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A simple, fast, highly-sensitive and selective method for the determination of 13 HAAs and dalapon in water has been optimized and validated. The method is based on large volume injection (200 μL) and analyte determination with liquid chromatography coupled to negative electrospray ionization-high resolution mass spectrometry (LVI-LC-ESI(−)-HRMS). High throughput is possible due to minimum sample manipulation and short analysis time (16 min in total). This is the first analytical LC-MS-based method that covers the whole suite of HAAs for which analytical standards are available and dalapon, and thus, represents a less costly option than ion-chromatography-based technologies developed for the same purpose. The method provided satisfactory trueness (91–120%) and precision (<17%) values for all analytes, except for CAA. Matrix effects, always in the form of ionization suppression effects, were not relevant (<25%), except in the case of CAA, and they were all well compensated with the use of internal standard calibration. This methodology allows quantifying HAAs in tap waters at concentrations below 1 μg L−1, except in the case of DBCAA and TCAA (3 μg L−1) and CAA and DCBAA (6 μg L−1). Thus, the presented analytical approach is satisfactory for the routine monitoring of HAA5 in drinking waters and obtaining additional knowledge on the formation and occurrence of other HAAs and dalapon that may be of relevance to ensure the provision of safe drinking water in the future. The concentrations of some of the brominated HAAs in chlorine-quenched disinfected water stored in the dark at −20 °C for seven days decreased between 26 and 46%, and thus, water samples should be analysed within 24 hours of their collection. As part of the validation method, the optimized approach was applied to evaluate two strategies to control HAA concentrations in water, i.e., lowering the water pH during the coagulation-flocculation step to improve process efficiency and using a household water pitcher filtration unit to remove HAAs in tap water. ; CP acknowledges support from Fundación General del Consejo Superior de Investigaciones Científicas (FGCSIC) through the 2nd edition of the ComFuturo Programme. This work was supported by the Government of Catalonia (Consolidated Research Groups 2017 SGR 01404) and the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S). Phenomenex is acknowledged for the gift of the HPLC column and AB Sciex for LC-MS instrumentation loan. Nicola Montemurro and Roser Chaler, from IDAEA-CSIC, are acknowledged for assisstance in the use of the analytical instrumentation. We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI). ; Peer reviewed

Iodine containing disinfection byproducts (I-DBPs) and haloacetaldehydes (HALs) are emerging disinfection by-product (DBP) classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes (I-THMs), iodo-haloacetic acids (I-HAAs) and selected HALs (mono-HALs and di-HALs species, including iodoacetaldehyde) were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments. ; C.P. acknowledges support from the European Union 7th R&D Framework Programme (FP7/2007-2013) under grant agreement 274379 (Marie Curie IOF) and the Secretary for Universities and Research of the Ministry of Economy and Knowledge of the Government of Catalonia and the COFUND Programme of the Marie Curie Actions of the EU's FP7 (2014 BP_B00064). The EU is not liable for any use that may be made of the information contained therein. This work has been financially supported by the Government of Catalonia (Consolidated Research Groups 2014 SGR 418-Water and Soil Quality Unit and 2014 SGR 291-ICRA). ; Peer reviewed

Reducing the formation of disinfection by-products (DBPs) during the process of water potabilization and proper risk assessment of drinking water requires exploring the potential of the source water and the applied treatment to generate these chemicals. This is actually more challenging in large drinking water networks that use different source waters to satisfy potable water demand. In this regard, this works investigated the formation of DBPs in water matrices that are commonly supplied to the city of Barcelona and its metropolitan area. The regulated trihalomethanes and haloacetic acids were the most abundant DBP classes in these waters, followed by haloacetamides and haloacetonitriles or trihalogenated acetaldehydes (THALs). On the contrary, the formation potential of iodo-DBPs was minor. Mixing of drinking water treatment plant (DWTP) finished waters with desalinated water decreased the overall DBP formation potential of the water but resulted in the increased formation of brominated DBPs after long chlorine contact time. The formation of most DBPs was enhanced at high water temperatures (except for Br-THALs) and increasing residence times. Potential cytotoxicity and genotoxicity of the DBP mixtures were mainly attributed to the presence of nitrogen-containing DBPs and HAAs. ; C.P. acknowledges support from the Secretary for Universities and Research of the Ministry of Economy and Knowledge of the Government of Catalonia and the COFUND Programme of the Marie Curie Actions of the EU's FP7 (2014 BP_B00064). This work was financially supported by the Government of Catalonia (Consolidated Research Groups 2017 SGR 1404-Water and Soil Quality Unit). ; Peer reviewed

This work presents an analytical methodology based on a "Quick, easy, cheap, effective, rugged, and safe" (QuEChERS) extraction and liquid chromatography-tandem mass spectrometry detection (LC-MS/MS) for the simultaneous determination of 35 psychoactive substances in fresh mussel samples. The compounds investigated include illicit drugs, new psychoactive substances, commonly prescribed psychiatric pharmaceuticals, and caffeine. The methodology was validated in terms of recovery (relative recoveries 77–118%), repeatability (relative standard deviation values <20%), and sensitivity (limits of detection and quantification <2 ng/g fresh weight (f.w.) and <6.7 ng/g f.w., respectively, for most compounds). The method was applied to the analysis of 15 samples, covering both commercially available mussels purchased from local food markets and wild fresh mussels collected in the Northeast coast of Spain in the Mediterranean Sea. Only one sample corresponding to wild mussels was found to contain 2 of the target analytes, namely, sertraline (1.5 ng/g f.w.) and caffeine, (12.8 ng/g f.w.). ; This work has been financially supported by the European Union Seventh Framework Programme through the project SOLUTIONS under grant agreement no. 603437 and by the Government of Catalonia (Consolidated Research Group 2017 SGR 01404- Water and Soil Quality Unit). It reflects only the author's views. The Community is not liable for any use that may be made of the information contained therein. Bekolut is acknowledged for the gift of QuEChERS kits. Marinel·la Farré Urgell from IDAEA-CSIC and Maria Rambla from Institute of Agrifood Research and Technology (IRTA) are acknowledged for the collection of the wild mussel samples. ; Peer reviewed

We present an analytical method developed and validated to study the potential uptake of 13 selected drugs (ten pharmaceuticals, one illicit drug, and two transformation products) into lettuce plants from contaminated water and soil. Some of the selected drugs (i.e., cocaine, methadone, cis-diltiazem, valsartan, and valsartan acid), which are commonly present in treated wastewater, were investigated for the first time in plant tissues. The method is based on ultrasonic solvent extraction with acetonitrile–methanol (1:1, v/v) and subsequent automated extract cleanup and analysis by means of online solid-phase extraction–liquid chromatography–tandem mass spectrometry. Optimum extraction conditions were selected after evaluation of analyte recoveries with four different extraction techniques (ultrasonic solvent extraction, solid–liquid extraction, pressurized liquid extraction, and a "quick, easy, cheap, effective, rugged, and safe" based method) and six different solvent mixtures. Furthermore, two different solid-phase extraction cleanup sorbents were evaluated. The method developed has high sensitivity (with limits of detection between 0.1 and 12.6 ng per gram dry weight and limits of quantification between 0.5 and 42.0 ng per gram dry weight), satisfactory accuracy (with analyte relative recoveries above 80% for all analytes but acridone and oxcarbazepine), and good repeatability (with relative standard deviations below 9% for all analytes). As part of the validation procedure, the analytical method was applied to the analysis of lettuce plants irrigated with water fortified with the selected compounds for the entire growing period. The results obtained evidenced the transfer of all the investigated drugs into lettuce leaves. [Figure not available: see fulltext.] © 2017 Springer-Verlag Berlin Heidelberg ; N.M. gratefully acknowledges the University of Bari for financial support provided through a predoctoral grant (29th Doctorate Program in Biodiversity, Agriculture and Environment). This work was financially supported by the Government of Catalonia (Consolidated Research Groups B2014 SGR 418—Water and Soil Quality Unit and B2014 SGR 291—Catalan Institute for Water Research), and by the EU's Seventh Framework Programme for research, technological development and demonstration (grant agreement no. 603437—SOLUTIONS), and it reflects only the authors' views. The EU is not liable for any use that may be made of the information contained herein. Merck is acknowledged for the gift of liquid chromatography columns. ; Peer reviewed

The disinfection of drinking water is required in order to protect consumers from potential waterborne infectious and parasitic pathogens. Water is commonly treated by adding chemical disinfectants, such as free chlorine, chloramines, chlorine dioxide, and ozone. However, although very effective in removing disease-causing microorganisms, these disinfectants can react with naturally occurring materials in the water and can form disinfection by-products (DBPs) which can be harmful to human health. In particular, compounds containing an iodo-group, i.e., iodinated DBPs (iodo-DBPs), may pose a greater health risk for the population exposed to them than their brominated and chlorinated analogues [1]. In recent years, several chemical classes of low molecular weight iodo-DBPs have been reported; however, many more may be still present in the unknown fraction (~50%) of halogenated material formed during disinfection treatments [2]. Therefore, complete characterization of iodo-DBPs present in DBP mixtures is crucial to further investigate their occurrence in disinfected waters and potential toxicity effects. The identification of emerging iodinated DBPs in water is difficult due to the complexity of this matrix and the low concentrations of these compounds. For this, analytical techniques with high resolving power, high mass accuracy and sensitivity are required. In this work, a novel gas chromatography (GC), coupled with high-resolution accurate mass Orbitrap mass spectrometer (the Thermo Scientific™ Q Exactive™ GC hybrid quadrupole-Orbitrap mass spectrometer), has been used for iodo-DBPs detection and accurate mass identification in chlorinated and chloraminated water samples ; C. P. acknowledges support provided by the European Union 7th R&D Framework Programme (FP7/2007e2013) under grant agreement 274379 (Marie Curie IOF) and the Secretary for Universities and Research of the Ministry of Economy and Knowledge of the Government of Catalonia and the COFUND programme of the Marie Curie Actions of the EU's FP7 (2014 BP_B00064). This work has been financially supported by the Generalitat de Catalunya (Consolidated Research Groups "2014 SGR 418 - Water and Soil Quality Unit" and 392 2014 SGR 291 - ICRA) and by the European Union's FP7 for research, technological development and demonstration under grant agreement nº 603437 (SOLUTIONS). The EU is not liable for any use that may be made of the information contained therein. ; Peer reviewed

Recent developments in gas chromatography (GC)-mass spectrometry (MS) have opened up the possibility to use the high resolution-accurate mass (HRAM) Orbitrap mass analyzer to further characterize the volatile and semivolatile fractions of environmental samples. This work describes the utilization of GC Orbitrap MS technology to characterize iodine-containing disinfection by-products (iodo-DBPs) in chlorinated and chloraminated DBP mixture concentrates. These DBP mixtures were generated in lab-scale disinfection reactions using Llobregat river water and solutions containing Nordic Lake natural organic matter (NOM). The DBPs generated were concentrated using XAD resins, and extracts obtained were analyzed in full scan mode with the GC Orbitrap MS. Integration of high resolution accurate mass information and fragment rationalization allowed the characterization of up to 11 different iodo-DBPs in the water extracts analyzed, including one new iodo-DBP reported for the first time. Overall, formation of iodo-DBPs was enhanced during chloramination reactions. As expected, NOM characteristics and iodide and bromide content of the tested waters affected the amount and type of iodo-DBPs generated. ; C.P. acknowledges support provided by the European Union 7th R&D Framework Programme (FP7/2007-2013) under grant agreement 274379 (Marie Curie IOF) and the Secretary for Universities and Research of the Ministry of Economy and Knowledge of the Government of Catalonia and the COFUND programme of the Marie Curie Actions of the EU's FP7 (2014 BP_B00064). This work was financially supported by the Government of Catalonia (Consolidated Research Groups "2014 SGR 418 - Water and Soil Quality Unit" and "2014 SGR 291 – ICRA") and by the EU's FP7 for research, technological development, and demonstration (grant agreement no. 603437 - SOLUTIONS). ; Peer reviewed

Oilseed crops are greatly extended all over the world. Their high fat content can interfere during pesticide multiresidue analysis through liquid chromatography-tandem mass spectrometry (LC-MS/MS). This work aimed at overcoming this issue by developing and validating two QuEChERS-based methods for LC-MS/MS determination of 42 pesticides in two fatty food matrices: olives and sunflower seeds. Optimization of the extraction method was achieved following a 26-2 fractional factorial design in a highly cost-effective way. Validation of the multi-residue methods demonstrated improved limits of detection, below the established maximum residue levels (MRLs) for almost all compounds, good precision, and trueness, in compliance with SANTE guidelines. Application of these methods to the analysis of real samples from the Iberian Peninsula showed the presence of some pesticides of relevant environmental concern, including four compounds contained in the Pesticide Action Network International list of highly hazardous pesticides, found at levels between 0.03 ng/g and 104 ng/g. ; This work has been funded by the European Union through the European Agricultural Fund for Rural Development (FitoFarmGest Operational Group PDR2020-101-030926), the Spanish Ministry of Science and Innovation (Project CEX2018-00794-S) and the Government of Catalonia (2017 SGR 01404). BEKOlut is acknowledged for the gift of QuEChERS kits. ; Peer reviewed

Contaminants of emerging concern (CECs) are widespread in the water cycle. Their levels in disinfected waters are usually low, as they may transform into CEC disinfection byproducts (DBPs) during disinfection processes or partially removed in previous water treatment steps. The occurrence of CEC DBPs in real waters has been scarcely addressed, although their presence may be of relevance in water circular economy scenarios, and thus deserves further study in water regeneration systems. In this work, a database of CEC DBPs (n=1338) after chlorination was generated and is ready to use in future screening studies to assess the relevance of these chemicals in contaminat mixtures. Moreover, the transformation of CECs during chlorination, their main reaction pathways with chlorine, and current knowledge gaps were critically reviewed. ; CP acknowledges support from Fundación General del CSIC through the ComFuturo Programme (2nd edition). This work was supported by the Government of Catalonia (Consolidated Research Groups 2017 SGR 01404), and the "Agencia Estatal de Investigación" from the Spanish Ministry of Science and Innovation (MEDISTRAES III, PID2019-110212RB-C22) and the IDAEA-CSIC, a Centre of Excellence Severo Ochoa (CEX2018-000794-S). CP acknowledges support from the Swedish University of Agricultural Sciences through the August T Larsson Guest Researcher Programme. We would also like to acknowledge the personnel from the WWTPs that kindly assisted in water sample collection. ; Peer reviewed

This work assesses the capacity of a microalgae-based system to remove three highly to medium polar pesticides typically found in freshwater: acetamiprid, bentazone, and propanil. Degradation of the pesticides was firstly studied individually at batch lab-scale reactors and abiotic and heated-killed controls were employed to clarify their removal pathways. At lab-scale, propanil and acetamiprid were completely removed after 7 days whereas bentazone was not removed. Four and two transformation products (TPs) were generated in the biodegradation process for acetamiprid and propanil, respectively. Then, the simultaneous removal of the pesticides was assessed in an outdoor pilot photobioreactor, operated with a hydraulic residence time of 8 days. During the steady-state, high removal efficiencies were observed for propanil (99%) and acetamiprid (71%). The results from batch experiments suggest that removal is mainly caused by algal-mediated biodegradation. Acetamiprid TPs raised throughout the operational time in the photobioreactor, while no propanil TP was detected at the pilot-scale. This suggests complete mineralization of propanil or residual formation of its TPs at concentrations below the analytical method detection limit. Aiming at biomass valorization, diverse microalgae harvesting methods were investigated for biomass concentration, and the effect of residual pesticides on the biogas yield was determined by biochemical methane potential tests. Anaerobic digestion was not inhibited by the pesticides as verified by the digestion performance. The results highlight the potential of microalgae-based systems to couple nutrient removal, biomass production, micropollutant biodegradation, and biofuel production. ; This work has been supported by the Spanish Ministry of Economy and Competitiveness State Research Agency (CTM2016-75587-C2-1-R and CTM2016-75587-C2-2-R) and co-financed by the European Union through the European Regional Development Fund (ERDF) and the Horizon 2020 research and innovation WATERPROTECT project (727450). This work was also partly supported by the Generalitat de Catalunya (Consolidate Research Groups 2017-SGR-01404 and 2017-SGR-014) and the Ministry of Science and Innovation (Project CEX2018-000794-S). ; Peer reviewed

It is possible to consult this version in open access at the following web address: arXiv:2011.11638 ; The occurrence of the extensively used herbicide diuron in the environment poses a severe threat to the ecosystem and human health. Four different ligninolytic fungi were studied as biodegradation candidates for the removal of diuron. Among them, T. versicolor was the most effective species, degrading rapidly not only diuron (83%) but also the major metabolite 3,4-dichloroaniline (100%), after 7-day incubation. During diuron degradation, five transformation products (TPs) were found to be formed and the structures for three of them are tentatively proposed. According to the identified TPs, a hydroxylated intermediate 3-(3,4-dichlorophenyl)-1-hydroxymethyl-1-methylurea (DCPHMU) was further metabolized into the N-dealkylated compounds 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU) and 3,4-dichlorophenylurea (DCPU). The discovery of DCPHMU suggests a relevant role of hydroxylation for subsequent N-demethylation, helping to better understand the main reaction mechanisms of diuron detoxification. Experiments also evidenced that degradation reactions may occur intracellularly and be catalyzed by the cytochrome P450 system. A response surface method, established by central composite design, assisted in evaluating the effect of operational variables in a trickle-bed bioreactor immobilized with T. versicolor on diuron removal. The best performance was obtained at low recycling ratios and influent flow rates. Furthermore, results indicate that the contact time between the contaminant and immobilized fungi plays a crucial role in diuron removal. This study represents a pioneering step forward amid techniques for bioremediation of pesticides-contaminated waters using fungal reactors at a real scale. ; This work has been supported by the Spanish Ministry of Economy and Competitiveness State Research Agency (CTM2016-75587-C2-1-R and CTM2016-75587-C2-2-R) and co-financed by the European Union through the European Regional Development Fund (ERDF) and the Horizon 2020 research and innovation WATERPROTECT project (727450). This work was partly supported by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-14) and the Ministry of Science and Innovation (Project CEX2018-000794-S). The Department of Chemical, Biological and Environmental Engineering of the Universitat Autònoma de Barcelona is a member of the Xarxa de Referència en Biotecnologia de la Generalitat de Catalunya. K. Hu acknowledges the financial support from the Chinese Scholarship Council. ; Peer reviewed