Abstract

AbstractWe measured carbonyl sulfide (COS) in air extracted from ice core samples from the West Antarctic Ice Sheet (WAIS) Divide, Antarctica, with the deepest sample dated to 54,300 years before present. These are the first ice core COS measurements spanning the Last Glacial Maximum (LGM), the last glacial/interglacial transition, and the early Holocene. The WAIS Divide measurements from the LGM and the last transition are the first COS measurements in air extracted from full clathrate (bubble‐free) ice. This study also includes new COS measurements from Taylor Dome, Antarctica, including some in bubbly glacial ice that are concurrent with the WAIS Divide data from clathrate glacial ice. COS hydrolyzes in ice core air bubbles, and the recovery of an atmospheric record requires correcting for this loss. The data presented here suggest that the in situ hydrolysis of COS is significantly slower in clathrate ice than in bubbly ice. The clathrate ice measurements are corrected for the hydrolysis loss during the time spent as bubbly ice only. The corrected WAIS Divide record indicates that atmospheric COS was 250–300 parts per trillion (ppt) during the LGM and declined by 80–100 ppt during the last glacial/interglacial transition to a minimum of 160–210 ppt at the beginning of the Holocene. This decline was likely caused by an increase in the gross primary productivity of terrestrial plants, with a possible contribution from a reduction in ocean sources. COS levels were above 300 ppt in the late Holocene, indicating that large changes in the COS biogeochemical cycle occurred during the Holocene.

Highlights

  • Carbonyl sulfide (COS) is the most abundant sulfur gas in the troposphere

  • This study presents the first ice core carbonyl sulfide (COS) measurements from the last glacial period and the last glacial/interglacial transition, including the first measurements of COS in air extracted from full clathrate ice

  • The results presented here suggest that the loss processes occurring in bubbly ice must either stop or occur at considerably slower rates in clathrate ice

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Summary

Introduction

The current global tropospheric mean is 480–490 parts per trillion (ppt), and the atmospheric lifetime is 2–3 years [Montzka et al, 2007; Suntharalingam et al, 2008]. COS is taken up by plant leaves and irreversibly hydrolyzed, linking atmospheric COS levels with terrestrial gross primary productivity [Montzka et al, 2007; Campbell et al, 2008]. This process accounts for 60–70% of the total COS removal from the atmosphere. COS is taken up by soils (20–30%) and destroyed by direct photolysis and reaction with OH (

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