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Methane Removal
Grantee Project

Ab Initio Calculation of Kinetic Isotope Effects (Kie) for Reaction of Ch4 with Oh, Cl, And O(¹d)– Improving the Constraints Needed to Monitor Atmospheric Ch4 Sinks

Research to better constrain the fingerprints of different atmospheric methane sinks

James Farquhar

September 2024

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August 2026

Project Summary

By providing full internally-consistent calibration of atmospheric CH4 isotopologue sinks, this work will lay the foundation for process-model inversions of global data that better constrain source apportionment and that can be used to monitor future engineering solutions for methane removal. Many constraints needed to do this do not yet exist, and of those that do exist, some add considerable uncertainty to the models (as described above). For deliverables, this work will reduce this part of model uncertainty, if successful from >10% to the % level, and add isotopologue constraints that reduce the number of free variables and allow for more complete representation of the atmospheric CH4 cycle and apportioning its sources. Furthermore, ab initio calibrations of kinetic isotope effect (KIE) allow constraints on related atmospheric CH4 isotopologues (e.g., 14CH4 and its oxidation products). This work addresses improved representations of atmospheric CH4 sink mechanisms into relevant Models.

Team

James Farquhar is Distinguished University Professor and Chair of the Department of Geology and a member of the Earth System Science Interdisciplinary Center (ESSIC) at the University of Maryland. Dr. Farquhar’s research is in the process of transitioning to focus on isotopic techniques fingerprinting and tracing atmospheric methane methane sources, both natural and anthropogenic, primarily in the mid-Atlantic states region – wetland emissions, emissions from combustion, emissions from human and agricultural sources. This is a new direction and draws on the recently acquired UMD Panorama to measure isotopologues (isotopic variants) of methane molecules with 0, 1, and 2 heavy isotope substitutions.

Dr. Farquhar’s past research focused on sulfur isotope geochemistry in a variety of terrestrial and extraterrestrial systems, spanning the modern to the ancient and extends from the atmosphere to the oceans and solid Earth. Farquhar and coworkers are best known for the discovery and interpretation of mass independent sulfur isotope signatures in samples from the early Earth that trace the evolution of oxygen and chemistry in the early atmosphere; in samples from Mars that tell of different conditions and reflect different reactions; and that provide tracers that track sulfur from surface reservoirs into other planetary reservoirs. Farquhar and coworkers have also used sulfur isotopes to trace metabolic and biogeochemical transformations for inorganic and organic sulfur compounds using laboratory experiments and ab initio approaches.

Mojhgan Haghnegahdar is a NSF Postdoctoral Fellow in the Department of Geology at the University of Maryland College Park and SERC. She received a B.S in chemistry from Shiraz University, an M.S in chemistry from California State University Northridge (CSUN), and an M.S in geochemistry from UCLA and earned her Ph.D. in geochemistry from UCLA. Broadly, her research projects focus on isotope geochemistry and its applications in biogeochemistry, atmospheric chemistry, along with economical geochemistry. For her postdoctoral projects as President's Postdoctoral Fellow at UMD and later NSF Postdoctoral Fellow, she is continuing her research path in isotope biogeochemistry of methane.

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