Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases

Wang, Zhengrong; Schauble, E. A.; Eiler, John M.

doi:10.1016/j.gca.2004.05.039

Cited by 304 publications

(451 citation statements)

References 37 publications

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“…11 the actual value of ∆47,T=∞, not reported permil notation, is used). This approximation ignores the contribution of other isotopologues at cardinal mass 47, which is reasonable for typical carbonate compositions given the analytical uncertainty on ∆47 values (Wang et al 2004). With a few simplifications described in Stolper and Eiler (2015), the derivative of reaction progress at a given time, t, can be defined as: …”

Section: A Dolomite Exchange-diffusion Reordering Modelmentioning

confidence: 99%

“…where R 47 is the measured abundance ratio of CO2 isotopologues of mass 47 Da (primarily 13 C 18 O 16 O) to the unsubstituted species ( 12 C 16 O2 at 44 Da), and R 47* is the expected ratio for a stochastic distribution of these isotopologues (Wang et al, 2004). ∆47 values of lab-grown dolomites are dependent on precipitation temperature, and thus ∆47 values in natural materials can be used to estimate the temperature of (re)crystallization (Bonifacie et al, 2017;Ghosh et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

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Experimental calibration of clumped isotope reordering in dolomite

Lloyd

Ryb

Eiler

2018

Geochimica et Cosmochimica Acta

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Section: A Dolomite Exchange-diffusion Reordering Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Experimental calibration of clumped isotope reordering in dolomite

Lloyd

Ryb

Eiler

2018

Geochimica et Cosmochimica Acta

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“…The technique is based on the temperature dependence of the abundance, relative to a stochastic distribution, of carbonate ion groups that contain both a (Ghosh et al 2006a;Eiler 2007). A thermodynamic driving force that increases with decreasing temperature makes it more favorable for 13 C and 18 O to ''clump'' into bonds with each other instead of being distributed randomly throughout the crystal lattice (Wang et al 2004;Schauble et al 2006). The 13 C-18 O-bond enrichment can be determined by measuring the d 18 O, d 13 C, and abundance of mass-47 species in CO 2 produced by phosphoric acid digestion of carbonate using gas-source isotope ratio mass spectrometry Affek and Eiler 2006;Huntington et al 2009 18 O of water data for ancient Earth-surface deposits to constrain paleoclimate and landscape evolution (e.g., Ghosh et al 2006b;Affek et al 2008;Huntington et al 2010;Passey et al 2010), but recent studies of altered fossil shells, carbonatites, and marbles suggest that the thermometer might also be applied to quantify temperatures of diagenesis.…”

Section: Introductionmentioning

confidence: 99%

Use of Clumped-Isotope Thermometry To Constrain the Crystallization Temperature of Diagenetic Calcite

Huntington¹,

Budd²,

Wernicke³

et al. 2011

Journal of Sedimentary Research

129

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We describe an approach to estimating the crystallization temperatures of diagenetic calcites using clumped-isotope thermometry, a paleothermometer based on the 13 C- 18O-bond enrichment in carbonates. Application of this thermometer to calcified gastropod shells and calcite cements in an early Eocene limestone from the Colorado Plateau reveals a record of calcite precipitation and replacement at temperatures varying from 14 to 123uC. The early Eocene host sediments were never deeply buried, but they experienced a significant thermal pulse associated with the emplacement of a late Miocene basalt flow. The combination of independent constraints on thermal history with clumped-isotope thermometry, petrographic (including cathodoluminescence) observations, and oxygen isotopic data provides an improved basis for estimation of the temperature and timing of diagenetic events and fluid sources. The petrography and calcite d 18O values, taken alone, suggest that the aragonite-tocalcite transformation of gastropod shell material occurred simultaneously with early formation of cements and lithification of the matrix in the same sample. However, addition of clumped-isotope thermometry demonstrates that this phase transformation of shell material occurred at temperatures of 94-123uC in a highly rock-buffered microenvironment (i.e., with the isotopic composition of fluid buffered by coexisting carbonate), millions of years after lithification of the matrix and formation of initial low-temperature (14-19uC) calcite cements within shell body cavities. Clumped-isotope temperatures in excess of reasonable Earth-surface conditions recorded by later-formed cements demand that cement growth occurred in association with the lava emplacement. Our results illustrate the potential for clumped-isotope thermometry to constrain conditions of diagenesis and guide interpretations that would not be possible on the basis of conventional stable-isotopic and petrographic data alone, and demonstrate how petrographic characterization of clumped-isotope thermometry samples can benefit paleoclimate studies.

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“…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). Furthermore, clumped isotopologue data provide another dimension for probing kinetic and equilibrium isotope effects and for constraining isotope exchange processes in natural settings (e.g., Eiler and Schauble, 2004;Yeung et al, 2012;Yeung, 2016 has an equilibrium constant K that varies between~1.007 at 0°C to 1.000 at temperatures approaching infinity (at which isotopes are randomly distributed amongst all possible isotopologues, i.e., the stochastic distribution) (see Wang et al, 2015, and references therein for details regarding calculations from which K is obtained).…”

Section: Introductionmentioning

confidence: 99%

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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Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases

Cited by 304 publications

References 37 publications

Experimental calibration of clumped isotope reordering in dolomite

Experimental calibration of clumped isotope reordering in dolomite

Use of Clumped-Isotope Thermometry To Constrain the Crystallization Temperature of Diagenetic Calcite

The geochemistry of methane isotopologues

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