Changes in atmospheric carbonyl sulfide over the last 54,000years inferred from measurements in Antarctic ice cores

We 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 54,300years 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 250-300parts per trillion (ppt) during the LGM and declined by 80-100ppt during the last glacial/interglacial transition to a minimum of 160-210ppt 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 300ppt in the late Holocene, indicating that large changes in the COS biogeochemical cycle occurred during the Holocene.