Photolysis of pyruvic acid in ice: Possible relevance to CO and CO2 ice core record anomalies

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Abstract

[1] The abnormal spikes detected in some CO and CO2 polar ice core records indicate persistent chemical activity in glacial ice. Since CO and CO2 spikes are correlated, and their amplitudes scale with reported CO/CO2 yields for the photolysis of dissolved natural organic matter, a common photochemical source is implicated. Given that sufficient actinic radiation is constantly generated throughout ice by cosmic muons (Colussi and Hoffmann, 2003), it remains to be shown that the photolyses of typical organic contaminants proceed by similar mechanisms in water and ice. Here we report that the photodecarboxylation of pyruvic acid (PA, an ubiquitous ice contaminant) indeed leads to the same products nearly as efficiently in both media. CO2 is promptly released from frozen PA/H2O films upon illumination and continues to evolve after photolysis. By analogy with our studies in water (Guzmán et al., 2006b), we infer that 3PA* reacts with PA in ice producing CH3C(O)C(O)O· and (CH3equation image (OH)C(O)OH) radicals. The barrierless decarboxylation, CH3C(O)C(O)O· → CH3C(O)· + CO2, accounts for prompt CO2 emissions down to ∼140 K. Bimolecular radical reactions subsequently ensue in fluid molecular environments, both in water and ice, leading to metastable intermediates that decarboxylate immediately in water, but protractedly in ice. The overall quantum yield of CO2 production in the λ ~313 nm photolysis of PA in ice at 250 K is ∼60% of that in water at 293 K. The in situ photolysis of natural organic matter is, therefore, a plausible explanation of CO and CO2 ice core record anomalies.

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