Measurement of rare isotopologues of nitrous oxide by high‐resolution multi‐collector mass spectrometry

Magyar, Paul; Orphan, Victoria J.; Eiler, John M.

doi:10.1002/rcm.7671

Cited by 41 publications

(41 citation statements)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because not all analyses in this study were calibrated independently and some of the differences are not fully resolved, we conclude that additional analyses and interlaboratory exchanges are needed to obtain more accurate values for the isotopic compositions of USGS51 and USGS52. The analytical methods may include decomposition of a common ammonium nitrate reference material and analysis by multiple laboratories and/or comparison with N 2 O allowed to reach isotopic equilibrium at moderate temperatures . Meanwhile, we suggest that the complete set of values reported by Laboratory 1 (Tokyo Institute of Technology, highlighted in bold type in Table ) can be used provisionally for normalizing N 2 O isotopic measurements to improve interlaboratory consistency following the reporting guidelines given below.…”

Section: Discussionmentioning

confidence: 99%

“…2,3 In addition, the recent development of double-focusing mass spectrometers for precise stable isotope analyses of rare isotopocules with high mass resolution and good sensitivity now enables clumped isotopic analysis of N 2 O. 4,5 Despite the strong interest in and long history of isotopic analyses of N 2 O, 6,7 there is a lack of isotopically characterized N 2 O isotopic reference materials (standards) to enable normalization 8 and reporting of compatible isotope-delta values (within analytical uncertainty) from different laboratories worldwide. Thus, while reported isotope-delta values for N 2 O may be consistent within one laboratory, disparity among laboratories can be substantial.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs

Ostrom

Gandhi

Coplen

et al. 2018

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

The agreement of isotope-delta values obtained in the interlaboratory comparison was not sufficient to provide reliable accurate isotope measurement values for USGS51 and USGS52. We propose that provisional values for the isotopic composition of USGS51 and USGS52 determined at the Tokyo Institute of Technology can be adopted for normalizing and reporting sample data until further refinements are achieved through additional calibration efforts.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs

Ostrom

Gandhi

Coplen

et al. 2018

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

show abstract

“…Diffusion through a liquid or solid has unknown effects on  18 . Similar diffusive fractionations have been described for multiplysubstituted isotopologues of CO 2 , O 2 (Yeung et al, 2012), and N 2 O (Magyar et al, 2016). Fractionation during diffusion through a liquid phase, which is an important transport mechanism for methane in aquatic environments, is unknown both theoretically and experimentally.…”

Section: Other Kinetic Isotope Effectsmentioning

confidence: 75%

“…This relationship allows methane clumped isotope abundances to be used as a geothermometer to constrain gas formation temperatures Wang et al, 2015). The temperature dependence of clumped-isotope abundances is not unique to methane and exists for all studied materials including CO 2 , carbonate-bearing minerals (Ghosh et al, 2006), O 2 (Yeung et al, 2012), and N 2 O (Magyar et al, 2016). Clumped isotope abundance in systems that are not in internal isotopic equilibrium can also be used to provide constraints on non-equilibrium processes including the chemical kinetics of various reactions, which we discuss here as well (Daëron et al, 2011;Saenger et al, 2012;Stolper et al, 2015;Wang et al, 2015;Yeung et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

Methane clumped isotopes: Progress and potential for a new isotopic tracer

Douglas

Stolper

Eiler

et al. 2017

Organic Geochemistry

Self Cite

114

127

View full text Add to dashboard Cite

Highlights:-We present a review and an expanded dataset of methane clumped isotope measurements.-Methane clumped isotope values often indicate equilibrium formation temperature.-Kinetic effects during or after methane production can affect clumped isotope values.-The wide variability in clumped isotope values suggests it will be a useful tracer. AbstractThe isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric 3 greenhouse gas concentrations, the global carbon cycle, and life in extreme environments.Recent analytical developments focusing on multiply substituted isotopologues ('clumped isotopes') are opening a valuable new window into methane geochemistry.When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions.We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism.

show abstract

“…Gas source mass spectrometry exhibits an intrinsic analytical mass fractionation that must be corrected for by comparison with a known standard. Site-specific and clumped isotope standards potentially can be prepared by selective chemical degradation followed by conventional analysis of the `pieces' (e.g., N 2 O, (Toyoda and Yoshida, 1999)), or by driving a standard to thermodynamic equilibrium at known temperature and assuming theoretical values of that equilibrium state (e.g., CO 2 , O 2 , CH 4 and N 2 O; (Wang et al, 2004;Stolper et al, 2014;Magyar et al, 2016;Piasecki, et al, 2016b)). Neither of these strategies has yet succeeded for propane; thus, we can only report variation in site-specific carbon isotope ratio as differences from a standard without knowing the absolute 13 C/ 12 C ratios of each carbon position.…”

Section: Reference Frame and Plotting Conventionsmentioning

confidence: 99%

Position-specific 13C distributions within propane from experiments and natural gas samples

Piasecki

Sessions

Lawson

et al. 2018

Geochimica et Cosmochimica Acta

Self Cite

View full text Add to dashboard Cite

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.Position-specific 13 C distributions within propane from experiments and natural gas samples method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ 13 C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ 13 C and then increasing in both center and terminal position δ 13 C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

show abstract

Measurement of rare isotopologues of nitrous oxide by high‐resolution multi‐collector mass spectrometry

Abstract: 7RATIONALE: Bulk and position-specific stable isotope characterization of nitrous oxide 8 represents one of the most powerful tools for identifying its environmental sources and sinks.

Cited by 41 publications

References 72 publications

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs

Methane clumped isotopes: Progress and potential for a new isotopic tracer

Position-specific 13C distributions within propane from experiments and natural gas samples

Contact Info

Product

Resources

About