Suchergebnisse

Contamination of soils with organic pollutants is an increasing global problem, so novel soil remediation techniques are urgently needed. One such technique is electrokinetic remediation, in which an electric field is applied over the soil to extract contaminants. Previous evaluations of the technique have been limited to a few specific compounds. In this study, we integrated the latest advances in high-resolution mass spectrometry (HRMS) to identify molecular fingerprints, and used the results to improve the mechanistic understanding necessary for successful remediation. A laboratory-scale 0.38 mA cm−2 electrodialytic treatment was applied for 21 days to a contaminated soil from a firefighter training facility in Sweden. Non-target analysis allowed generic evaluation of changes in the soil organic fraction by tentatively determining the elemental composition of compounds present. The results showed that smaller oxygen-rich molecules were significantly transported to the anode by electromigration, while larger hydrogen-saturated molecules were transported to the cathode by electroosmotic flow. Wide suspect screening with >3000 per- and polyfluoroalkyl substances (PFASs) tentatively identified seven new PFASs in the test soil, including perfluoroheptanesulfonic acid (PFHpS), and PFASs with butoxy, ethoxy, ethanol, and ethylcyclohexanesulfonate functional groups ; This work was supported by the project PFAS-PURE from VINNOVA, Sweden (2015-03561). Pablo Gago-Ferrero acknowledges the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement Smart-Workflow No 747698

Contamination of soils with organic pollutants is an increasing global problem, so novel soil remediation techniques are urgently needed. One such technique is electrokinetic remediation, in which an electric field is applied over the soil to extract contaminants. Previous evaluations of the technique have been limited to a few specific compounds. In this study, we integrated the latest advances in high-resolution mass spectrometry (HRMS) to identify molecular fingerprints, and used the results to improve the mechanistic understanding necessary for successful remediation. A laboratory-scale 0.38 mA cm−2 electrodialytic treatment was applied for 21 days to a contaminated soil from a firefighter training facility in Sweden. Non-target analysis allowed generic evaluation of changes in the soil organic fraction by tentatively determining the elemental composition of compounds present. The results showed that smaller oxygen-rich molecules were significantly transported to the anode by electromigration, while larger hydrogen-saturated molecules were transported to the cathode by electroosmotic flow. Wide suspect screening with >3000 per- and polyfluoroalkyl substances (PFASs) tentatively identified seven new PFASs in the test soil, including perfluoroheptanesulfonic acid (PFHpS), and PFASs with butoxy, ethoxy, ethanol, and ethylcyclohexanesulfonate functional groups. ; This work was supported by the project PFAS-PURE from VINNOVA, Sweden (2015-03561). Pablo Gago-Ferrero acknowledges the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement Smart-Workflow No 747698. The authors acknowledge the Trace Analysis and Mass Spectrometry Group (TrAMS of the University of Athens) for support with chemometric tools, and the Danish Technical University (DTU BYG) for experimental support. ; Peer reviewed

Comunicació de congrés presentada a: 16 th International Conference on Environmental Science and Technology, celebrat a l'Illa de Rodes (Grecia), del 4 a 7 de setembre de 2019 ; This work aims at integrating the last advances in high resolution mass spectrometry (HRMS) and statistical analysis of data to develop and optimize a smart methodology (workflow) for the assessment of the performance of innovative water treatments using different technological approaches based on advanced oxidation processes with UV-254nm: (i) UV/K2S2O8, where oxidation takes place mainly following the initial formation of sulfate radicals, (ii) UV/KHSO5, where oxidation begins with the formation of both sulfate and hydroxyl radicals and (iii) UV/H2O2, when only the formation of hydroxyl radicals takes place initially. Experiments were carried out using secondary effluent from a local wastewater treatment plant. The developed workflow allows the evaluation of the treatments in terms of overall oxidation through the careful study of Van Krevelen diagrams, where all the masses of the HRMS chromatograms are considered. The potential formation of transformation products with sulfur due to the sulfate radicals was also evaluated using statistical tools based on the isotopic pattern and accurate mass. Finally, the behavior of a large number of micropollutants with a wide range of physicochemical properties was studied using suspect screening strategies ; This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement SMARTWORKFLOW (747698), the Spanish Ministry of Science and Innovation (grant number CTQ2015-69832-C4), and the Economy and Knowledge Department of the Catalan Government (Consolidated Research Group program: ICRATECH - 2017 SGR 1318 and ICRA-ENV - 2017 SGR 01124)

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

A monitoring campaign was conducted which collected seven-day composite effluent samples (n=33) from 33 conventional wastewater treatment plants (WWTPs) across Germany to measure the concentrations of linear alkylbenzene sulfonates (LAS) and alkyl ethoxysulfates (AES). In addition, seven-day composite influent samples of four WWTPs were taken and analyzed for the same set of compounds, to determine the removal rates of the aforementioned surfactants during conventional wastewater treatment. This study encompasses the analysis of four LAS homologs (C10–C13) and two AES homologs with each 10 ethoxymers (C12 and C14 with 0-9 ethoxy units). Sample pretreatment was carried out by removing the aqueous phase using a rotational vacuum concentrator and reconstituting the analytes in a defined volume of ultra-pure water and acetonitrile. The identification and quantification of target compounds were performed by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The analytical performance of the methods was validated in tap water and effluent water, obtaining good trueness and precision for both matrices. Based on the estimated average effluent concentrations of individual LAS homologs, the average total LAS concentration in monitored WWTP effluents was 14.4 μg/L. Total AES effluent concentrations were lower compared to LAS, with an average total AES effluent concentration of 0.57 μg/L. No correlation between total LAS and AES effluent concentrations was found. Total LAS influent concentrations averaged at 3,200 μg/L, which translates to an average removal rate of 99.6%. The average total influent concentration of AES was 680 μg/L, indicating an average removal rate greater than 99.9%. Retrospective screening of 1,564 suspect list surfactants and their transformation products (TP) by a second laboratory was performed using ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS). The LAS-byproducts dialkyltetralin sulfonates (DATSs), the metabolites sulfophenyl alkyl carboxylic acids (SPACs) and sulfo-tetralin alkyl carboxylic acids (STACs) reached maximum concentration levels of 19 μg/L, 17 μg/L and 5.3 μg/L, respectively. It was shown that in many cases the sum of concentrations of all LAS-related byproducts and TPs surpassed the concentration of the four precursor LAS homologs (C10 – C13) themselves. High concentrations of up to 7.4 μg/L for 41 polyethylenoglycols (PEGs), the longest homolog series so far reported for PEGs, were detected. All quantified surfactants and their TPs and by-products together accounted for concentrations of up to 82 μg/L in effluent wastewater.

This study presents the development and validation of a comprehensive quantitative target methodology for the analysis of 2316 emerging pollutants in water based on Ultra-Performance Liquid Chromatography Quadrupole-Time-Of-Flight Mass Spectrometry (UPLC-Q-ToF-HRMS/MS). Target compounds include pesticides, pharmaceuticals, drugs of abuse, industrial chemicals, doping compounds, surfactants and transformation products, among others. The method was validated for 195 analytes, chosen to be representative of the chemical space of the target list, enabling the assessment of the performance of the method. The method involves a generic sample preparation based on mixed mode solid phase extraction, a UPLC-QTOF-MS/MS screening method using Data Independent Acquisition (DIA) mode, which provides MS and MS/MS spectra simultaneously and an elaborate strong post-acquisition evaluation of the data. The processing method was optimized to provide a successful identification rate >95 % and to minimize the number of false positive results (< 5 %). Decision limit (CCα) and detection capability (CCβ) were also introduced in the validation scheme to provide more realistic metrics on the performance of a HRMS-based wide-scope screening method. A new system of identification points (IPs) based on the one described in the Commission Decision 2002/657/EC was applied to communicate the confidence level in the identification of the analytes. This system considers retention time, mass accuracy, isotopic fit and fragmentation; taking full advantage of the capacities of the HRMS instruments. Finally, 398 contaminants were detected and quantified in real wastewater ; This project was implemented under the Operational Program "Education and Lifelong Learning" and funded by the European Union (European Social Fund) and Greek National Resources – ARISTEIA 624 (TREMEPOL project). Pablo Gago-Ferrero acknowledges the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement Smart-Workflow ...

AbstractA large number of apex predator samples are available in European research collections, environmental specimen banks and natural history museums that could be used in chemical monitoring and regulation. Apex predators bioaccumulate pollutants and integrate contaminant exposure over large spatial and temporal scales, thus providing key information for risk assessments. Still, present assessment practices under the different European chemical legislations hardly use existing chemical monitoring data from top predators. Reasons include the lack of user-specific guidance and the fragmentation of data across time and space. The European LIFE APEX project used existing sample collections and applied state-of-the-art target and non-target screening methods, resulting in the detection of > 4,560 pollutants including legacy compounds. We recommend establishing infrastructures that include apex predators as an early warning system in Europe. Chemical data of apex species from freshwater, marine and terrestrial compartments should become an essential component in future chemical assessment and management across regulations, with the purpose to (1) validate registration data with 'real world' measurements and evaluate the predictability of current models; (2) identify and prioritise hazardous chemicals for further assessment; (3) use data on food web magnification as one line of evidence to assess biomagnification; (4) determine the presence of (bio)transformations products and typical chemical mixtures, and (5) evaluate the effectiveness of risk management measures by trend analysis. We highlight the achievements of LIFE APEX with regard to novel trend and mixture analysis tools and prioritisation schemes. The proposed advancements complement current premarketing regulatory assessments and will allow the detection of contaminants of emerging concern at an early stage, trigger risk management measures and evaluations of their effects with the ultimate goal to protect humans and the environment. This is the second policy brief of the LIFE APEX project.

AbstractMonitoring data from apex predators were key drivers in the development of early chemicals legislations due to the population declines of many species during the twentieth century, which was linked to certain persistent organic pollutants (POPs). Besides triggering the development of global treaties (e.g. the Stockholm Convention), chemical monitoring data from apex predators have been particularly important for identifying compounds with bioaccumulative properties under field conditions. Many apex predators are protected species and only a few environmental specimen banks (ESBs) regularly collect samples as many ESBs were established during the 1980–1990s when apex predators were scarce. Today, many POPs have been banned, which contributed to the recovery of many apex predator populations. As a consequence, apex predator samples are now available in research collections (RCs) and natural history museums (NHMs). These samples can be used for routine analysis as well as for screening studies using novel analytical techniques and advanced data treatment workflows, such as suspect and non-target screening. The LIFE APEX project has demonstrated how these samples can be used in a cost-efficient way to generate data on legacy compounds and contaminants of emerging concern. Furthermore, it has described quality assurance/control measures to ensure high quality and comparable data, with a view to uses in chemicals risk assessment and management. To increase the visibility of available sample collections and monitoring data from apex predators we developed accessible online database systems. Additionally, the acquired high-resolution mass spectrometric data were stored in a digital sample freezing platform that allows retrospective suspect screening in previously analysed samples for substances that may be of concern/under assessment in the future. These databases provide open access to a wide range of chemical data, for use by regulators, researchers, industry and the general public, and contribute to a stronger link between science and policy.

Abstract
Background
Prioritisation of chemical pollutants is a major challenge for environmental managers and decision-makers alike, which is essential to help focus the limited resources available for monitoring and mitigation actions on the most relevant chemicals. This study extends the original NORMAN prioritisation scheme beyond target chemicals, presenting the integration of semi-quantitative data from retrospective suspect screening and expansion of existing exposure and risk indicators. The scheme utilises data retrieved automatically from the NORMAN Database System (NDS), including candidate substances for prioritisation, target and suspect screening data, ecotoxicological effect data, physico-chemical data and other properties. Two complementary workflows using target and suspect screening monitoring data are applied to first group the substances into six action categories and then rank the substances using exposure, hazard and risk indicators. The results from the 'target' and 'suspect screening' workflows can then be combined as multiple lines of evidence to support decision-making on regulatory and research actions.

Results
As a proof-of-concept, the new scheme was applied to a combined dataset of target and suspect screening data. To this end, > 65,000 substances on the NDS, of which 2579 substances supported by target wastewater monitoring data, were retrospectively screened in 84 effluent wastewater samples, totalling > 11 million data points. The final prioritisation results identified 677 substances as high priority for further actions, 7455 as medium priority and 326 with potentially lower priority for actions. Among the remaining substances, ca. 37,000 substances should be considered of medium priority with uncertainty, while it was not possible to conclude for 19,000 substances due to insufficient information from target monitoring and uncertainty in the identification from suspect screening. A high degree of agreement was observed between the categories assigned via target analysis and suspect screening-based prioritisation. Suspect screening was a valuable complementary approach to target analysis, helping to prioritise thousands of substances that are insufficiently investigated in current monitoring programmes.

Conclusions
This updated prioritisation workflow responds to the increasing use of suspect screening techniques. It can be adapted to different environmental compartments and can support regulatory obligations, including the identification of specific pollutants in river basins and the marine environments, as well as the confirmation of environmental occurrence levels predicted by modelling tools.

Graphical Abstract

AbstractIncreasing production and use of chemicals and awareness of their impact on ecosystems and humans has led to large interest for broadening the knowledge on the chemical status of the environment and human health by suspect and non-target screening (NTS). To facilitate effective implementation of NTS in scientific, commercial and governmental laboratories, as well as acceptance by managers, regulators and risk assessors, more harmonisation in NTS is required. To address this, NORMAN Association members involved in NTS activities have prepared this guidance document, based on the current state of knowledge. The document is intended to provide guidance on performing high quality NTS studies and data interpretation while increasing awareness of the promise but also pitfalls and challenges associated with these techniques. Guidance is provided for all steps; from sampling and sample preparation to analysis by chromatography (liquid and gas—LC and GC) coupled via various ionisation techniques to high-resolution tandem mass spectrometry (HRMS/MS), through to data evaluation and reporting in the context of NTS. Although most experience within the NORMAN network still involves water analysis of polar compounds using LC–HRMS/MS, other matrices (sediment, soil, biota, dust, air) and instrumentation (GC, ion mobility) are covered, reflecting the rapid development and extension of the field. Due to the ongoing developments, the different questions addressed with NTS and manifold techniques in use, NORMAN members feel that no standard operation process can be provided at this stage. However, appropriate analytical methods, data processing techniques and databases commonly compiled in NTS workflows are introduced, their limitations are discussed and recommendations for different cases are provided. Proper quality assurance, quantification without reference standards and reporting results with clear confidence of identification assignment complete the guidance together with a glossary of definitions. The NORMAN community greatly supports the sharing of experiences and data via open science and hopes that this guideline supports this effort.

AbstractThe chemical industry is the leading sector in the EU in terms of added value. However, contaminants pose a major threat and significant costs to the environment and human health. While EU legislation and international conventions aim to reduce this threat, regulators struggle to assess and manage chemical risks, given the vast number of substances involved and the lack of data on exposure and hazards. The European Green Deal sets a 'zero pollution ambition for a toxic free environment' by 2050 and the EU Chemicals Strategy calls for increased monitoring of chemicals in the environment. Monitoring of contaminants in biota can, inter alia: provide regulators with early warning of bioaccumulation problems with chemicals of emerging concern; trigger risk assessment of persistent, bioaccumulative and toxic substances; enable risk assessment of chemical mixtures in biota; enable risk assessment of mixtures; and enable assessment of the effectiveness of risk management measures and of chemicals regulations overall. A number of these purposes are to be addressed under the recently launched European Partnership for Risk Assessment of Chemicals (PARC). Apex predators are of particular value to biomonitoring. Securing sufficient data at European scale implies large-scale, long-term monitoring and a steady supply of large numbers of fresh apex predator tissue samples from across Europe. Natural science collections are very well-placed to supply these. Pan-European monitoring requires effective coordination among field organisations, collections and analytical laboratories for the flow of required specimens, processing and storage of specimens and tissue samples, contaminant analyses delivering pan-European data sets, and provision of specimen and population contextual data. Collections are well-placed to coordinate this. The COST Action European Raptor Biomonitoring Facility provides a well-developed model showing how this can work, integrating a European Raptor Biomonitoring Scheme, Specimen Bank and Sampling Programme. Simultaneously, the EU-funded LIFE APEX has demonstrated a range of regulatory applications using cutting-edge analytical techniques. PARC plans to make best use of such sampling and biomonitoring programmes. Collections are poised to play a critical role in supporting PARC objectives and thereby contribute to delivery of the EU's zero-pollution ambition.