High resolution measurements of carbon monoxide along a late Holocene Greenland ice core: evidence for in-situ production

Abstract

Abstract. We present high-resolution measurements of carbon monoxide (CO) concentrations from continuous analysis of a shallow ice core from the North Greenland Eemian Ice Drilling project (NEEM-2011-S1). An Optical Feedback – Cavity Enhanced Absorption Spectrometer (OF-CEAS) was coupled to a continuous melter system during a 4-week laboratory-based measurement campaign. This analytical setup generates highly stable measurements of CO concentrations with an external precision of 7.8 ppbv (1 sigma) based on a comparison of replicate cores. The NEEM-2011-S1 CO record spans 1800 yr and exhibits highly variable concentrations at the scale of annual layers, ranging from 75 to 1327 ppbv. The most recent section of this record (i.e. since 1700 AD) agrees with existing discrete CO measurements from the Eurocore ice core and the deep NEEM firn. However, it is difficult to interpret in terms of atmospheric CO variation due to high frequency, high amplitude spikes in the data. 68% of the elevated CO spikes are observed in ice layers enriched with pyrogenic aerosols. Such aerosols, originating from boreal biomass burning emissions, contain organic compounds, which can be oxidized or photodissociated to produce CO in-situ. We suggest that elevated CO concentration features could present a new integrative proxy for past biomass burning history. Furthermore, the NEEM-2011-S1 record reveals an increase in baseline CO level prior to 1700 AD (129 m depth), with the concentration remaining high even for ice layers depleted in dissolved organic carbon (DOC). Overall, the processes driving in-situ production of CO within the NEEM ice are complex and may involve multiple chemical pathways.