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Martin Elsner - One of the best experts on this subject based on the ideXlab platform.

  • 13c and 15n Isotope Analysis of desphenylchloridazon by liquid chromatography Isotope ratio mass spectrometry and derivatization gas chromatography Isotope ratio mass spectrometry
    Analytical Chemistry, 2019
    Co-Authors: Aileen Melsbach, Thomas B Hofstetter, Violaine Ponsin, Clara Torrento, Christina Lihl, Daniel Hunkeler, Martin Elsner
    Abstract:

    The widespread application of herbicides impacts surface water and groundwater. Metabolites (e.g., desphenylchloridazon from chloridazon) may be persistent and even more polar than the parent herbicide, which increases the risk of groundwater contamination. When parent herbicides are still applied, metabolites are constantly formed and may also be degraded. Evaluating their degradation on the basis of concentration measurements is, therefore, difficult. This study presents compound-specific stable-Isotope Analysis (CSIA) of nitrogen- and carbon-Isotope ratios at natural abundances as an alternative analytical approach to track the origin, formation, and degradation of desphenylchloridazon (DPC), the major degradation product of the herbicide chloridazon. Methods were developed and validated for carbon- and nitrogen-Isotope Analysis (δ13C and δ15N) of DPC by liquid chromatographyIsotope-ratio mass spectrometry (LC-IRMS) and derivatization gas chromatography–IRMS (GC-IRMS), respectively. Injecting standard...

  • 13C- and 15N‑Isotope Analysis of Desphenylchloridazon by Liquid Chromatography–Isotope-Ratio Mass Spectrometry and Derivatization Gas Chromatography–Isotope-Ratio Mass Spectrometry
    2019
    Co-Authors: Aileen Melsbach, Thomas B Hofstetter, Violaine Ponsin, Christina Lihl, Daniel Hunkeler, Clara Torrentó, Martin Elsner
    Abstract:

    The widespread application of herbicides impacts surface water and groundwater. Metabolites (e.g., desphenylchloridazon from chloridazon) may be persistent and even more polar than the parent herbicide, which increases the risk of groundwater contamination. When parent herbicides are still applied, metabolites are constantly formed and may also be degraded. Evaluating their degradation on the basis of concentration measurements is, therefore, difficult. This study presents compound-specific stable-Isotope Analysis (CSIA) of nitrogen- and carbon-Isotope ratios at natural abundances as an alternative analytical approach to track the origin, formation, and degradation of desphenylchloridazon (DPC), the major degradation product of the herbicide chloridazon. Methods were developed and validated for carbon- and nitrogen-Isotope Analysis (δ13C and δ15N) of DPC by liquid chromatography–Isotope-ratio mass spectrometry (LC-IRMS) and derivatization gas chromatography–IRMS (GC-IRMS), respectively. Injecting standards directly onto an Atlantis LC-column resulted in reproducible δ13C-Isotope Analysis (standard deviation

  • current challenges in compound specific stable Isotope Analysis of environmental organic contaminants
    Analytical and Bioanalytical Chemistry, 2012
    Co-Authors: Martin Elsner, Thomas B Hofstetter, Daniel Hunkeler, Anat Bernstein, Maik A Jochmann, Torsten C Schmidt, Arndt Schimmelmann
    Abstract:

    Compound-specific stable-Isotope Analysis (CSIA) has greatly facilitated assessment of sources and transformation processes of organic pollutants. Multielement Isotope Analysis is one of the most promising applications of CSIA because it even enables distinction of different transformation pathways. This review introduces the essential features of continuous-flow Isotope-ratio mass spectrometry (IRMS) and highlights current challenges in environmental Analysis as exemplified for the Isotopes of nitrogen, hydrogen, chlorine, and oxygen. Strategies and recent advances to enable isotopic measurements of polar contaminants, for example pesticides or pharmaceuticals, are discussed with special emphasis on possible solutions for Analysis of low concentrations of contaminants in environmental matrices. Finally, we discuss different levels of calibration and referencing and point out the urgent need for compound-specific Isotope standards for gas chromatography–Isotope-ratio mass spectrometry (GC–IRMS) of organic pollutants.

  • small and reproducible Isotope effects during methylation with trimethylsulfonium hydroxide tmsh a convenient derivatization method for Isotope Analysis of negatively charged molecules
    Analytical Chemistry, 2010
    Co-Authors: Sandra Reinnicke, Anat Bernstein, Martin Elsner
    Abstract:

    Negatively charged analytes must be derivatized prior to gas chromatography-Isotope ratio mass spectrometry (GC-IRMS), with stringent control of Isotope fractionation. Current methods require offline sample preparation. This study tests for the first time trimethylsulfonium hydroxide (TMSH) as online methylation agent prior to Isotope Analysis, addressing the herbicides bentazone and MCPA. Fully automated derivatization was achieved in a temperature-programmable GC injector, where reactants were injected into a packed liner, solvents were removed by split flow, and subsequent flash heating triggered the derivatization, thereby transferring derivatives onto the chromatographic column. Stoichiometric addition of TMSH resulted in complete conversion giving accurate and reproducible nitrogen Isotope values of bentazone. In contrast, reproducible carbon Isotope Analysis required TMSH in > or = 250-fold excess. Contrary to expectations, delta(13)C values became more negative at smaller TMSH excess. This indicates that elevated methyl group concentrations in the pore space of the injection liner facilitated close-to-equilibrium rather than kinetic Isotope fractionation resulting in reproducible derivatization conditions. delta(13)C results under these conditions compared favorably with liquid chromatography-IRMS: low standard deviations (0.3 per thousand for GC-IRMS, 0.1 per thousand for LC-IRMS) and a comparable offset of 1 per thousand compared to elemental analyzer-IRMS demonstrate that both methods represent expedient ways for online Isotope Analysis of anionic target compounds.

  • intramolecular carbon and nitrogen Isotope Analysis by quantitative dry fragmentation of the phenylurea herbicide isoproturon in a combined injector capillary reactor prior to gc separation
    Analytical Chemistry, 2007
    Co-Authors: Holger Penning And, Martin Elsner
    Abstract:

    Potentially, compound-specific Isotope Analysis may provide unique information on source and fate of pesticides in natural systems. Yet for Isotope Analysis, LC-based methods that are based on the use of organic solvents often cannot be used and GC-based Analysis is frequently not possible due to thermolability of the analyte. A typical example of a compound with such properties is isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), belonging to the worldwide extensively used phenylurea herbicides. To make isoproturon accessible to carbon and nitrogen Isotope Analysis, we developed a GC-based method during which isoproturon was quantitatively fragmented to dimethylamine and 4-isopropylphenylisocyanate. Fragmentation occurred only partially in the injector but was mainly achieved on a heated capillary column. The fragments were then chromatographically separated and individually measured by Isotope ratio mass spectrometry. The reliability of the method was tested in hydrolysis experiments with three isot...

Christina Lihl - One of the best experts on this subject based on the ideXlab platform.

Julian Renpenning - One of the best experts on this subject based on the ideXlab platform.

Violaine Ponsin - One of the best experts on this subject based on the ideXlab platform.

Aileen Melsbach - One of the best experts on this subject based on the ideXlab platform.