Persistent Water-Nitric Acid Condensate with Saturation Water Vapor Pressure Greater than That of Hexagonal Ice.

A laboratory chilled mirror hygrometer (CMH), exposed to an airstream containing water vapor (H2O) and nitric acid (HNO3), has been used to demonstrate the existence of a persistent water-nitric acid condensate that has a saturation H2O vapor pressure greater than that of hexagonal ice (Ih). The condensate was routinely formed on the mirror by removing HNO3 from the airstream following the formation of an initial condensate on the mirror that resembled nitric acid trihydrate (NAT). Typical conditions for the formation of the persistent condensate were a H2O mixing ratio greater than 18 ppm, pressure of 128 hPa, and mirror temperature between 202 and 216 K. In steady-state operation, a CMH maintains a condensate of constant optical diffusivity on a mirror through control of only the mirror temperature. Maintaining the persistent condensate on the mirror required that the mirror temperature be below the H2O saturation temperature with respect to Ih by as much as 3 K, corresponding to up to 63% H2O supersaturation with respect to Ih. The condensate was observed to persist in steady state for up to 16 h. Compositional analysis of the condensate confirmed the co-condensation of H2O and HNO3 and thereby strongly supports the conclusion that the Ih supersaturation is due to residual HNO3 in the condensate. Although the exact structure or stoichiometry of the condensate could not be determined, other known stable phases of HNO3 and H2O are excluded as possible condensates. This persistent condensate, if it also forms in the upper tropical troposphere, might explain some of the high Ih supersaturations in cirrus and contrails that have been reported in the tropical tropopause region.

The spectroscopic foundation of radiative forcing of climate by carbon dioxide.

The radiative forcing (RF) of carbon dioxide (CO2) is the leading contribution to climate change from anthropogenic activities. Calculating CO2 RF requires detailed knowledge of spectral line parameters for thousands of infrared absorption lines. A reliable spectroscopic characterization of CO2 forcing is critical to scientific and policy assessments of present climate and climate change. Our results show that CO2 RF in a variety of atmospheres is remarkably insensitive to known uncertainties in the three main CO2 spectroscopic parameters: the line shapes, line strengths, and half widths. We specifically examine uncertainty in RF due to line mixing as this process is critical in determining line shapes in the far wings of CO2 absorption lines. RF computed with a Voigt line shape is also examined. Overall, the spectroscopic uncertainty in present-day CO2 RF is less than 1%, indicating a robust foundation in our understanding of how rising CO2 warms the climate system.

UV absorption spectrum of the ClO dimer (Cl2O2) between 200 and 420 nm.

The UV photolysis of Cl(2)O(2) (dichlorine peroxide) is a key step in the catalytic destruction of polar stratospheric ozone. In this study, the gas-phase UV absorption spectrum of Cl(2)O(2) was measured using diode array spectroscopy and absolute cross sections, sigma, are reported for the wavelength range 200-420 nm. Pulsed laser photolysis of Cl(2)O at 248 nm or Cl(2)/Cl(2)O mixtures at 351 nm at low temperature (200-228 K) and high pressure (approximately 700 Torr, He) was used to produce ClO radicals and subsequently Cl(2)O(2) via the termolecular ClO self-reaction. The Cl(2)O(2) spectrum was obtained from spectra recorded following the completion of the gas-phase ClO radical chemistry. The spectral analysis used observed isosbestic points at 271, 312.9, and 408.5 nm combined with reaction stoichiometry and chlorine mass balance to determine the Cl(2)O(2) spectrum. The Cl(2)O(2) UV absorption spectrum peaks at 244.5 nm with a cross section of 7.6(-0.5)(+0.8) x 10(-18) cm(2) molecule(-1) where the quoted error limits are 2sigma and include estimated systematic errors. The Cl(2)O(2) absorption cross sections obtained for wavelengths in the range 300-420 nm are in good agreement with the Cl(2)O(2) spectrum reported previously by Burkholder et al. (J. Phys. Chem. A 1990, 94, 687) and significantly higher than the values reported by Pope et al. (J. Phys. Chem. A 2007, 111, 4322). A possible explanation for the discrepancy in the Cl(2)O(2) cross section values with the Pope et al. study is discussed. Representative, atmospheric photolysis rate coefficients are calculated and a range of uncertainty estimated based on the determination of sigma(Cl(2)O(2))(lambda) in this work. Although improvements in our fundamental understanding of the photochemistry of Cl(2)O(2) are still desired, this work indicates that major revisions in current atmospheric chemical mechanisms are not required to simulate observed polar ozone depletion.

The large contribution of projected HFC emissions to future climate forcing.

The consumption and emissions of hydrofluorocarbons (HFCs) are projected to increase substantially in the coming decades in response to regulation of ozone depleting gases under the Montreal Protocol. The projected increases result primarily from sustained growth in demand for refrigeration, air-conditioning (AC) and insulating foam products in developing countries assuming no new regulation of HFC consumption or emissions. New HFC scenarios are presented based on current hydrochlorofluorocarbon (HCFC) consumption in leading applications, patterns of replacements of HCFCs by HFCs in developed countries, and gross domestic product (GDP) growth. Global HFC emissions significantly exceed previous estimates after 2025 with developing country emissions as much as 800% greater than in developed countries in 2050. Global HFC emissions in 2050 are equivalent to 9-19% (CO(2)-eq. basis) of projected global CO(2) emissions in business-as-usual scenarios and contribute a radiative forcing equivalent to that from 6-13 years of CO(2) emissions near 2050. This percentage increases to 28-45% compared with projected CO(2) emissions in a 450-ppm CO(2) stabilization scenario. In a hypothetical scenario based on a global cap followed by 4% annual reductions in consumption, HFC radiative forcing is shown to peak and begin to decline before 2050.

Aviation and global climate change in the 21st century.

Aviation emissions contribute to the radiative forcing (RF) of climate. Of importance are emissions of carbon dioxide (CO2), nitrogen oxides (NO x ), aerosols and their precursors (soot and sulphate), and increased cloudiness in the form of persistent linear contrails and induced-cirrus cloudiness. The recent Fourth Assessment Report (AR4) of the Intergovernmental Panel on Climate Change (IPCC) quantified aviation's RF contribution for 2005 based upon 2000 operations data. Aviation has grown strongly over the past years, despite world-changing events in the early 2000s; the average annual passenger traffic growth rate was 5.3% yr-1 between 2000 and 2007, resulting in an increase of passenger traffic of 38%. Presented here are updated values of aviation RF for 2005 based upon new operations data that show an increase in traffic of 22.5%, fuel use of 8.4% and total aviation RF of 14% (excluding induced-cirrus enhancement) over the period 2000-2005. The lack of physical process models and adequate observational data for aviation-induced cirrus effects limit confidence in quantifying their RF contribution. Total aviation RF (excluding induced cirrus) in 2005 was ∼55 mW m-2 (23-87 mW m-2, 90% likelihood range), which was 3.5% (range 1.3-10%, 90% likelihood range) of total anthropogenic forcing. Including estimates for aviation-induced cirrus RF increases the total aviation RF in 2005-78 mW m-2 (38-139 mW m-2, 90% likelihood range), which represents 4.9% of total anthropogenic forcing (2-14%, 90% likelihood range). Future scenarios of aviation emissions for 2050 that are consistent with IPCC SRES A1 and B2 scenario assumptions have been presented that show an increase of fuel usage by factors of 2.7-3.9 over 2000. Simplified calculations of total aviation RF in 2050 indicate increases by factors of 3.0-4.0 over the 2000 value, representing 4-4.7% of total RF (excluding induced cirrus). An examination of a range of future technological options shows that substantive reductions in aviation fuel usage are possible only with the introduction of radical technologies. Incorporation of aviation into an emissions trading system offers the potential for overall (i.e., beyond the aviation sector) CO2 emissions reductions. Proposals exist for introduction of such a system at a European level, but no agreement has been reached at a global level.

Experimental and theoretical study of the atmospheric chemistry and global warming potential of SO2F2.

In this work, potential atmospheric loss processes for SO2F2, a commercially used biocide (fumigant), have been studied and its global warming potential calculated. Rate coefficients for the gas-phase reactions OH + SO2F2 --> products, k1, and Cl + SO2F2 --> products, k4, were determined using a relative rate technique to be k1 < 1 x 10(-16) cm3 molecule-1 s-1 at 296 and 333 K and k4(296 K) < 5 x 10(-17) cm3 molecule(-1) s(-1). UV absorption cross sections of SO2F2 were measured at 184.9, 193, and 213.9 nm, and its photolysis quantum yield at 193 nm was determined to be <0.02. The atmospheric lifetime of SO2F2 with respect to loss by OH, Cl, and O(1D) reaction and UV photodissociation is estimated to be >300, >10000, 700, and >4700 years, respectively. The stratospheric lifetime of SO2F2 is calculated using a two-dimensional model to be 630 years. The global warming potential (GWP) for SO2F2 was calculated to be 4780 for the 100 year time horizon using infrared absorption cross sections measured in this work and a SO2F2 globally averaged atmospheric lifetime of 36 years, which is determined primarily by ocean uptake, reported by Mühle et al. (Mühle, J.; Huang, J.; Weiss, R. F.; Prinn, R. G.; Miller, B. R.; Salameh, P. K.; Harth, C. M.; Fraser, P. J.; Porter, L. W.; Greally, B. R.; O'Doherty, S.; Simonds, P. G. J. Geophys. Res., submitted for publication, 2008). Reaction channels and the possible formation of stable adducts in reactions 1 and 4 were evaluated using ab initio, CCSD(T), and density functional theory, B3P86, quantum mechanical electronic structure calculations. The most likely reaction product channels were found to be highly endothermic, consistent with the upper limits of the rate coefficients measured in this work.

The importance of the Montreal Protocol in protecting climate.

The 1987 Montreal Protocol on Substances that Deplete the Ozone Layer is a landmark agreement that has successfully reduced the global production, consumption, and emissions of ozone-depleting substances (ODSs). ODSs are also greenhouse gases that contribute to the radiative forcing of climate change. Using historical ODSs emissions and scenarios of potential emissions, we show that the ODS contribution to radiative forcing most likely would have been much larger if the ODS link to stratospheric ozone depletion had not been recognized in 1974 and followed by a series of regulations. The climate protection already achieved by the Montreal Protocol alone is far larger than the reduction target of the first commitment period of the Kyoto Protocol. Additional climate benefits that are significant compared with the Kyoto Protocol reduction target could be achieved by actions under the Montreal Protocol, by managing the emissions of substitute fluorocarbon gases and/or implementing alternative gases with lower global warming potentials.