Constraints on emissions of carbon monoxide, methane, and a suite of hydrocarbons in the Colorado Front Range using observations of ¹⁴CO₂

Abstract

Abstract. Atmospheric radiocarbon (14CO) represents an important observational constraint on emissions of fossil-fuel derived carbon into the atmosphere due to the absence of 14CO in fossil fuel reservoirs. The high sensitivity and precision that accelerator mass spectrometry (AMS) affords in atmospheric 14CO analysis has greatly increased the potential for using such measurements to evaluate bottom-up emissions inventories of fossil fuel CO2 (CO2ff), as well as those for other co-emitted species. Here we use observations of 14CO2 and a series of hydrocarbons and combustion tracers from discrete air samples collected between June 2009 and September 2010 at the National Oceanic and Atmospheric Administration Boulder Atmospheric Observatory (BAO; Lat: 40.050° N, Lon: 105.004° W) to derive emission ratios of each species to CO2ff. From these emission ratios, we estimate emissions of these species by using the Vulcan CO2ff high resolution data product as a reference. The species considered in this analysis are carbon monoxide (CO), methane (CH4), acetylene (C2H2), benzene (C6H6), and C3–C5 alkanes. Comparisons of top-down emissions estimates are made to existing inventories of these species for Denver and adjacent counties, as well as to previous efforts to estimate emissions from atmospheric observations over the same area. We find that CO is overestimated in the 2008 National Emissions Inventory (NEI, 2008) by a factor of ~2. A close evaluation of the inventory suggests that the ratio of CO emitted per unit fuel burned from on-road gasoline vehicles is likely over-estimated by a factor of 2.5. The results also suggest that while the oil and gas sector is the largest contributor to the CH4 signal in air arriving from the north and east, it is very likely that other sources, including agricultural sources, contribute to this signal and must be accounted for when attributing these signals to oil and gas industry activity from a top-down perspective. Our results are consistent with ~60% of the total CH4 emissions from regions to the north and east of the BAO tower stemming from the oil and gas industry, equating to ~70 Gg yr−1 or ~1.7% of total natural gas production in the region.