18O13C16O in Earth's atmosphere

The chemistry and budgets of atmospheric gases are constrained by their bulk stable isotope compositions (e.g., delta(13)C values), which are based on mixing ratios of isotopologues containing one rare isotope (e.g., (OCO)-O-16-C-13-O-16). Atmospheric gases also have isotopologues containing two or more rare isotopes (e.g., (OCO)-O-18-C-13-O-16). These species have unique physical and chemical properties and could help constrain origins of atmospheric gases and expand the scope of stable isotope geochemistry generally. We present the first measurements of the abundance of (OCO)-O-18-C-13-O-16 from natural and synthetic sources, discuss the factors influencing its natural distribution and, as an example of its applied use, demonstrate how its abundance constrains the sources of CO2 in the Los Angeles basin. The concentration of (OCO)-O-18-C-13-O-16 in air can be explained as a combination of ca. 1parts per thousand enrichment (relative to the abundance expected if C and O isotopes are randomly distributed among all possible isotopologues) due to enhanced thermodynamic stability of this isotopologue during isotopic exchange with leaf and surface waters, ca. 0.1parts per thousand depletion due to diffusion through leaf stomata, and subtle (ca. 0.05parts per thousand) dilution by (OCO)-O-18-C-13-O-16-poor anthropogenic CO2. Some air samples are slightly (ca. 0.05parts per thousand) lower in (OCO)-O-18-C-13-O-16 c than can be explained by these factors alone. Our results suggest that (OCO)-O-18-C-13-O-16 abundances should vary by up to ca. 0.2parts per thousand with latitude and season, and might have measurable sensitivities to stomatal conductances of land plants. We suggest the greatest use of Delta(47) measurements will be to "leverage" interpretation of the delta(18)O of atmospheric CO2. Copyright (C) 2004 Elsevier Ltd.