase in human activities. Lipophilic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) or polychlorinated biphenyls (PCBs), have been monitored for decades within monitoring programs. However, until now, little information on the detection of so-called "emerging contaminants" such as hydrophilic organic compounds in the marine environment and no data on its metabolites or transformation products in marine organisms is available. In this report, a sensitive analytical methodology for identification and confirmation of venlafaxine (VEN) residues and five of its main metabolites in the marine mussels Mytilus galloprovincialis was validated. The sample preparation procedure was based on the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) approach. An analytical method was developed to quantify these compounds at trace levels by liquid chromatography coupled to high-resolution mass spectrometry. The method was then applied to marine mussels collected from the Mediterranean Sea in southeastern France. Residues of the antidepressant VEN were occasionally detected at ng/g dw level. In addition, the approach allowed us to identify several transformation products in the analyzed samples. N-desmethylvenlafaxine (NDV) was the most frequently detected metabolite followed by N,O-di-desmethylvenlafaxine (NODDV).

Fast and easy extraction combined with high resolution-mass spectrometry for residue analysis of two anticonvulsants and their transformation products in marine mussels.

Environmental field studies have shown that carbamazepine (Cbz) is one of the most frequently detected human pharmaceuticals in different aquatic compartments. However, little data is available on the detection of this substance and its transformation products in aquatic organisms. This study was thus mainly carried out to optimize and validate a simple and sensitive analytical methodology for the detection, characterization and quantification of Cbz and oxcarbazepine (Ox), two anticonvulsants, and six of their main transformation products in marine mussels (Mytilus galloprovincialis). A modified QuEChERS extraction method followed by analysis with liquid chromatography coupled to high resolution mass spectrometry (HRMS) was used. The analyses were performed using two-stage fragmentation to reveal the different fragmentation pathways that are highly useful for the identification of isomeric compounds, a common problem when several transformation products are analyzed. The developed analytical method allowed determination of the target analytes in the lower ng/g concentration levels. The mean recovery ranged from 67 to 110%. The relative standard deviation was under 11% in the intra-day and 18% in the inter-day analyses, respectively. Finally, the method was applied to marine mussel samples collected from Mediterranean Sea cultures in southeastern France. Residues of the psychiatric drug Cbz were occasionally found at levels up to 3.5ng/g dw. Lastly, in this study, other non-target compounds, such as caffeine, metoprolol, cotinine and ketoprofen, were identified in the real samples analyzed.

Determination of drugs in river and wastewaters using solid-phase extraction by packed multi-walled carbon nanotubes and liquid chromatography-quadrupole-linear ion trap-mass spectrometry.

The present paper describes a solid-phase extraction by packed multi-walled carbon nanotubes, followed by liquid chromatography-mass spectrometry, method for the determination of some of the most consumed drugs including four ß-blockers and eight non-steroidal anti-inflammatory drugs, in river and wastewater samples. High extraction efficiency was found for most drugs due to the large specific surface area and high adsorption capacity of this nanomaterial compared with other conventional solid-phase extraction sorbents, and matrix effect was present only for two of the twelve studied drugs. Only 20mg of carbon nanotubes was enough to preconcentrate the analytes with recoveries from 68% to 107% for most of them. The pharmaceuticals were analyzed by liquid chromatography coupled to a hybrid triple quadrupole-linear ion trap-mass spectrometer at ultra-trace levels. Data acquisition was carried out in selected reaction monitoring mode, using two transitions for simultaneous identification and quantification of the analytes. Additionally, an information dependent acquisition scan was performed to carry out the identification of those analytes whose second transition was absent or was present at low intensity. The analytical performance of the whole method was evaluated in two environmental water matrices (river and wastewaters). Matrix effect was not found in river water, quantitation being carried out with calibration graphs built with solvent based standard. On the contrary, matrix effect was present in wastewater for some of the target drugs and, therefore, quantitation was carried out using the standard addition method. Limits of detection and quantitation in river waters were in the range of 9-36 and 23-121ngL(-1), respectively and the relative standard deviation of the full method was less than 17%. The proposed methodology was applied to the analysis of three river water and two wastewater (influent and effluent) samples, all of them from Almería (Spain). Some pharmaceuticals were found in river water at concentration levels near to or lower than their quantitation limits, whereas the most consumed pharmaceuticals were found at high concentration levels in influent wastewater and were not detected or were found at lower levels in the effluent wastewater sample.

Simultaneous measurement in mass and mass/mass mode for accurate qualitative and quantitative screening analysis of pharmaceuticals in river water.

A new approach for the analysis of pharmaceuticals (target and non-target) in water by LC-QTOF-MS is described in this work. The study has been designed to assess the performance of the simultaneous quantitative screening of target compounds, and the qualitative analysis of non-target analytes, in just one run. The features of accurate mass full scan mass spectrometry together with high MS/MS spectral acquisition rates - by means of information dependent acquisition (IDA) - have demonstrated their potential application in this work. Applying this analytical strategy, an identification procedure is presented based on library searching for compounds which were not included a priori in the analytical method as target compounds, thus allowing their characterization by data processing of accurate mass measurements in MS and MS/MS mode. The non-target compounds identified in river water samples were ketorolac, trazodone, fluconazole, metformin and venlafaxine. Simultaneously, this strategy allowed for the identification of other compounds which were not included in the library by screening the highest intensity peaks detected in the samples and by analysis of the full scan TOF-MS, isotope pattern and MS/MS spectra - the example of loratadine (histaminergic) is described. The group of drugs of abuse selected as target compounds for evaluation included analgesics, opioids and psychostimulants. Satisfactory results regarding sensitivity and linearity of the developed method were obtained. Limits of detection for the selected target compounds were from 0.003 to 0.01 µg/L and 0.01 to 0.5 µg/L, in MS and MS/MS mode, respectively - by direct sample injection of 100 µL.

Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: two years pilot survey monitoring.

This work summarized all results obtained during almost two-years of a monitoring programme carried out in five municipal sewage treatment plants (STPs) located in the north, centre and south-east of Spain. The study evaluated the occurrence and persistence of a group of 100 organic compounds belonging to several chemical groups (pharmaceuticals, personal care products, pesticides and metabolites). The average removal efficiencies of the STPs studied varied from 20% (erythromycin) to 99% (acetaminophen). In analysed samples, we identified a large number of compounds at mean range concentrations between 7-59,495 ng/L and 5-32,720 ng/L for influent and effluent samples, respectively. This study also identified 20 of the mostly detected and persistent compounds in wastewater effluent, of which hydrochlorothiazide, atenolol, gemfibrozil, galaxolide and three metabolites (fenofibric acid, 4-AAA and 4-FAA), presented the highest average contribution percentages, in relation to the total load of contaminants for the different STPs effluent studied.

Development of a solvent-free method for the simultaneous identification/quantification of drugs of abuse and their metabolites in environmental water by LC-MS/MS.

This work details a rapid analytical method using direct sample injection for the simultaneous identification/quantification of 22 drugs of abuse, including some of their major metabolites, in environmental samples. This has been developed using a hybrid triple quadrupole-linear ion trap-mass spectrometer (QqLIT). With the increasing sensitivity of today's tandem mass spectrometers, direct injection analysis of water samples has become an attractive alternative to traditional analytical protocols, which often include a preliminary pre-concentration step. What's more, this kind of analysis is in accordance with many of the main objectives of so-called green analytical chemistry, or environmentally friendly practice. The analytical performance of the LC-MS/MS method was evaluated in three different water matrices (surface water, influent and effluent wastewater). Data acquisition was carried out in selected reaction monitoring (SRM) mode under time-scheduled conditions, monitoring two SRM transitions for simultaneous identification/quantification of all target compounds in the samples. Additionally, an experiment was performed using the information-dependent acquisition (IDA) scan to carry out the identification of those analytes for which the second transition was present at a low intensity. Finally, the two methodologies developed were applied to real samples for evaluation.