Stable isotope measurements confirm volatile organic compound oxidation as a major urban summertime source of carbon monoxide in Indianapolis, USA

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.