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Atmospheric carbon monoxide (CO) is a key player in global atmospheric chemistry and a regulated pollutant in urban areas. Oxidation of volatile organic compounds (VOCs) is an important component of the global CO budget and has also been hypothesized to contribute substantially to the summertime urban CO budget. In principle, stable isotopic analysis of CO could constrain the magnitude of this source. However, the isotopic signature of VOC-produced CO has not been well quantified, especially for the oxygen isotopes. We performed measurements of CO stable isotopes on air samples from two sites around Indianapolis, US, over three summers to investigate the isotopic signature of VOC-produced CO. One of the sites is located upwind of the city, allowing us to quantitatively remove the background air signal and isolate the urban CO enhancements. as well as the isotopic signature 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 the VOC-derived component of the CO enhancement. Combining these measurements and analyses, we are able to determine the carbon and oxygen isotopic signatures of CO derived from VOC oxidation as -32.8‰±0.5‰ and 3.6‰±1.2‰ , respectively. Additionally, we analyzed CO stable isotopes for 1 year at Beech Island, South Carolina, US, a site thought to have large VOC-derived contributions to the summertime CO budget. The Beech Island results are consistent with isotopic signatures of VOC-derived CO determined from the Indianapolis data. This study represents the first direct determination of the isotopic signatures of VOC-derived CO and will allow for improved use of isotopes in constraining the global and regional CO budgets. [ABSTRACT FROM AUTHOR]

Atmospheric carbon monoxide (CO) is a regulated pollutant in urban centers. Oxidation of volatile organic compounds (VOCs) has been hypothesized to contribute substantially to the summertime urban CO budget. We performed measurements of CO stable isotopes on air samples from three sites in and around Indianapolis, USA over three summers to investigate the VOC contribution to urban CO. One of the sites is located upwind of the city, allowing us to quantitatively remove the background air signal and isolate the urban CO enhancements. The distinct isotopic signatures of CO produced from fossil fuel combustion and VOC oxidation allow us to separate contributions from these two sources. Our results provide the strongest empirical evidence to date of large contributions from VOC oxidation to the urban summertime CO source and show that this contribution varies in time and location between 0 and 58 %. We attribute the remainder of the Indianapolis summertime CO budget to fossil fuel combustion. We assess the reactivities of different VOCs and determine that biogenic sources are likely responsible for the majority of CO produced by VOC oxidation reactions within Indianapolis. [ABSTRACT FROM AUTHOR]