James H. Butler

Non-CO2 greenhouse gases and climate change

Earth’s climate is warming as a result of anthropogenic emissions of greenhouse gases, particularly carbon dioxide (CO2) from fossil fuel combustion. Anthropogenic emissions of non-CO2 greenhouse gases, such as methane, nitrous oxide and ozone-depleting substances (largely from sources other than fossil fuels), also contribute significantly to warming. Some non-CO2 greenhouse gases have much shorter lifetimes than CO2, so reducing their emissions offers an additional opportunity to lessen future climate change. Although it is clear that sustainably reducing the warming influence of greenhouse gases will be possible only with substantial cuts in emissions of CO2, reducing non-CO2 greenhouse gas emissions would be a relatively quick way of contributing to this goal.

Decline in the Tropospheric Abundance of Halogen from Halocarbons: Implications for Stratospheric Ozone Depletion

Analyses of air sampled from remote locations across the globe reveal that tropospheric chlorine attributable to anthropogenic halocarbons peaked near the beginning of 1994 and was decreasing at a rate of 25 ± 5 parts per trillion per year by mid-1995. Although bromine from halons was still increasing in mid-1995, the summed abundance of these halogens in the troposphere is decreasing. To assess the effect of this trend on stratospheric ozone, estimates of the future stratospheric abundance of ozone-depleting gases were made for mid-latitude and polar regions on the basis of these tropospheric measurements. These results suggest that the amount of reactive chlorine and bromine will reach a maximum in the stratosphere between 1997 and 1999 and will decline thereafter if limits outlined in the adjusted and amended Montreal Protocol on Substances That Deplete the Ozone Layer are not exceeded in future years.

Present and future trends in the atmospheric burden of ozone-depleting halogens

The burden of ozone-depleting chemicals in the lower atmosphere has been decreasing since 1994 as a result of the Montreal Protocol. Here we show how individual chemicals have influenced this decline, in order to estimate how the burden could change in the near future. Our measurements of atmospheric concentrations of the persistent, anthropogenic chemicals that account for most ozone-depleting halogens in todays stratosphere show that the decline stems predominantly from the decrease in the atmospheric load of trichloroethane (CH3CCl3), a previously common cleaning solvent. The influence of this chemical on the decline has now peaked, however, and will become much smaller over the next five to ten years. As this influence lessens, a decrease in theburden of ozone-depleting halogen will be sustained only if emissions of other halocarbons fall. Although emissions of most gases regulated by the Montreal Protocol have decreased substantially over the past ten years (refs 4), emissions of the potent ozone-depleting gas CBrClF2 (halon-1211) have remained fairly constant during this period, despite stringent limits on production in developed countries since 1994. The consequent atmospheric accumulation of this halon is retarding the decline of ozone-depleting halogens in the atmosphere more than any other persistent gas.

A record of atmospheric halocarbons during the twentieth century from polar firn air

Measurements of trace gases in air trapped in polar firn (unconsolidated snow) demonstrate that natural sources of chlorofluorocarbons, halons, persistent chlorocarbon solvents and sulphur hexafluoride to the atmosphere are minimal or non-existent. Atmospheric concentrations of these gases, reconstructed back to the late nineteenth century, are consistent with atmospheric histories derived from anthropogenic emission rates and known atmospheric lifetimes. The measurements confirm the predominance of human activity in the atmospheric budget of organic chlorine, and allow the estimation of atmospheric histories of halogenated gases of combined anthropogenic and natural origin. The pre-twentieth-century burden of methyl chloride was close to that at present, while the burden of methyl bromide was probably over half of todays value.

Tropospheric SF6: Observed latitudinal distribution and trends, derived emissions and interhemispheric exchange time

Sulfur hexafluoride (SF6), an anthropogentically produced compound that is a potent greenhouse gas, has been measured in a number of NOAA GMDL air sampling programs. These include high resolution latitudinal profiles over the Atlantic and Pacific oceans, weekly flask samples from seven remote, globally distributed sites, hourly in situ measurements in rural North Carolina, and a series of archived air samples from Niwot Ridge, Colorado. The observed increase in atmospheric mixing ratio is consistent with an overall quadratic growth rate, at 6.9±0.2% yr−1 (0.24±0.01 ppt yr−1) for early 1996. From these data we derive an early 1996 emission rate of 5.9±0.2 Gg SF6 yr−1 and an interhemispheric exchange time of 1.3±0.1 years.

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.

A Net Sink for Atmospheric CH3Br in the East Pacific Ocean

Surface waters along a cruise track in the East Pacific Ocean were undersaturated in methyl bromide (CH3Br) in most areas except for coastal and upwelling regions, with saturation anomalies ranging from + 100 percent in coastal waters to –50 percent in open ocean areas, representing a regionally weighted mean of –16 (–13 to –20) percent. The partial lifetime of atmospheric CH3Br with respect to calculated oceanic degradation along this cruise track is 3.0 (2.9 to 3.6) years. The global, mean dry mole fraction of CH3Br in the atmosphere was 9.8 � 0.6 parts per trillion, with an interhemispheric ratio of 1.31 � 0.08. These data indicate that ∼8 percent (0.2 parts per trillion) of the observed interhemispheric difference in atmospheric CH3Br could be attributed to an uneven global distribution of oceanic sources and sinks.

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.

Atmospheric chemistry: Better budgets for methyl halides?

In research into ozone depletion in the stratosphere, most attention has centred on man-made halocarbon compounds (the chlorofluorocarbons — CFCs — for instance). Other ozone-depleting compounds such as methyl bromide and methyl chloride are largely produced in the natural world. Three new studies look at the sources and reactions concerned.

Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models

biomass burning are also included in the model. The model captures 40% of the variance in the observed seawater CH3I(aq) concentrations. Simulated concentrations at midlatitudes in summer are too high, perhaps because of a missing biological sink of CH3I(aq). We define a marine convection index (MCI) as the ratio of upper tropospheric (8–12 km) to lower tropospheric (0–2.5 km) CH3I concentrations averaged over coherent oceanic regions. The MCI in the observations ranges from 0.11 over strongly subsiding regions (southeastern subtropical Pacific) to 0.40 over strongly upwelling regions (western equatorial Pacific). The model reproduces the observed MCI with no significant global bias (offset of only +11%) but accounts for only 15% of its spatial and seasonal variance. The MCI can be used to test marine convection in global models, complementing the use of radon-222 as a test of continental convection. INDEX TERMS: 0312 Atmospheric Composition and Structure: Air/sea constituent fluxes (3339, 4504); 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; KEYWORDS: methyl iodide, marine convection, atmospheric tracer, global budget of methyl iodide