Graph from the paper.
Carbon monoxide clumped isotope values (expressed as Δ 31) versus CO concentrations from lower tropospheric atmosphere samples collected at Stony Brook, NY between 2019 and 2022. The solid line is a Rayleigh distillation curve using the kinetic isotope (KIE) effect predicted by combining the previously measured KIEs for 13CO and 18CO. Variations in the positive anomaly in Δ31 can reflect varying degrees of reaction of CO with OH in the background air and/or mixing of this reacted CO with more locally emitted combustion CO that has a Δ31 of zero (dashed line). Credit: Henkes et al. [2024], Figure 3
Editors’ Highlights are summaries of recent papers by AGU’s journal editors.
Source: AGU Advances

The main sources of atmospheric carbon monoxide (CO) are incomplete combustion of organic or fossil fuels and the oxidation of atmospheric methane, while the main sink is oxidation to carbon dioxide (CO2) by reaction with hydroxyl radicals (OH). By influencing the concentration of OH, CO impacts greenhouse gases like methane and tropospheric ozone. Thus, understanding how sources and OH reaction rates control CO concentrations is fundamental for atmospheric chemistry.

To date, investigations using stable isotopes have been limited to singly substituted (13C, 18O) constituents. Henkes et al. [2024] develop and test a clever method to measure the ‘clumped’ isotope species 13C18O (mass 31). They report the first atmospheric measurements using samples collected near New York during 2019-2022. These indicate the kinetic isotope effect (KIE) for 13C18O is predictable from separately measured KIE for reaction of OH with 13C16O and 12C18O. The atmospheric lifetime of CO averages a few months – thus regions far from emissions sources would be expected to have low CO concentrations and Δ31 values reflecting the degree of chemical ‘aging’.  Regions with high fossil fuel emissions such as the Northeastern United States reflect both mixing of this aged ‘background’ with local CO sources having Δ31 of about 0.  

To better isolate mixing from OH reaction effects, the authors propose new measurements in the southern hemisphere.  Importantly, the clumped isotope approaches developed here for CO can and likely will be applied to study other atmospheric gases.    

Citation: Henkes, G. A., Place, P. F., & Mak, J. E. (2024). Large, negative atmospheric carbon monoxide clumped isotope values result from kinetic isotope fractionation, tracing OH• reactivity. AGU Advances, 5, e2023AV000922. https://doi.org/10.1029/2023AV000922

—Susan Trumbore, Editor-in-Chief, AGU Advances

Text © 2024. The authors. CC BY-NC-ND 3.0
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