A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases

Young, Edward; Rumble, Douglas; Freedman, Philip A.; Mills, Mark P.

doi:10.1016/j.ijms.2016.01.006

Cited by 81 publications

(144 citation statements)

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“…Data shown in this thesis for δ 13 C, δD, and ∆ 13 CH 3 D assume that reference gas AL1 has the isotopic composition −34.5‰, −147.7‰, and +2.41 ± 0.07‰ (95% CI) respectively, consistent with Wang et al (2015) and with the values we provided to the UCLA group (Young et al, 2016). The D term corrects the observation that measured ∆…”

Section: C23 Calibration Of Isotopic Composition Of In-house Standasupporting

confidence: 71%

“…These samples were contained in IsoTubes (Isotech Laboratories, Illinois, USA) at pressures of~3 bar. We subsampled aliquots of these gases through a septum adapter fitting (available from Isotech) using a 25 ml gastight syringe (SGE Analytical Science), and introduced the aliquots into our sample preparation system as described above.Data shown in this thesis for δ 13 C, δD, and ∆ 13 CH 3 D assume that reference gas AL1 has the isotopic composition −34.5‰, −147.7‰, and +2.41 ± 0.07‰ (95% CI) respectively, consistent with Wang et al (2015) and with the values we provided to the UCLA group (Young et al, 2016). The D term corrects the observation that measured ∆ 13 CH3D values are lower than their true values when δD of the sample is lower than that of the reference gas (and vice versa).…”

supporting

confidence: 73%

“…These include John Eiler's lab at Caltech (Stolper et al, 2014b), Shuhei Ono's lab at MIT , and Ed Young's lab at UCLA (Young et al, 2016). For those interested in the race towards measuring intact methane isotopologues, readers are referred to Jones (2012).…”

Section: Preview Of Thesis Contentmentioning

confidence: 99%

“…Measurements of 13 C/ 12 C and D/H ratios in environmental methane samples can be used to assess whether they have experienced partial oxidation (Hornibrook et al, 1997;Chanton et al, 2005). Recently, methods were developed to determine the abundance of multiply-substituted "clumped" isotopologues (e.g., 13 CH 3 D) in methane samples to sub-permille precision Stolper et al, 2014b;Young et al, 2016). Measurements of the abundance of multiply-substituted isotopologues are of geochemical interest because of their potential for use as an isotopic geothermometer that can be accessed via analyses of a single compound (Wang et al, 2004;Eiler, 2007).…”

Section: Introductionmentioning

confidence: 99%

“…5.1) that shows several insights into the origin and fate of the methane stable isotopologues in the environment. As of the time of writing, methane clumped isotoplogue data have appeared in at least a dozen articles Stolper et al, 2014a;Stolper et al, 2014b;Inagaki et al, 2015;Stolper et al, 2015;Wang et al, 2015;Douglas et al, 2016;Lopes et al, 2016;Wang et al, 2016;Young et al, 2016;Whitehill et al, 2017;Young et al, 2017). The ∆ 13 CH 3 D data were shown to be independent of and complementary to δ 13 C and δD.…”

mentioning

confidence: 98%

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The geochemistry of methane isotopologues

Wang¹

2017

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This thesis documents the origin, distribution, and fate of methane and several of its isotopic forms on Earth. Using observational, experimental, and theoretical approaches, I illustrate how the relative abundances of 12 CH 4 , 13 CH 4 , 12 CH 3 D, and 13 CH 3 D record the formation, transport, and breakdown of methane in selected settings.Chapter 2 reports precise determinations of 13 CH 3 D, a "clumped" isotopologue of methane, in samples collected from various settings representing many of the major sources and reservoirs of methane on Earth. The results show that the information encoded by the abundance of 13 CH 3 D enables differentiation of methane generated by microbial, thermogenic, and abiogenic processes. A strong correlation between clumped-and hydrogen-isotope signatures in microbial methane is identified and quantitatively linked to the availability of H 2 and the reversibility of microbially-mediated methanogenesis in the environment. Determination of 13 CH 3 D in combination with hydrogen-isotope ratios of methane and water provides a sensitive indicator of the extent of C-H bond equilibration, enables fingerprinting of methane-generating mechanisms, and in some cases, supplies direct constraints for locating the waters from which migrated gases were sourced. Chapter 3 applies this concept to constrain the origin of methane in hydrothermal fluids from sediment-poor vent fields hosted in mafic and ultramafic rocks on slow-and ultraslow-spreading mid-ocean ridges. The data support a hypogene model whereby methane forms abiotically within plutonic rocks of the oceanic crust at temperatures above ca. 300• C during respeciation of magmatic volatiles, and is subsequently extracted during active, convective hydrothermal circulation. Chapter 4 presents the results of culture experiments in which methane is oxidized in the presence of O 2 by the bacterium Methylococcus capsulatus strain Bath. The results show that the clumped isotopologue abundances of partially-oxidized methane can be predicted from knowledge of 13 C/ 12 C and D/H isotope fractionation factors alone.: Shuhei Ono, Ph.D. Acknowledgments I fear that this section will not do justice to the people I have not the space to thank individually. Alas, here goes. To those whose names are not specifically listed here, thank you too. I wish first to thank Shuhei Ono. The work this thesis represents could not have happened without his bold vision and the license to explore and question that working in his lab afforded. His unbridled optimism, breadth of scientific curiosity, personal integrity, and accessibility to his personnel are traits I one day hope to emulate. I thank him for his nonjudgmental yet appropriately measured support of many of my ideas-even those that led nowhere-, for believing in me even when I found it difficult to do so myself, and for teaching me to change pump oil, build vacuum lines, and drink Icelandic vodka.I also wish to thank my thesis committee members Jeff Seewald, Roger Summons, and John Pohlman, for their in...

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Section: C23 Calibration Of Isotopic Composition Of In-house Standasupporting

confidence: 71%

supporting

confidence: 73%

Section: Preview Of Thesis Contentmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 98%

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The geochemistry of methane isotopologues

Wang¹

2017

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A model for ¹²CH₂D₂ and ¹³CH₃D as complementary tracers for the budget of atmospheric CH₄

Haghnegahdar

Schauble

Young

2017

Global Biogeochemical Cycles

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We present a theoretical model to investigate the potential of 13CH3D and 12CH2D2, the doubly substituted mass‐18 isotopologues of methane, as tools for tracking atmospheric methane sources and sinks. We use electronic structure methods to estimate kinetic isotope fractionations associated with the major sink reactions of methane in air (reactions with OH and Cl radicals) and combine literature data with reconnaissance measurements of the relative abundances of 13CH3D and 12CH2D2 to estimate the compositions of the largest atmospheric sources. This model atmospheric budget is investigated with a simplified box model in which we explore both steady state and dynamical (nonsteady state) conditions triggered by changes in emission or sink fluxes. The steady state model predicts that sink reactions will generate a marked (>100‰) clumped isotope excess in atmospheric Δ12CH2D2 relative to the net source composition. 12CH2D2 measurements may thus be useful for tracing both atmospheric source and sink fluxes. The effect of sinks on Δ13CH3D is much less pronounced, indicating that 13CH3D in air will give a more focused picture of the source composition.

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Geochemical, biological and clumped isotopologue evidence for substantial microbial methane production under carbon limitation in serpentinites of the Samail Ophiolite, Oman

Nothaft

Templeton

Rhim

et al. 2020

Preprint

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A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases

Cited by 81 publications

References 19 publications

The geochemistry of methane isotopologues

The geochemistry of methane isotopologues

A model for ¹²CH₂D₂ and ¹³CH₃D as complementary tracers for the budget of atmospheric CH₄

Geochemical, biological and clumped isotopologue evidence for substantial microbial methane production under carbon limitation in serpentinites of the Samail Ophiolite, Oman

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A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases

Cited by 81 publications

References 19 publications

The geochemistry of methane isotopologues

The geochemistry of methane isotopologues

A model for 12CH2D2 and 13CH3D as complementary tracers for the budget of atmospheric CH4

Geochemical, biological and clumped isotopologue evidence for substantial microbial methane production under carbon limitation in serpentinites of the Samail Ophiolite, Oman

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Resources

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A model for ¹²CH₂D₂ and ¹³CH₃D as complementary tracers for the budget of atmospheric CH₄