Theoretical Investigations of Clouds and Aerosols in the Stratosphere and Upper Troposphere

support of the Atmospheric Chemistry Modeling and Data Analysis Program. We investigated a wide variety of issues involving ambient stratospheric aerosols, polar stratospheric clouds or heterogeneous chemistry, analysis of laboratory data, and particles in the upper troposphere. The papers resulting from these studies are listed below. In addition, I participated in the 1999-2000 SOLVE mission as one of the project scientists and in the 2002 CRYSTAL field mission as one of the project scientists. Several CU graduate students and research associates also participated in these mission, under support from the ACMAP program, and worked to interpret data. During the past few years my group has completed a number of projects under th

Influence of Nucleation Mechanisms on the Radiative Properties of Deep Convective Clouds and Subvisible Cirrus in CRYSTAL/FACE

During the past few years we have conducted work on several different topics, as reflected by our publications. As one of the Co-Project scientists for The Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL FACE) we worked to help design the mission and then conduct it in the field. Another major activity during the past two years has been to pull together various groups to formulate plans for follow on missions to CRYSTAL FACE. We organized a workshop at the University of Colorado during the summer of 2003 to assess the best locations for future missions. Working with a group of about 10 scientists from around the country we prepared a science-planning document (Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4)) that outlined the rationale, locations, strategy to accomplish the goals, and possible payloads for a set of three tropical missions. We also prepared background materials for various NRAs being prepared at NASA Headquarters for missions in Costa Rica, Darwin and Guam. In conjunction with the group at NASA Ames we have helped build a new numerical model for deep convection and have applied that model to simulate the CRYSTAL data. Our goal in particular has been to better understand how convection distributes water vapor isotopes. CRYSTAL observations of water isotopes are very different from those suggested by previous workers who assumed the isotopes would obey Rayleigh fractionation. The water isotope study has several implications. First it is a check on the realism of the deep convection model. Second, the isotopes are a measure of the precipitation removal in the atmosphere. Hence they provide a constraint on a parameter that is difficult to otherwise measure. Finally it has been suggested that isotopes may be the key to unraveling the water transport into the stratosphere and upper troposphere. Such transport is critical both for the radiation balance and for stratospheric chemistry. Ours is the first model that is able to treat this transport. Our initial results have just been submitted to Geophys. Res. Lett (Smith et al., 2005). Essentially we are able to explain the vertical profiles of isotopes in the tropical tropopause transition layer. We are also able to account for stratospheric humidity and isotope abundances with this model. We have also been heavily involved in trying to improve our understanding of nitric acid condensation on ice. Gao et al (2004) have shown that water supersaturations above ice occur when the atmosphere is supersaturated with respect to nitric acid trihydrate. As one of the co-authors of that work, we suggested the mechanism that may explain why this is occurring. Essentially, ice does not like to grow near unit supersaturation, but does so because the water molecules can find sites on the ice surface to attach themselves to before they fly off the ice surface. This phenomena was well known in the 1960s when it was a source of debate about whether condensation and evaporation coefficients for ice would be the same. Evaporation does not require any molecular orientation, while condensation does, so it was possible that the coefficients would differ. They don't differ because the water molecules rapidly move across the surface and find places to attach. Nitric acid may be occupying these preferred sites and therefore the water molecules can't find a desirable place to attach. We anticipate that this research will be the subject of laboratory work during the coming few years. Another possibility that has been suggested is that cubic ice is forming in clouds. We have measured the vapor pressure of cubic ice, and plan to publish that result in the next few months. We have also been working on additional aspects of the condensation of nitric acid on ice. With Y. Kondo we studied the condensation of NOy on ice using the SOLVE data. Gamblin et al. have continued this work. The CRYSTAL NOy and HNO, groups have shown th their data can be fit using standard Langmuir isotherms as suggested in some, but not all, laboratory studies. We have found in the SOLVE data set that this is not the case. Moreover some laboratory studies show there are important kinetic effects that may be occurring in the atmosphere limiting the transfer of nitric acid to the ice. The SOLVE data seem consistent with these studies. We are currently re-analyzing the CRYSTAL data to look for these kinetic effects. There are a number of implications of these studies. One of the more interesting is that the nitric acid coating on ice can be used as a cloud clock to determine how long the cloud parcel has been in existence. We have also been involved with several laboratory studies. We have worked to improve the database on ice optical constants, which are critical for remote sensing. We have also studied the ways in which ice nucleates on clays. We suspect now that the standard theories used for depositional ice nucleation are completely incorrect. Further work will be needed to develop a new theory

Investigations of Desert Dust and Smoke in the North Atlantic in Support of the TOMS Instrument

During the initial period of the work we concentrated on Saharan dust storms and published a sequence of papers (Colarco et a1 2002,2003a,b, Toon, 2004). The U.S. Air Force liked the dust model so well that they appropriated it for operational dust storm forecasting (Barnum et al., 2004). The Air Force has used it for about 5 yrs in the Middle East where dust storms cause significant operational problems. The student working on this project, Peter Colarco, has graduated and is now a civil servant at Goddard where he continues to interact with the TOMS team. This work helped constrain the optical properties of dust at TOMS wavelengths, which is useful for climate simulations and for TOMS retrievals of dust properties such as optical depth. We also used TOMS data to constrain the sources of dust in Africa and the Middle East, to determine the actual paths taken by Saharan dust storms, to learn more about the mechanics of variations in the optical depths, and to learn more about the mechanisms controlling the altitudes of the dust. During the last two years we have been working on smoke from fires. Black carbon aerosols are one of the leading factors in radiative forcing. The US Climate Change Science Program calls this area out for specific study. It has been suggested by Jim Hansen, and Mark Jacobsen among others, that by controlling emissions of black carbon we might reduce greenhouse radiative forcing in a relatively painless manner. However, we need a greatly improved understanding of the amount of black carbon in the atmosphere, where it is located, where it comes from, how it is mixed with other particles, what its actual optical properties are, and how it evolves. In order to learn about these issues we are using a numerical model of smoke. We have applied this model to the SAFARI field program data, and used the TOMS satellite observations in that period (Sept. 2000). Our goal is to constrain source function estimates for black carbon, and smoke optical properties

Physical processes in polar stratospheric ice clouds

A one dimensional model of cloud microphysics was used to simulate the formation and evolution of polar stratospheric ice clouds. Some of the processes which are included in the model are outlined. It is found that the clouds must undergo preferential nucleation upon the existing aerosols just as do tropospheric cirrus clouds. Therefore, there is an energy barrier between stratospheric nitric acid particles and ice particles implying that nitric acid does not form a continuous set of solutions between the trihydrate and ice. The Kelvin barrier is not significant in controlling the rate of formation of ice particles. It was found that the cloud properties are sensitive to the rate at which the air parcels cool. In wave clouds, with cooling rates of hundreds of degrees per day, most of the existing aerosols nucleate and become ice particles. Such clouds have particles with sizes on the order of a few microns, optical depths on order of unity and are probably not efficient at removing materials from the stratosphere. In clouds which form with cooling rates of a few degrees per day or less, only a small fraction of the aerosols become cloud particles. In such clouds the particle radius is larger than 10 microns, the optical depths are low and water vapor is efficiently removed. Seasonal simulations show that the lowest water vapor mixing ratio is determined by the lowest temperature reached, and that the time when clouds disappear is controlled by the time when temperatures begin to rise above the minimum values

Stratospheric dynamics

A global circulation model is being used to study the dynamical behavior of stratospheric planetary waves (waves having horizontal wavelengths of tens of thousands of kilometers) forced by growing cyclonic disturbances of intermediate scale, typically with wavelengths of a few thousand kilometers, which occur in the troposphere. Planetary scale waves are the dominant waves in the stratosphere, and are important for understanding the distribution of atmospheric trace constituents. Planetary wave forcing by intermediate scale tropospheric cyclonic disturbances is important for producing eastward travelling planetary waves of the sort which are prominent in the Southern Hemisphere during winter. The same global circulation model is also being used to simulate and understand the rate of dispersion and possible stratospheric climatic feedbacks of the El Chichon volcanic aerosol cloud. By comparing the results of the model calculation with an established data set now in existence for the volcanic cloud spatial and temporal distribution, stratospheric transport processes will be better understood, and the extent to which the cloud modified stratospheric wind and temperature fields can be assessed

On the size and composition of particles in polar stratospheric clouds

Attenuation measurements of the solar radiation between 1.5 and 15 micron wavelengths were performed with the airborne (DC-8) JPL MARK 4 interferometer during the 1987 Antarctic Expedition. The opacities not only provide information about the abundance of stratospheric gases but also about the optical depths of polar stratospheric clouds (PSCs) at wavelengths of negligible gas absorption (windows). The optical depth of PSCs can be determined for each window once the background attenuation, due to air-molecules and aerosol has been filtered out with a simple extinction law. The ratio of optical thicknesses at different wavelengths reveals information about particle size and particle composition. Among the almost 700 measured spectra only a few PSC cases exist. PSC events are identified by sudden reductions in the spectrally integrated intensity value and are also verified with backscattering data from an upward directed lidar instrument, that was mounted on the DC-8. For the selected case on September 21st at 14.40 GMT, lidar data indicate an optically thin cloud at 18k and later an additional optically thick cloud at 15 km altitude. All results still suffer from: (1) often arbitrary definitions of a clear case, that often already may have contained PSC particles and (2) noise problems that restrict the calculations of optical depths to values larger than 0.001. Once these problems are handled, this instrument may become a valuable tool towards a better understanding of the role PSCs play in the Antarctic stratosphere

Studies of stratospheric particulates

A sophisticated computer model of polar stratospheric clouds was developed and used to study the properties of ice clouds. The model has recently been extended to investigate nitric acid clouds and ice clouds as well as their interactions with stratospheric gases. The model is now being applied to interpret data collected during recent expeditions to the Antarctic and the Arctic. Some work has also been done to understand the properties of noctilucent clouds and their implications for the chemistry and dynamics of the upper stratosphere

Spectroscopic Evidence Against Nitric Acid Trihydrate in Polar Stratospheric Clouds

Heterogeneous reactions on polar stratospheric clouds (PSC's) play a key role in the photochemical mechanisms thought to be responsible for ozone depletion in the Antarctic and the Arctic. Reactions on PSC particles activate chlorine to forms that are capable of photochemical ozone destruction, and sequester nitrogen oxides (NOx) that would otherwise deactivate the chlorine. Although the heterogeneous chemistry is now well established, the composition of the clouds themselves is uncertain. It is commonly thought that they are composed of nitric acid trihydrate, although observations have left this question unresolved. Here we reanalyse infrared spectra of type I PCS's obtained in Antarctica in September 1987, using recently measured optical constraints of the various compounds that might be present in PSC's. We find that these PSC's were not composed of nitric acid trihydrate but instead had a more complex composition perhaps that of a ternary solution. Because cloud formation is sensitive to their composition, this finding will alter our understanding of the locations and conditions in which PSCs form. In addition, the extent of ozone loss depends on the ability of the PSC's to remove NOx permanently through sedimentation. The sedimentation rates depend on PSC particle size which in turn is controlled by the composition and formation mechanism

An overview of mesoscale aerosol processes, comparisons, and validation studies from DRAGON networks

Over the past 24 years, the AErosol RObotic NETwork (AERONET) program has provided highly accurate remote-sensing characterization of aerosol optical and physical properties for an increasingly extensive geographic distribution including all continents and many oceanic island and coastal sites. The measurements and retrievals from the AERONET global network have addressed satellite and model validation needs very well, but there have been challenges in making comparisons to similar parameters from in situ surface and airborne measurements. Additionally, with improved spatial and temporal satellite remote sensing of aerosols, there is a need for higher spatial-resolution ground-based remote-sensing networks. An effort to address these needs resulted in a number of field campaign networks called Distributed Regional Aerosol Gridded Observation Networks (DRAGONs) that were designed to provide a database for in situ and remote-sensing comparison and analysis of local to mesoscale variability in aerosol properties. This paper describes the DRAGON deployments that will continue to contribute to the growing body of research related to meso- and microscale aerosol features and processes. The research presented in this special issue illustrates the diversity of topics that has resulted from the application of data from these networks

Nitrogen Incorporation in CH_4-N_2 Photochemical Aerosol Produced by Far Ultraviolet Irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH_4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets. Key Words: Titan—Photochemical aerosol—CH_4-N_2 photolysis—Far UV—Nitrogen activation