Current stratospheric models have difficulties in fully explaining the observed midlatitude ozone depletion in the lowermost stratosphere, particularly near the tropopause. Such models assume that only long-lived source gases provide significant contributions to the stratospheric halogen budget, while all the short-lived compounds are removed in the troposphere, the products being rained out. Here we show this assumption to be flawed. Using bromine species as an example, we show that in the lowermost stratosphere, where the observed midlatitude ozone trend maximizes, bromoform (CHBr3) alone likely contributes more inorganic bromine than all the conventional long-lived sources (halons and methyl bromide) combined. Copyright 1999 by the American Geophysical Union.

Measurements and models of the spatiotemporal variability of surface N 2O mixing ratios and isotopic compositions are increasingly used to constrain the global N2O budget. However, large variability observed on the small spatial scales of soil chambers and shipboard sampling, which appears to be very sensitive to local environmental conditions, has made extrapolation to the global scale difficult. In this study, we present measurements of the isotopic composition of N2O (δ ¹⁵N^bulk, δ¹⁵N, δ¹⁵N, and δ¹⁸O) from whole-air samples collected at altitudes of 0.5 to 19km by the NASA DC-8 and WB-57 aircraft during the Costa Rica-Aura Validation Experiment (CR-AVE) and the Tropical Composition, Cloud and Climate Coupling Experiment (TC4) campaigns in January-February 2006 and July-August 2007, respectively. The vertical profiles of isotopic composition showed predictable, repeating patterns consistent with the influence of a surface source at lower altitudes and the influence of stratospheric photochemistry in the lower stratosphere. Their correlations with marine tracers at lower altitudes are consistent with a predominantly oceanic source, although a soil source cannot be ruled out. Measurements in a combustion plume revealed a strong depletion in ¹⁵N at the central nitrogen atom (i.e., low δ¹⁵N values), providing new information on N2O isotopic compositions from combustion. This new data set demonstrates that a coherent picture of the isotopic composition of tropospheric N2O is possible at currently attainable precisions and that its variations from 0.5 km to the lower stratosphere are a useful tool in investigating the sources and distributions of this important greenhouse gas. Copyright 2010 by the American Geophysical Union.

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.