Isotope effects associated with the preparation and methylation of fatty acids by boron trifluoride in methanol for compound-specific stable hydrogen isotope analysis via gas chromatography/thermal conversion/isotope ratio mass spectrometry

2012 ◽  
Vol 26 (10) ◽  
pp. 1232-1240 ◽  
Author(s):  
David Chivall ◽  
Robert Berstan ◽  
Ian D. Bull ◽  
Richard P. Evershed
Keyword(s):  
Mass Spectrometry ◽  
Fatty Acids ◽  
Isotope Ratio ◽  
Hydrogen Isotope ◽  
Boron Trifluoride ◽  
Isotope Effects ◽  
Isotope Analysis ◽  
Isotope Ratio Mass Spectrometry ◽  
Thermal Conversion ◽  
Stable Hydrogen Isotope

scholarly journals Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

2018 ◽  
Author(s):  
Frank Keppler ◽  
Enno Bahlmann ◽  
Markus Greule ◽  
Heinz Friedrich Schöler ◽  
Julian Wittmer ◽  
...  
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Isotope Analysis ◽  
Isotope Ratio Mass Spectrometry ◽  
Detailed Knowledge ◽  
Mass Spectrometric Measurement ◽  
Isotopic Analyses ◽  
Chlorine Radicals ◽  
Stable Hydrogen Isotope

Abstract. Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but yet lacks detailed knowledge of its budget. Stable isotope analysis is potentially a powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog-chamber at 293 ± 1 K. We measured the increasing stable hydrogen isotope values of the unreacted CH3Cl using compound specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −242 ± 7 mUr (or ‰) and −280 ± 11 mUr, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of −205 ± 6 mUr which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

scholarly journals Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

2018 ◽  
Vol 18 (9) ◽  
pp. 6625-6635 ◽  
Author(s):  
Frank Keppler ◽  
Enno Bahlmann ◽  
Markus Greule ◽  
Heinz Friedrich Schöler ◽  
Julian Wittmer ◽  
...  
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Isotope Analysis ◽  
Isotope Ratio Mass Spectrometry ◽  
Detailed Knowledge ◽  
Mass Spectrometric Measurement ◽  
Isotopic Analyses ◽  
Chlorine Radicals ◽  
Stable Hydrogen Isotope

Abstract. Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be -264±45 and -280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of -205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Compound-Specific Hydrogen Isotope Analysis of Heteroatom-Bearing Compounds via Gas Chromatography–Chromium-Based High-Temperature Conversion (Cr/HTC)–Isotope Ratio Mass Spectrometry

2015 ◽  
Vol 87 (18) ◽  
pp. 9443-9450 ◽  
Author(s):  
Julian Renpenning ◽  
Steffen Kümmel ◽  
Kristina L. Hitzfeld ◽  
Arndt Schimmelmann ◽  
Matthias Gehre
Keyword(s):  
Mass Spectrometry ◽  
Gas Chromatography ◽  
High Temperature ◽  
Isotope Ratio ◽  
Hydrogen Isotope ◽  
Isotope Analysis ◽  
Isotope Ratio Mass Spectrometry
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