Compound‐specific bromine isotope ratio analysis using gas chromatography/quadrupole mass spectrometry

Zakon, Yevgeni; Halicz, Ludwik; Lev, Ovadia; Gelman, Faina

doi:10.1002/rcm.7672

Cited by 13 publications

(5 citation statements)

References 25 publications

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“…This approach is chosen here for measurement of 18 O/ 16 O ratios of O 2 as shown in Figure 8b because O 2 isotoplogues can be ionized and measured directly in a isotope ratio mass spectrometer (Pati, Bolotin, et al, 2016). The same strategy is pursued, for example, for analysis of halogen isotopes in organic compounds where isotopologue ratios are determined in fragments of the target analyte (Bernstein et al, 2011;Elsner & Hunkeler, 2008;Zakon et al, 2016).…”

Section: Instrumental Strategiesmentioning

confidence: 99%

Characterization of Substrate, Cosubstrate, and Product Isotope Effects Associated With Enzymatic Oxygenations of Organic Compounds Based on Compound-Specific Isotope Analysis

Pati

Köhler

Hofstetter

2017

Measurement and Analysis of Kinetic Isotope Effects

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Enzymatic oxygenations are among the most important biodegradation and detoxification reactions of organic pollutants. In the environment, however, such natural attenuation processes are extremely difficult to monitor. Changes of stable isotope ratios of aromatic pollutants at natural isotopic abundances serve as proxies for isotope effects associated with oxygenation reactions. Such isotope fractionations offer new avenues for revealing the pathway and extent of pollutant transformation and provide new insights into the mechanisms of catalysis by Rieske non-heme ferrous iron oxygenases. Based on compound-specific C, H, N, and O isotope analysis, we present a comprehensive methodology with which isotope effects can be derived from the isotope fractionation measured in substrates, the cosubstrate O, and organic oxygenation products. We use dioxygenation of nitrobenzene and 2-nitrotoluene by nitrobenzene dioxygenase as illustrative examples to introduce different mathematical procedures for deriving apparent substrate and product isotope effects. We present two experimental approaches to control reactant and product turnover for isotope fractionation analysis in experimental systems containing purified enzymes, E. coli clones, and pure strains of environmental microorganisms. Finally, we present instrumental procedures and sample treatment instructions for analysis of C, H, and N isotope analysis in organic compounds and O isotope analysis in aqueous O by gas and liquid chromatography coupled to isotope ratio mass spectrometry.

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Section: Instrumental Strategiesmentioning

confidence: 99%

Characterization of Substrate, Cosubstrate, and Product Isotope Effects Associated With Enzymatic Oxygenations of Organic Compounds Based on Compound-Specific Isotope Analysis

Pati

Köhler

Hofstetter

2017

Measurement and Analysis of Kinetic Isotope Effects

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“…Gas chromatography coupled with electron ionization quadrupole mass spectrometry (GC-EI-qMS) has been recently employed to conduct compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) of halogenated organic compounds (HOCs) such as tetrachloroethene, trichloroethene, cis-dichloroethene, 1 p,p'dichlorodiphenyltrichloroethane (p,p'-DDT), pentachlorophenol, 2 chlorinated acetic acids, 3 bromoform, 3-bromophenol and 4-bromotoluene. 4 Performances of CSIA-Cl methods using GC-EI-qMS were found to be comparable with those of conventional methods using GC continuous flow isotope ratio MS (GC-IRMS) and preparative GC followed by offline IRMS. 3,5 Moreover, CSIA-Cl methods using GC-qMS significantly simplify sample pretreatment and therefore are more cost-effective and applicable.…”

Section: Introductionmentioning

confidence: 89%

Chlorine and bromine isotope fractionations of halogenated organic compounds in fragmentation by gas chromatography-electron ionization high resolution mass spectrometry

Tang

Tan

Shi

et al. 2019

Journal of Chromatography A

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Revelation of chlorine and bromine isotope fractionation of halogenated organic compounds (HOCs) in electron ionization mass spectrometry (EI-MS) is crucial for compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) using gas chromatography EI-MS (GC-EI-MS). This study systematically investigated chlorine/bromine isotope fractionation in EI-MS of HOCs including 12 organochlorines and 5 organobromines using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). Chlorine/bromine isotope fractionation behaviors of the HOCs in EI-MS showed varied isotope fractionation patterns and extents depending on compounds. Besides, isotope fractionation patterns and extents varied at different EI energies, demonstrating potential impacts of EI energy on the chlorine/bromine isotope fractionation. Hypotheses of inter-ion and intra-ion isotope fractionations were applied to interpreting the isotope fractionation behaviors. The inter-ion and intra-ion isotope fractionations counteractively contributed to the apparent isotope ratio for a certain dehalogenated product ion. The isotope fractionation mechanisms were tentatively elucidated on basis of the quasi-equilibrium theory. In the light of the findings of this study, isotope ratio evaluation scheme using complete molecular ions and the EI source with sufficient stable EI energies may be helpful to achieve optimal precision and accuracy of CSIA-Cl/Br data. The method and results of this study can help to predict isotope fractionation of HOCs during dehalogenation processes and further to reveal the dehalogenation pathways.

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“…This approach has been optimized and applied for different chlorinated compounds, including chlorinated methanes (Heckel et al, 2017), chlorinated phenols (Aeppli et al, 2013;Marchesi et al, 2018) and chlorinated ethenes and ethanes (Buchner et al, 2015;Palau et al, 2016;Rosell et al, 2019b). Recently, the method was also extended for bromine CSIA of brominated organic compounds (Gelman and Dybala-Defratyka, 2019;Tang et al, 2017;Zakon et al, 2016). Despite the recent advances on halogen CSIA, there is still a lack of methods able to simultaneously determine isotopic ratios of different halogen elements of a given organic compound.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous determination of stable chlorine and bromine isotopic ratios for bromochlorinated trihalomethanes using GC-qMS

Jin

Zhang

et al. 2021

Chemosphere

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Compound‐specific bromine isotope ratio analysis using gas chromatography/quadrupole mass spectrometry

Cited by 13 publications

References 25 publications

Characterization of Substrate, Cosubstrate, and Product Isotope Effects Associated With Enzymatic Oxygenations of Organic Compounds Based on Compound-Specific Isotope Analysis

Characterization of Substrate, Cosubstrate, and Product Isotope Effects Associated With Enzymatic Oxygenations of Organic Compounds Based on Compound-Specific Isotope Analysis

Chlorine and bromine isotope fractionations of halogenated organic compounds in fragmentation by gas chromatography-electron ionization high resolution mass spectrometry

Simultaneous determination of stable chlorine and bromine isotopic ratios for bromochlorinated trihalomethanes using GC-qMS

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