Geoff Dutton

Evaluation of source gas lifetimes from stratospheric observations

Simultaneous in situ measurements of the long-lived trace species N2O, CH4, 12, CFC-113, CFC-11, CCl4, CH3CCl3, H-1211, and SF6 were made in the lower stratosphere and upper troposphere on board the NASA ER-2 high-altitude aircraft during the 1994 campaign Airborne Southern Hemisphere Ozone Experiment/ Measurements for Assessing the Effects of Stratospheric Aircraft. The observed extratropical tracer abundances exhibit compact mutual correlations that show little interhemispheric difference or seasonal variability except at higher altitudes in southern hemisphere spring. The environmental impact of the measured source gases depends, among other factors, on the rate at which they release ozone-depleting chemicals in the stratosphere, that is, on their stratospheric lifetimes. We calculate the mean age of the air from the SF6 measurements and show how stratospheric lifetimes of the other species may be derived semiempirically from their observed gradients with respect to mean age at the extratropical tropopause. We also derive independent stratospheric lifetimes using the CFC-11 lifetime and the slopes of the tracers correlations with CFC-11. In both cases, we correct for the influence of tropospheric growth on stratospheric tracer gradients using the observed mean age of the air, time series of observed tropospheric abundances, and model-derived estimates of the width of the stratospheric age spectrum. Lifetime results from the two methods are consistent with each other. Our best estimates for stratospheric lifetimes are 122±24 years for N2O, 93±18 years for CH4, 87±17 years for CFC-12, 100±32 years for CFC-113, 32±6 years for CCl4, 34±7 years for CH3CCl3, and 24±6 years for H-1211. Most of these estimates are significantly smaller than currently recommended lifetimes, which are based largely on photochemical model calculations. Because the derived stratospheric lifetimes are identical to atmospheric lifetimes for most of the species considered, the shorter lifetimes would imply a faster recovery of the ozone layer following the phaseout of industrial halocarbons than currently predicted.

Quantifying Transport Between the Tropical and Mid-Latitude Lower Stratosphere

Airborne in situ observations of molecules with a wide range of lifetimes (methane, nitrous oxide, reactive nitrogen, ozone, chlorinated halocarbons, and halon-1211), used in a tropical tracer model, show that mid-latitude air is entrained into the tropical lower stratosphere within about 13.5 months; transport is faster in the reverse direction. Because exchange with the tropics is slower than global photochemical models generally assume, ozone at mid-latitudes appears to be more sensitive to elevated levels of industrial chlorine than is currently predicted. Nevertheless, about 45 percent of air in the tropical ascent region at 21 kilometers is of mid-latitude origin, implying that emissions from supersonic aircraft could reach the middle stratosphere.

Mixing of polar vortex air into middle latitudes as revealed by tracer‐tracer scatterplots

The occurrence of mixing of polar vortex air with midlatitude air is investigated by examining the scatterplots of insitu measurements of long-lived tracers from the NASA ER-2 aircraft during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE, April, May 1993; northern hemisphere) and the Airborne Southern Hemisphere Ozone Experiment / Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA, March-October 1994; southern hemisphere) campaigns. The tracer-tracer scatterplots from SPADE form correlation curves which differ from those measured during previous aircraft campaigns (Airborne Antarctic Ozone Experiment (AAOE), Airborne Arctic Stratospheric Experiments I (AASE I) and II (AASE II)). It is argued that these anomalous linear correlation curves are mixing lines resulting from the recent mixing of polar vortex air into the middle latitude environment. Further support for this mixing scenario is provided by contour advection calculations and calculations with a simple one-dimensional strain-diffusion model. The scatterplots from the midwinter deployments of ASHOE/MAESA are consistent with those from previous midwinter measurements (i.e., no mixing lines), but the spring CO 2 :N 2 O scatterplots form altitude-dependent mixing lines which indicate that air from the vortex edge region (but not from the inner vortex) is mixing with midlatitude air during this period. These results suggest that at altitudes above about 16 km the mixing of polar vortex air into middle latitudes varies with season: in northern and southern midwinter this mixing rarely occurs, in southern spring mixing of vortex-edge air occurs, and after the vortex breakup mixing of inner vortex air occurs.

Airborne gas chromatograph for in situ measurements of long-lived species in the upper troposphere and lower stratosphere

A new instrument, the Airborne Chromatograph for Atmospheric Trace Species IV (ACATS-IV), for measuring long-lived species in the upper troposphere and lower stratosphere is described. Using an advanced approach to gas chromatography and electron capture detection, the instrument can detect low levels of CFC-11 (CCl 3 F), CFC-12 (CCl 2 F 2 ), CFC-113 (CCl 2 F-CClF 2 ), methyl chloroform (CH 3 CCl 3 ), carbon tetrachloride (CCl 4 ), nitrous oxide N 2 O), sulfur hexafluoride (SF 6 ), Halon-1211 (CBrClF 2 ), hydrogen (H 2 ), and methane (CH 4 ) acquired in ambient samples every 180 or 360 s. The instrument operates fully-automated onboard the NASA ER-2 high-altitude aircraft on flights lasting up to 8 hours or more in duration. Recent measurements include 24 successful flights covering a broad latitude range (70°S-61°N) during the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/ MAESA) campaign in 1994.

Distribution of halon‐1211 in the upper troposphere and lower stratosphere and the 1994 total bromine budget

We report here on the details of the first, in situ, real-time measurements of H-1211 (CBrClF2) and sulfur hexafluoride (SF6) mixing ratios in the stratosphere up to 20 km. Stratospheric air was analyzed for these gases and others with a new gas Chromatograph, flown aboard a National Aeronautics and Space Administration ER-2 aircraft as part of the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission conducted in 1994. The mixing ratio of SF6, with its nearly linear increase in the troposphere, was used to estimate the mean age of stratospheric air parcels along the ER-2 flight path. Measurements of H-1211 and mean age estimates were then combined with simultaneous measurements of CFC-11 (CCl3F), measurements of brominated compounds in stratospheric whole air samples, and records of tropospheric organic bromine mixing ratios to calculate the dry mixing ratio of total bromine in the lower stratosphere and its partitioning between organic and inorganic forms. We estimate that the organic bromine-containing species were almost completely photolyzed to inorganic species in the oldest air parcels sampled. Our results for inorganic bromine are consistent with those obtained from a photochemical, steady state model for stratospheric air parcels with CFC-11 mixing ratios greater than 150 ppt. For stratospheric air parcels with CFC-11 mixing ratios less than 50 ppt (mean age ≥5 years) we calculate inorganic bromine mixing ratios that are approximately 20% less than the photochemical, steady state model. There is a 20% reduction in calculated ozone loss resulting from bromine chemistry in old air relative to some previous estimates as a result of the lower bromine levels.

An examination of the total hydrogen budget of the lower stratosphere

We analyze the hydrogen budget of the lower stratosphere using simultaneous in situ measurements of northern hemispheric water vapor (H2O) and methane (CH4) obtained during the spring Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE), as well as previously published in situ H2 data. Based on this data, we conclude that approximately two H2O molecules are produced for each CH4 molecule destroyed. This implies that H2 production from CH4 oxidation is balanced by H2 oxidation. The uncertainty in this analysis is greatly reduced by the use of multiple data sets. Additionally, we infer that, on an annual and global average, H2O enters the stratosphere with a mixing ratio of 4.2±0.5 ppmv, and that the quasi-conserved quantity 2×[CH4] + [H2O] has a value of 7.6±0.6 ppmv in these northern hemisphere air parcels (where [ξ] denotes the mixing ratio of the constituent ξ).

Three-dimensional simulations of long-lived tracers using winds from MACCM2

Three-dimensional simulations of the stratospheric constituents CH4, N2O, O3, SF6, and CO2 over an annual cycle have been performed using a semiLagrangian chemical transport model [Rasch and Williamson, 1990; Rasch et al., 1994] driven by archived wind data from the Middle Atmosphere version of the National Center for Atmospheric Research Community Climate Model version 2 (MACCM2) general circulation model. The constituents undergo chemical production and loss at rates calculated by two-dimensional photochemical models. We compare these “off-line” simulations of CH4 and N2O with “on-line” simulations in which the trace constituent distributions are computed interactively within the MACCM2 general circulation model and find good agreement even when daily averaged wind data and no subgrid scale parameterized mixing are used in the off-line simulations. We also compare the model simulations to satellite, aircraft, and balloon measurements. In most regions and seasons, the zonally averaged model CH4, N2O, and O3 fields agree well with observations. Notable discrepancies are (1) a lack of a “double peak” structure in the zonally averaged mixing ratios of model CH4 and N2O at equinox, (2) an overall underestimate of CH4 and N2O in the upper stratosphere, and (3) an underestimate of the height of the mixing ratio peak in O3, particularly at high latitudes. We find good agreement between modeled CO2 and SF6 and recent aircraft observations in the lower stratosphere, and balloon measurements in the lower and middle stratosphere. From the SF6 distribution we determine the mean age of air in the model stratosphere, with values as old as 10 years in the wintertime polar upper stratosphere. In addition, we simulate the annual cycle of CO2, a stringent test of model transport, which supplements the mean age. We obtain good agreement with aircraft measurements in phase and magnitude at the tropical tropopause, and the vertical profiles of CO2 are similar to those observed. However, the amplitude of the cycle attenuates too rapidly with height in the model stratosphere, suggesting the influence of midlatitude air and/or the vertical diffusion are too large in the model tropics.

Measurements of polar vortex air in the midlatitudes

The Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE) was conducted in the spring of 1993 from Moffett Field, California (NASA Ames Research Center), utilizing the NASA high-altitude ER-2 aircraft. These northern midlatitude aircraft flights showed laminae containing high ozone concentrations, traceable to the April 1993 polar vortex breakup and corroborated by laminae of other trace gases such as CFCs, CH4, N2O, and CO2. These laminae are clearly traceable as polar vortex breakup fragments using Rossby-Ertels potential vorticity and isentropic trajectory calculations. Laminae in stratospheric ozone profiles are commonly observed in the northern hemisphere from fall to spring, and are hypothesized to originate from very low frequency transverse waves, and/or via Rossby wave breaking. On the basis of these results, the ozone laminae observed during SPADE were a result of Rossby wave breaking during the breakdown of the polar vortex. In addition, it is shown that conventional once-per-day meteorological analyses were adequate for representing the transport of this material into the lower stratosphere midlatitudes over the course of the spring vortex breakup.

Closure of the total hydrogen budget of the northern extratropical lower stratosphere

Methane (CH4), molecular hydrogen (H2), and water vapor (H2O) were measured concurrently on board the NASA ER-2 aircraft during the 1995–1996 Stratospheric Tracers of Atmospheric Transport (STRAT) and 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaigns. Correlations between these three main hydrogen reservoirs in the northern extratropical lower stratosphere are examined to evaluate H2O production from CH4 and H2 oxidation. The expected ratio of stratospheric H2O production (PH2O)to CH4 destruction (LCH4) = −1.973±0.003 is calculated from an evaluation of CH4 and H2 oxidation reactions and the relationship between H2 and CH4 mixing ratios measured during STRAT. Correlations between H2O and CH4 were tight and linear only for air masses with mean ages ≥3.8 years, restricting this analysis predominantly to latitudes between 40° and 90°N and potential temperatures between 470 and 540 K. The mean observed ΔH2O/CH4 (−2.15±0.18) is in statistical agreement with the expected PH2O/LCH4. The annual mean stratospheric entry mixing ratio for H2O calculated from this slope is 4.0 ± 0.3 ppm. The quantity H2O + 2·CH4 is quasi-conserved at 7.4 ± 0.5 ppm in older air masses in the northern extratropical lower stratosphere. Significant departure of H2O + 2·CH4 from the mean value is a sensitive indicator of processes which influence H2O without affecting CH4, such as dehydration in a polar vortex or near the tropical tropopause. No significant trend is observed in ER-2 aircraft data for H2O + 2·CH4 in the lower stratosphere from 1993 through 1997.

In Situ Measurements of Long-Lived Trace Gases in the Lower Stratosphere by Gas Chromatography

Abstract Detailed information on the four-channel Airborne Chromatograph for Atmospheric Trace Species (ACATS-IV), used to measure long-lived atmospheric trace gases, is presented. Since ACATS-IV was last described in the literature, the temporal resolution of some measurements was tripled during 1997–99, chromatography was significantly changed, and data processing improved. ACATS-IV presently measures CCl3F [chlorofluorocarbon (CFC)-11], CCl2FCClF2 (CFC-113), CH3CCl3 (methyl chloroform), CCl4 (carbon tetrachloride), CH4 (methane), H2 (hydrogen), and CHCl3 (chloroform) every 140 s, and N2O (nitrous oxide), CCl2F2 (CFC-12), CBrClF2 (halon-1211), and SF6 (sulfur hexafluoride) every 70 s. An in-depth description of the instrument operation, standardization, calibration, and data processing is provided, along with a discussion of precision and uncertainties of ambient air measurements for several airborne missions.