Atmospheric history of carbon monoxide since preindustrial times reconstructed from multiple Greenland ice cores

Abstract

<p>Carbon monoxide (CO) is a regulated pollutant and one of the key components determining the oxidizing capacity of the atmosphere. Obtaining a reliable record of atmospheric CO mixing ratios since pre-industrial times is necessary to evaluate climate-chemistry models in conditions different from today. We present high-resolution measurements of CO mixing ratios from ice cores drilled at five different sites on the Greenland ice sheet which experience a range of snow accumulation rates, mean surface temperatures, and different chemical compositions. An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) was coupled to continuous melter systems and operated during four analytical campaigns conducted between 2013 and 2019. The CFA-based CO measurements exhibit excellent external precision (ranging 3.3 - 6.6 ppbv, 1σ), and achieve consistently low blanks (ranging from 4.1±1.2 to 12.6±4.4 ppbv). Good accuracy and absolute calibration of CFA-based CO records enable paleo-atmospheric interpretations. The five CO records all exhibit variability in CO mixing ratios that is too large and rapid to reflect past atmospheric mixing ratio changes. Complementary tests conducted on discrete ice samples demonstrate that such patterns are not related to the analytical process (i.e., production of CO from organics in the ice during melting), but very likely are related to in situ CO production within the ice before analyses. Evaluation of signal resolution and co-investigation of high-resolution records of CO and TOC show that past atmospheric CO concentration can be extracted from the records’ baselines at four sites with accumulation rates higher than 20 cm water equivalent per year (weq yr<sup>-1</sup>). However, such baselines should be taken as upper bounds of past atmospheric CO burden. CO records from four sites are combined to produce a multisite average ice core reconstruction of past atmospheric CO for the Northern Hemisphere high latitudes, covering the period from 1700 to 1957 CE. From 1700 to 1875 CE, this record reveals stable or slightly increasing values remaining in the 100-115 ppbv range. From 1875 to 1957 CE, the record indicates a monotonic increase from 114±4 ppbv to 147±6 ppbv. The ice-core multisite CO record exhibits an excellent overlap with the atmospheric CO record from Greenland firn air which span the 1950-2010 time period. The combined ice-core and firn air CO history, spanning 1700-2010 CE, largely exhibits patterns that are consistent with the recent anthropogenic and biomass burning CO emission inventories. This brand new time series will be compared with the most recent results from Earth System Models involved in the CMIP6-AerChemMIP multi-model exercise.</p>