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Abstract The history of tropospheric O3, an important atmospheric oxidant, is poorly constrained because of uncertainties in its historical budget and a dearth of independent records. Here, we estimate the mean tropospheric O3burden during the Last Interglacial period (LIG; 115 to 130 thousand years ago) using a record of the clumped isotopic composition of O2(i.e., Δ36values) preserved in Antarctic ice. The measured LIG Δ36value is 0.03 ± 0.02‰ (95% CI) higher than the late pre‐industrial Holocene (PI; 1,590–1,850 CE) value and corresponds to a modeled 9% reduction in LIG tropospheric O3burden (95% CI: 3%–15%), caused in part by a substantial reduction in biomass burning emissions during the LIG relative to the PI. These results are consistent with the hypothesis that late‐Pleistocene megafaunal extinctions caused woody and grassy fuels to accumulate on land, leading to enhanced biomass burning in the preindustrial Holocene.
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Effects of Ozone Isotopologue Formation on the Clumped‐Isotope Composition of Atmospheric O 2
Abstract Tropospheric18O18O is an emerging proxy for past tropospheric ozone and free‐tropospheric temperatures. The basis of these applications is the idea that isotope‐exchange reactions in the atmosphere drive18O18O abundances toward isotopic equilibrium. However, previous work used an offline box‐model framework to explain the18O18O budget, approximating the interplay of atmospheric chemistry and transport. This approach, while convenient, has poorly characterized uncertainties. To investigate these uncertainties, and to broaden the applicability of the18O18O proxy, we developed a scheme to simulate atmospheric18O18O abundances (quantified as ∆36values) online within the GEOS‐Chem chemical transport model. These results are compared to both new and previously published atmospheric observations from the surface to 33 km. Simulations using a simplified O2isotopic equilibration scheme within GEOS‐Chem show quantitative agreement with measurements only in the middle stratosphere; modeled ∆36values are too high elsewhere. Investigations using a comprehensive model of the O‐O2‐O3isotopic photochemical system and proof‐of‐principle experiments suggest that the simple equilibration scheme omits an important pressure dependence to ∆36values: the anomalously efficient titration of18O18O to form ozone. Incorporating these effects into the online ∆36calculation scheme in GEOS‐Chem yields quantitative agreement for all available observations. While this previously unidentified bias affects the atmospheric budget of18O18O in O2, the modeled change in the mean tropospheric ∆36value since 1850 CE is only slightly altered; it is still quantitatively consistent with the ice‐core ∆36record, implying that the tropospheric ozone burden increased less than 40% over the twentieth century.
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- PAR ID:
- 10375103
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Atmospheres
- Volume:
- 126
- Issue:
- 14
- ISSN:
- 2169-897X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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