Ultratrace-level determination of glyphosate, aminomethylphosphonic acid and glufosinate in natural waters by solid-phase extraction followed by liquid chromatography-tandem mass spectrometry: performance tuning of derivatization, enrichment and detection

A sensitive and robust analytical method for the quantification of glyphosate, aminomethylphosphonic acid (AMPA) and glufosinate in natural water has been developed on the basis of a derivatization with 9-fluorenylmethylchloroformate (FMOC-Cl), solid-phase extraction (SPE) and liquid chromatography followed by electrospray tandem mass spectrometry (LC-ESI-MS/MS). In order to maximize sensitivity, the derivatization was optimized regarding organic solvent content, amount of FMOC-Cl and reaction time. At an acetonitrile content of 10% a derivatization yield of 100% was reached within two hours in groundwater and surface water samples. After a twofold dilution the low acetonitrile content allowed solid-phase extraction of a sample of originally 80mL over 200mg Strata-X cartridges. In order to decrease the load of the LC column and mass spectrometer with derivatization by-products (e.g., 9-fluorenylmethanol FMOC-OH), a rinsing step was performed for the SPE cartridge with dichloromethane. Acidification of the sample and addition of EDTA was used to minimize complexation of the target compounds with metal ions in environmental samples. Due to the large sample volume and the complete FMOC-OH removal, limits of quantification of 0.7ng/L, 0.8ng/L and 2.3ng/L were achieved in surface water for glyphosate, AMPA and glufosinate, respectively. The limits of detection were as low as 0.2ng/L, 0.2ng/L and 0.6ng/L for glyphosate, AMPA and glufosinate, respectively. Surface water and ground water samples spiked at 2ng/L showed recoveries of 91-107%. Figure LC-MS/MS chromatogram of a water sample from a remote alpine region spiked at 1ng/

LC-high resolution MS in environmental analysis: from target screening to the identification of unknowns

This article provides an overview of the state-of-the-art and future trends of the application of LC-high resolution mass spectrometry to the environmental analysis of polar micropollutants. Highly resolved and accurate hybrid tandem mass spectrometry such as quadrupole/time-of-flight and linear ion trap/orbitrap technology allows for a more reliable target analysis with reference standards, a screening for suspected analytes without reference standards, and a screening for unknowns. A reliable identification requires both high resolving power and high mass spectral accuracy to increase selectivity against the matrix background and for a correct molecular formula assignment to unknown compounds. For the identification and structure elucidation of unknown compounds within a reasonable time frame and with a reasonable soundness, advanced automated software solutions as well as improved prediction systems for theoretical fragmentation patterns, retention times, and ionization behavior are needed. Figure a Plot of nominal m/z vs. mass defect of all matrix ions observed in two retention time (Rt) windows of a full-scan HRMS chromatogram at a resolution of 60,000 from a background soil extract. b Extracted ion chromatograms of the herbicide linuron spiked into a background soil extract and of a suspected transformation product of lenacil in a soil extract, both showing a different mass defec

Überwachung von NSO-Heterocyclen an Teeröl-kontaminierten Standorten

Kurzfassung: An Teeröl-kontaminierten Standorten kommen neben Schadstoffen wie homocyclischen aromatischen Kohlenwasserstoffen auch NSO-heterocyclische Kohlenwasserstoffe vor, die bislang nicht routinemäßig überwacht werden, obwohl die Bundes-Bodenschutz- und Altlastenverordnung dies explizit fordert. Im Zuge des BMBF-Förderschwerpunktes "KORA - Kontrollierter natürlicher Rückhalt und Abbau von Schadstoffen bei der Sanierung kontaminierter Grundwässer und Böden” wurden mehrere Teeröl-kontaminierte Standorte in Deutschland untersucht und in Verbindung mit weiteren Literaturdaten zu Toxizität und Persistenz Prioritärsubstanzen abgeleitet, die wir empfehlen, in die Routineanalytik zur Beurteilung von Natural Attenuation- Prozessen aufzunehmen. Für den Nachweis und die Quantifizierung der Verbindungen wurden verschiedene Analysemethoden entwickel

Removal of highly polar micropollutants from wastewater by powdered activated carbon

Due to concerns about ecotoxicological effects of pharmaceuticals and other micropollutants released from wastewater treatment plants, activated carbon adsorption is one of the few processes to effectively reduce the concentrations of micropollutants in wastewater. Although aimed mainly at apolar compounds, polar compounds are also simultaneously removed to a certain extent, which has rarely been studied before. In this study, adsorption isotherm and batch kinetic data were collected with two powdered activated carbons (PACs) to assess the removal of the polar pharmaceuticals 5-fluorouracil (5-Fu) and cytarabine (CytR) from ultrapure water and wastewater treatment plant effluent. At pH 7.8, single-solute adsorption isotherm data for the weak acid 5-Fu and the weak base CytR showed that their adsorption capacities were about 1 order of magnitude lower than those of the less polar endocrine disrupting chemicals bisphenol A (BPA) and 17-α-ethinylestradiol (EE2). To remove 90% of the adsorbate from a single-solute solution 14, 18, 70, and 87mg L−1 of HOK Super is required for EE2, BPA, CytR, and 5-Fu, respectively. Effects of solution pH, ionic strength, temperature, and effluent organic matter (EfOM) on 5-Fu and CytR adsorption were evaluated for one PAC. Among the studied factors, the presence of EfOM had the highest effect, due to a strong competition on 5-Fu and CytR adsorption. Adsorption isotherm and kinetic data and their modeling with a homogeneous surface diffusion model showed that removal percentage in the presence of EfOM was independent on the initial concentration of the ionizable compounds 5-Fu and CytR. These results are similar to neutral organic compounds in the presence of natural organic matter. Overall, results showed that PAC doses sufficient to remove >90% of apolar adsorbates were able to remove no more than 50% of the polar adsorbates 5-Fu and CytR and that the contact time is a critical paramete

Establish data infrastructure to compile and exchange environmental screening data on a European scale

Robust techniques based on liquid (LC) and gas chromatography (GC) coupled with high-resolution mass spectrometry (HR-MS) enable sensitive screening, identification, and (semi)quantification of thousands of substances in a single sample. Recent progress in computational sciences has enabled archiving and processing of HR-MS ‘big data’ at the routine level. As a result, community-based databases containing thousands of environmental pollutants are rapidly growing and large databases of substances with unique identifiers allowing for inter-comparison at the global scale have become available. A data-archiving infrastructure is proposed, allowing for retrospective screening of HR-MS data, which will help define the ‘chemical universe’ of organic substances and enable prioritisation of toxicants causing adverse environmental effects at the local, river basin, and national and European scale in support of the European water and chemicals management policy

MetFrag relaunched: incorporating strategies beyond in silico fragmentation

Background: The in silico fragmenter MetFrag, launched in 2010, was one of the first approaches combining compound database searching and fragmentation prediction for small molecule identification from tandem mass spectrometry data. Since then many new approaches have evolved, as has MetFrag itself. This article details the latest developments to MetFrag and its use in small molecule identification since the original publication.Results: MetFrag has gone through algorithmic and scoring refinements. New features include the retrieval of reference, data source and patent information via ChemSpider and PubChem web services, as well as InChIKey filtering to reduce candidate redundancy due to stereoisomerism. Candidates can be filtered or scored differently based on criteria like occurence of certain elements and/or substructures prior to fragmentation, or presence in so-called “suspect lists”. Retention time information can now be calculated either within MetFrag with a sufficient amount of user-provided retention times, or incorporated separately as “user-defined scores” to be included in candidate ranking. The changes to MetFrag were evaluated on the original dataset as well as a dataset of 473 merged high resolution tandem mass spectra (HR-MS/MS) and compared with another open source in silico fragmenter, CFM-ID. Using HR-MS/MS information only, MetFrag2.2 and CFM-ID had 30 and 43 Top 1 ranks, respectively, using PubChem as a database. Including reference and retention information in MetFrag2.2 improved this to 420 and 336 Top 1 ranks with ChemSpider and PubChem (89 and 71 %), respectively, and even up to 343 Top 1 ranks (PubChem) when combining with CFM-ID. The optimal parameters and weights were verified using three additional datasets of 824 merged HR-MS/MS spectra in total. Further examples are given to demonstrate flexibility of the enhanced features.Conclusions: In many cases additional information is available from the experimental context to add to small molecule identification, which is especially useful where the mass spectrum alone is not sufficient for candidate selection from a large number of candidates. The results achieved with MetFrag2.2 clearly show the benefit of considering this additional information. The new functions greatly enhance the chance of identification success and have been incorporated into a command line interface in a flexible way designed to be integrated into high throughput workflows. Feedback on the command line version of MetFrag2.2 available at http://c-ruttkies.github.io/MetFrag/ is welcome

Importance of Dietary Uptake for in Situ Bioaccumulation of Systemic Fungicides Using Gammarus pulex as a Model Organism

Bioaccumulation of organic contaminants from contaminated food sources might pose an underestimated risk toward shredding invertebrates. This assumption is substantiated by monitoring studies observing discrepancies of predicted tissue concentrations determined from laboratory-based experiments compared with measured concentrations of systemic pesticides in gammarids. To elucidate the role of dietary uptake in bioaccumulation, gammarids were exposed to leaf material from trees treated with a systemic fungicide mixture (azoxystrobin, cyprodinil, fluopyram, and tebuconazole), simulating leaves entering surface waters in autumn. Leaf concentrations, spatial distribution, and leaching behavior of fungicides were characterized using liquid chromatography coupled with high-resolution tandem mass spectrometry (LC-HRMS/MS) and matrix-assisted laser desorption ionization-mass spectrometric imaging. The contribution of leached fungicides and fungicides taken up from feeding was assessed by assembling caged (no access) and uncaged (access to leaves) gammarids. The fungicide dynamics in the test system were analyzed using LC-HRMS/MS and toxicokinetic modeling. In addition, a summer scenario was simulated where water was the initial source of contamination and leaves contaminated by sorption. The uptake, translocation, and biotransformation of systemic fungicides by trees were compound-dependent. Internal fungicide concentrations of gammarids with access to leaves were much higher than in caged gammarids of the autumn scenario, but the difference was minimal in the summer scenario. In food choice and dissectioning experiments gammarids did not avoid contaminated leaves and efficiently assimilated contaminants from leaves, indicating the relevance of this exposure pathway in the field. The present study demonstrates the potential impact of dietary uptake on in situ bioaccumulation for shredders in autumn, outside the main application period. The toxicokinetic parameters obtained facilitate modeling of environmental exposure scenarios. The uncovered significance of dietary uptake for detritivores warrants further consideration from scientific as well as regulatory perspectives. Environ Toxicol Chem 2023;00:1-14. (c) 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC

Uptake and release kinetics of 22 polar organic chemicals in the Chemcatcher passive sampler

The Chemcatcher passive sampler, which uses Empore™ disks as sampling phase, is frequently used to monitor polar organic chemicals in river water and effluents. Uptake kinetics need to be quantified to calculate time-weighted average concentrations from Chemcatcher field deployments. Information on release kinetics is needed if performance reference compounds (PRCs) are used to quantify the influence of environmental conditions on the uptake. In a series of uptake and elimination experiments, we used Empore™ SDB disks (poly(styrenedivinylbenzene) copolymer modified with sulfonic acid groups) as a sampling phase and 22 compounds with a logK ow (octanol-water partitioning coefficient) range from −2.6 to 3.8. Uptake experiments were conducted in river water or tap water and lasted up to 25days. Only 1 of 22 compounds (sulfamethoxazole) approached equilibrium in the uptake trials. Other compounds showed continuing non-linear uptake, even after 25days. All compounds could be released from SDB disks, and desorption was proportionally higher in disks loaded for shorter periods. Desorption showed two-phase characteristics, and desorption was proportionally higher for passively sorbed compounds compared to actively loaded compounds (active loading was performed by pulling spiked river water over SDB disks using vacuum). We hypothesise that the two-phase kinetics and better retention of actively loaded compounds—and compounds loaded for a longer period—may be caused by slow diffusion of chemicals within the polymer. As sorption and desorption did not show isotropic kinetics, it is not possible to develop robust PRCs for adsorbent material like SDB disk

Targeting aquatic microcontaminants for monitoring: exposure categorization and application to the Swiss situation

Background, aim, and scope: Aquatic microcontaminants (MCs) comprise diverse chemical classes, such as pesticides, biocides, pharmaceuticals, consumer products, and industrial chemicals. For water pollution control and the evaluation of water protection measures, it is crucial to screen for MCs. However, the selection and prioritization of which MCs to screen for is rather difficult and complex. Existing methods usually are strongly limited because of a lack of screening regulations or unavailability of required data. Method and models: Here, we present a simple exposure-based methodology that provides a systematic overview of a broad range of MCs according to their potential to occur in the water phase of surface waters. The method requires input of publicly available data only. Missing data are estimated with quantitative structure-property relationships. The presented substance categorization methodology is based on the chemicals' distribution behavior between different environmental media, degradation data, and input dynamics. Results: Seven different exposure categories are distinguished based on different compound properties and input dynamics. Ranking the defined exposure categories based on a chemical's potential to occur in the water phase of surface waters, exposure categories I and II contain chemicals with a very high potential, categories III and IV contain chemicals with a high potential, and categories V and VI contain chemicals with a moderate to low potential. Chemicals in category VII are not evaluated because of a lack of data. We illustrate and evaluate the methodology on the example of MCs in Swiss surface waters. Furthermore, a categorized list containing potentially water-relevant chemicals is provided. Discussion: Chemicals of categories I and III continuously enter surface waters and are thus likely to show relatively steady concentrations. Therefore, they are best suited for water monitoring programs requiring a relatively low sampling effort. Chemicals in categories II and IV have complex input dynamics. They are consequently more difficult to monitor. However, they should be considered if an overall picture is needed that includes contaminants from diffuse sources. Conclusions: The presented methodology supports compound selection for (a) water quality guidance, (b) monitoring programs, and (c) further research on the chemical's ecotoxicology. The results from the developed categorization procedure are supported by data on consumption and observed concentrations in Swiss surface waters. The presented methodology is a tool to preselect potential hazardous substances based on exposure-based criteria for policy guidance and monitoring programs and a first important step for a detailed risk assessment for potential microcontaminant