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. Atmospheric carbon monoxide (CO) is a key player in global atmosphericchemistry and a regulated pollutant in urban areas. Oxidation of volatileorganic compounds (VOCs) is an important component of the global CO budgetand has also been hypothesized to contribute substantially to the summertimeurban CO budget. In principle, stable isotopic analysis of CO couldconstrain the magnitude of this source. However, the isotopic signature ofVOC-produced CO has not been well quantified, especially for the oxygenisotopes. We performed measurements of CO stable isotopes on air samplesfrom two sites around Indianapolis, US, over three summers to investigatethe isotopic signature of VOC-produced CO. One of the sites is locatedupwind of the city, allowing us to quantitatively remove the background airsignal and isolate the urban CO enhancements. as well as the isotopicsignature of these enhancements. In addition, we use measurements of Δ14CO2 in combination with the CO:CO2 emission ratio from fossil fuels to constrain the fossil-fuel-derived CO and thereby isolate theVOC-derived component of the CO enhancement. Combining these measurementsand analyses, we are able to determine the carbon and oxygen isotopicsignatures of CO derived from VOC oxidation as - 32.8 ‰ ± 0.5 ‰ and 3.6 ‰±1.2 ‰ , respectively. Additionally, we analyzed CO stableisotopes for 1 year at Beech Island, South Carolina, US, a site thoughtto have large VOC-derived contributions to the summertime CO budget. TheBeech Island results are consistent with isotopic signatures of VOC-derivedCO determined from the Indianapolis data. This study represents the firstdirect determination of the isotopic signatures of VOC-derived CO and willallow for improved use of isotopes in constraining the global and regionalCO budgets.

atmospheric chemistry and physics

An improved estimate for the &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;13&amp;lt;/sup&amp;gt;C and &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O signatures of carbon monoxide produced from atmospheric oxidation of volatile organic compounds