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The Interaction Between Dynamics and Chemistry of Ozone in the Set-up Phase of the Northern Hemisphere Polar Vortex

The morphology and evolution of the stratospheric ozone (O3) distribution at high latitudes in the Northern Hemisphere (NH) are examined for the late summer and fall seasons of 1999. This time period sets the O3 initial condition for the SOLVE/THESEO field mission performed during winter 1999-2000. In situ and satellite data are used along with a three-dimensional model of chemistry and transport (CTM) to determine the key processes that control the distribution of O3 in the lower-to-middle stratosphere. O3 in the vortex at the beginning of the winter season is found to be nearly constant from 500 to above 800 K with a value at 3 ppmv +/- approx. 10%. Values outside the vortex are up to a factor of 2 higher and increase significantly with potential temperature. The seasonal time series of data from POAM shows that relatively low O3 mixing ratios, which characterize the vortex in late fall, are already present at high latitudes at the end of summer before the vortex circulation sets up. Analysis of the CTM output shows that the minimum O3 and increase in variance in late summer are the result of: 1) stirring of polar concentric O3 gradients by nascent wave-driven transport, and 2) an acceleration of net photochemical loss with decreasing solar illumination. The segregation of low O3 mixing ratios into the vortex as the circulation strengthens through the fall suggests a possible feedback role between O3 chemistry and the vortex formation dynamics. Trajectory calculations from O3 sample points early in the fall, however, show only a weak correlation between initial O3 mixing ratio and potential vorticity later in the season consistent with order-of-magnitude calculations for the relative importance of O3 in the fall radiative balance at high latitudes. The possible connection between O3 chemistry and the dynamics of vortex formation does suggest that these feedbacks and sensitivities need to be better understood in order to make confident predictions of the recovery of NH O3.

Kawa, S. R.↗

Comparison of Aerosol Optical Properties and Water Vapor Among Ground and Airborne Lidars and Sun Photometers During TARFOX

We compare aerosol optical thickness (AOT) and precipitable water vapor (PWV) measurements derived from ground and airborne lidars and sun photometers during the Tropospheric Aerosol Radiative Forcing Observational Experiment. Such comparisons are important to verify the consistency between various remote sensing measurements before employing them in any assessment of the impact of aerosols on the global radiation balance. Total scattering ratio and extinction profiles measured by the ground-based NASA Goddard Space Flight Center scanning Raman lidar system, which operated from Wallops Island, Virginia (37.86 deg N, 75.51 deg W); are compared with those measured by the Lidar Atmospheric Sensing Experiment (LASE) airborne lidar system aboard the NASA ER-2 aircraft. Bias and root-mean-square differences indicate that these measurements generally agreed within about 10%. Aerosol extinction profiles and estimates of AOT are derived from both lidar measurements using a value for the aerosol extinction/backscattering ratio S(sub a) = 60 sr for the aerosol extinction/backscattering ratio, which was determined from the Raman lidar measurements. The lidar measurements of AOT are found to be generally within 25% of the AOT measured by the NASA Ames Airborne Tracking Sun Photometer (AATS-6). However, during certain periods the lidar and Sun photometer measurements of AOT differed significantly, possibly because of variations in the aerosol physical characteristics (e.g., size, composition) which affect S(sub a). Estimates of PWV, derived from water vapor mixing ratio profiles measured by LASE, are within 5-10% of PWV derived from the airborne Sun photometer. Aerosol extinction profiles measured by both lidars show that aerosols were generally concentrated in the lowest 2-3 km.

Ferrare, R.↗

Luminescence from VUV Irradiated Cosmic Ice Analogs and Organic Residues

The optical luminescent properties for a variety of vacuum-ultraviolet (VUV) irradiated cosmic ice analogs and the complex organic residues produced from irradiation might be applicable to Solar System and interstellar observations and processes for various astronomical objects with an ice heritage. Some examples include grain temperature determination and vaporization rates, nebula radiation balance, albedo values, color analysis, and biomarker identification. Detailed results are presented for the mixed molecular ice: H2O:CH3OH:NH3:CO (100:50:1:1), a realistic representation for an interstellar/precometary ice. The irradiated ices and the room-temperature residues resulting from this energetic processing have remarkable photoluminescent properties in the visible (520-570 nm). The luminescence dependence on temperature, thermal cycling, and VUV exposure of the residue is described.

Gudipati, Murthy S.↗

The Distribution of Ozone in the Early Stages of Polar Vortex Development

Previous analysis has shown that the distribution of O3 at high northern latitudes in the lower-to-middle stratosphere at the beginning of the winter season, 1999-2000 has a characteristic distribution, which is consistent between in situ and satellite measurements [Kawa et al., The Interaction Between Dynamics and Chemistry of Ozone in the Set-up Phase of the Northern Hemisphere Polar Vortex, submitted manuscript, 2001 ]. Initial O3 profiles in the vortex are similar to each other and are quite different from outside the vortex at the same latitude and also from a zonal mean climatology. In the vortex, O3 is nearly constant from 500 to above 800 K with a value at 3 ppmv +/- approx.10%. Values outside the vortex are up to a factor of 2 higher and increase significantly with potential temperature. The seasonal time series of POAM data shows that relatively low O3 mixing ratios, which characterize the vortex in late fall, are already present at high latitudes at the end of summer in September before the vortex circulation sets up. This suggests a possible feedback role between O3 chemistry and the formation of the vortex, which is dominated by the seasonal radiation balance. Here we show that these characteristic O3 distributions are consistent from year to year and between the hemispheres. We will attempt to determine whether variations in fall vortex O3 are related in any way to O3 abundances and vortex structure later during winter and into spring.

Kawa, S. R.↗

Luminescence from Vacuum-Ultraviolet-Irradiated Cosmic Ice Analogs and Residue

Here we report a study of the optical luminescent properties for a variety of vacuum-ultraviolet (VUV)-irradiated cosmic ice analogs and the complex organic residues produced. Detailed results are presented for the irradiated, mixed molecular ice: H2O: CH3OH:NH3:CO(100:50:1:1), a realistic representation for an interstellar/precometary ice that reproduces all the salient infrared spectral features associated with interstellar ices. The irradiated ices and the room-temperature residues resulting from this energetic processing have remarkable photoluminescent properties in the visible (520-570 nm). The luminescence dependence on temperature, thermal cycling, and VUV exposure is described. It is suggested that this type of luminescent behavior might be applicable to solar system and interstellar observations and processes for various astronomical objects with an ice heritage. Some examples include grain temperature determination and vaporization rates, nebula radiation balance, albedo values, color analysis, and biomarker identification.

Gudipati, Murthy S.↗

Luminescence from Vacuum-Ultraviolet-Irradiated Cosmic Ice Analogs and Residues

Here we report a study of the optical luminescent properties for a variety of vacuum-ultraviolet (VUV)- irradiated cosmic ice analogs and the complex organic residues produced. Detailed results are presented for the irradiated, mixed molecular ice: H2O:CH3OH:NH3:CO (100:50:1:1), a realistic representation for an interstellar/precometary ice that reproduces all the salient infrared spectral features associated with interstellar ices. The irradiated ices and the room-temperature residues resulting from this energetic processing have remarkable photoluminescent properties in the visible (520-570 nm). The luminescence dependence on temperature, thermal cycling, and VUV exposure is described. It is suggested that this type of luminescent behavior might be applicable to solar system and interstellar observations and processes for various astronomical objects with an ice heritage. Some examples include grain temperature determination and vaporization rates, nebula radiation balance, albedo values, color analysis, and biomarker identification.

Gudipati, Murthy S.↗

Estimation of the Anthropogenic Influence in the Sahel by Terra and Aqua

Saharan dust impacts the Earth radiation balance. It was suggested that anywhere between 20-50% of the dust is anthropogenic, generated from human activity in the Sahel. Recent study By Prospero et al noticed that most of the sources should be north of Latitude of 15 deg. where population density is small. Here we use Aqua and Terra data to study the dust sources and their possible anthropogenic origin. Dust packages emitted from the Bodele depression and other sources in the southern part of the Sahara, are transported in the winter by a Northern East winds over the Sahel to the ocean. We are tracking these packages with MODIS from their sources to the ocean, showing that most of the dust reaching the Ocean from the Sahelian shore is generated in the Sahara, suggesting that the anthropogenic influence in the area is negligible. Saharan dust was suggested to be the main source of nutrients to the Amazon forest. Here we are also showing that these South Saharan sources around the Bodele depression are very active in the winter and rather passive in the summer, suggesting that the type of dust reaching Brazil, and its mineral content from these sources may be different from the dust that arrives to North America and Europe emitted in the summer from different sources.

Koren, I.↗

Dehydration in the Winter Arctic Tropopause Region

Recent work has shown that limited amounts of tropospheric air can penetrate as much as 1 km into the middleworld stratosphere during the arctic winter. This, coupled with temperatures that are cold enough to produce saturation mixing ratios of less than 5 ppmv at the tropopause, results in stratospheric cloud formation and upper tropospheric dehydration. Even though these "cold outbreaks" occupy only a small portion of the area in the arctic (1-2%), their importance is magnified by an order of magnitude because of the air flow through them. This is reinforced by evidence of progressive drying through the winter measured during SOLVE-1. The significance of this process lies in its effect on the upper tropospheric water content of the middle and high latitude tropopause region, which plays an important role in regulating the earth's radiative balance. There appears to be significant year-to-year variability in the incidence of the cold outbreaks. This work has two parts. First, we describe case studies of dehydration taken from the SOLVE and SOLVE2 aircraft sampling missions during the Arctic winters of 2000 and 2003 respectively. Trajectory based microphysical modeling is employed to examine the sensitivity of the dehydration to microphysical parameters and the nature of sub-grid scale temperature fluctuations. We then examine the year-to-year variations in potential dehydration using a trajectory climatology.

Pfister, Leonhard↗

Atmospheric carbon dioxide concentrations before 2.2 billion years ago

The composition of the Earth's early atmosphere is a subject of continuing debate. In particular, it has been suggested that elevated concentrations of atmospheric carbon dioxide would have been necessary to maintain normal surface temperatures in the face of lower solar luminosity in early Earth history. Fossil weathering profiles, known as palaeosols, have provided semi-quantitative constraints on atmospheric oxygen partial pressure (pO2) before 2.2 Gyr ago. Here we use the same well studied palaeosols to constrain atmospheric pCO2 between 2.75 and 2.2 Gyr ago. The observation that iron lost from the tops of these profiles was reprecipitated lower down as iron silicate minerals, rather than as iron carbonate, indicates that atmospheric pCO2 must have been less than 10(-1.4) atm--about 100 times today's level of 360 p.p.m., and at least five times lower than that required in one-dimensional climate models to compensate for lower solar luminosity at 2.75 Gyr. Our results suggest that either the Earth's early climate was much more sensitive to increases in pCO2 than has been thought, or that one or more greenhouse gases other than CO2 contributed significantly to the atmosphere's radiative balance during the late Archaean and early Proterozoic eons.

NASA Discipline Exobiology↗

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.

Toon, Owen B.↗

Models for Water Isotopes Constrained with Data from Crystal Face

During the year covered by this proposal we conducted work on several different topics, as reflected by our publications listed below. One major activity was to work with a group of about 10 scientists from around the country to prepare a science-planning document (Tropical Composition, Cloud and Climate Coupling Experiment (TC4)) 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. Unfortunately budgetary constraints prevented these missions from moving forward. In conjunction with the group NASA Ames we built a new numerical model for deep convection and have applied that model to simulate the CRYSTAL isotope data. Our goal in particular has been to better understanding 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 are now in press in Geophys. Res. Lett. 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 ana isotope abundances with this model. The data suggest that isotopes do not provide a clear constraint on the mechanism by which water enters the stratosphere- whether by convection, or by slow ascent. Our work is relevant for the water isotope comparison experiments recently done by NASA. We are conducting numerical experiments related to this project to help understand that data.

Toon, Owen B.↗

Improvement of Raman lidar algorithm for quantifying aerosol extinction

Aerosols are particles of different composition and origin and influence the formation of clouds which are important in atmospheric radiative balance. At the present there is high uncertainty on the effect of aerosols on climate and this is mainly due to the fact that aerosol presence in the atmosphere can be highly variable in space and time. Monitoring of the aerosols in the atmosphere is necessary to better understanding many of these uncertainties. A lidar (an instrument that uses light to detect the extent of atmospheric aerosol loading) can be particularly useful to monitor aerosols in the atmosphere since it is capable to record the scattered intensity as a function of altitude from molecules and aerosols. One lidar method (the Raman lidar) makes use of the different wavelength changes that occur when light interacts with the varying chemistry and structure of atmospheric aerosols. One quantity that is indicative of aerosol presence is the aerosol extinction which quantifies the amount of attenuation (removal of photons), due to scattering, that light undergoes when propagating in the atmosphere. It can be directly measured with a Raman lidar using the wavelength dependence of the received signal. In order to calculate aerosol extinction from Raman scattering data it is necessary to evaluate the rate of change (derivative) of a Raman signal with respect to altitude. Since derivatives are defined for continuous functions, they cannot be performed directly on the experimental data which are not continuous. The most popular technique to find the functional behavior of experimental data is the least-square fit. This procedure allows finding a polynomial function which better approximate the experimental data. The typical approach in the lidar community is to make an a priori assumption about the functional behavior of the data in order to calculate the derivative. It has been shown in previous work that the use of the chi-square technique to determine the most likely functional behavior of the data prior to actually calculating the derivative eliminates the need for making a priori assumptions. We note that the a priori choice of a model itself can lead to larger uncertainties as compared to the method that is validated here. In this manuscript, the chi-square technique that determines the most likely functional behavior is validated through numerical simulation and by application to a large body of Raman lidar measurements. In general, we show that the chi-square approach to evaluate aerosol extinction yields lower extinction uncertainty than the traditional technique. We also use the technique to study the feasibility of developing a general characterization of the extinction uncertainty that could permit the uncertainty in Raman lidar aerosol extinction measurements to be estimated accurately without the use of the chi-square technique.

Russo, Felicita↗

Sensitivity of Multi-Angle Remote Sensing Observations to Aerosol Sphericity

Multi-angle, multi-spectral remote sensing observations, such as those anticipated from the Earth Observing System (EOS) Multi-angle Imaging SpectroRadiometer (MISR), can distinguish spherical from non-spherical particles over calm ocean for mineral-dust-like particles with the range of sizes and column amounts expected under natural conditions. The ability to make such distinctions is critical if remote sensing of atmospheric aerosol properties is to provide significant new contributions to our understanding of the global-scale, clear-sky solar radiation balance.

MISR aerosol aerosol properties↗

Maritime Aerosol Network (MAN) as a Component of AERONET

The World Ocean produces a large amount of natural aerosols that have all impact on the Earth's albedo and climate. Sea-salt is the major contributor to aerosol optical depth over the oceans. [Mahowald et al. 2006; Chin et al. 2002; Satheesh et al. 1999; Winter and Chylek, 1997] and therefore affects the radiative balance over the ocean through the direct [Haywood et al. 1999] and indirect aerosol effect [O'Dowd et al. 1999]. Aerosols over the oceans (produced marine and advected from land sources) are important for various atmospheric processes [Lewis and Schwartz, 2004] and remote sensing studies [Gordon, 1997].

Smirnov, A.↗

Vertical Cloud Climatology During TC4 Derived from High-Altitude Aircraft Merged Lidar and Radar Profiles

Aircraft lidar works by shooting laser pulses toward the earth and recording the return time and intensity of any of the light returning to the aircraft after scattering off atmospheric particles and/or the Earth s surface. The scattered light signatures can be analyzed to tell the exact location of cloud and aerosol layers and, with the aid of a few optical assumptions, can be analyzed to retrieve estimates of optical properties such as atmospheric transparency. Radar works in a similar fashion except it sends pulses toward earth at a much larger wavelength than lidar. Radar records the return time and intensity of cloud or rain reflection returning to the aircraft. Lidar can measure scatter from optically thin cirrus and aerosol layers whose particles are too small for the radar to detect. Radar can provide reflection profiles through thick cloud layers of larger particles that lidar cannot penetrate. Only after merging the two instrument products can accurate measurements of the locations of all layers in the full atmospheric column be achieved. Accurate knowledge of the vertical distribution of clouds is important information for understanding the Earth/atmosphere radiative balance and for improving weather/climate forecast models. This paper describes one such merged data set developed from the Tropical Composition, Cloud and Climate Coupling (TC4) experiment based in Costa Rica in July-August 2007 using the nadir viewing Cloud Physics Lidar (CPL) and the Cloud Radar System (CRS) on board the NASA ER-2 aircraft. Statistics were developed concerning cloud probability through the atmospheric column and frequency of the number of cloud layers. These statistics were calculated for the full study area, four sub-regions, and over land compared to over ocean across all available flights. The results are valid for the TC4 experiment only, as preferred cloud patterns took priority during mission planning. The TC4 Study Area was a very cloudy region, with cloudy profiles occurring 94 percent of the time during the ER-2 flights. One to three cloud layers were common, with the average calculated at 2.03 layers per profile. The upper troposphere had a cloud frequency generally over 30%, reaching 42 percent near 13 km during the study. There were regional differences. The Caribbean was much clearer than the Pacific regions. Land had a much higher frequency of high clouds than ocean areas. One region just south and west of Panama had a high probability of clouds below 15 km altitude with the frequency never dropping below 25% and reaching a maximum of 60% at 11-13 km altitude. These cloud statistics will help characterize the cloud volume for TC4 scientists as they try to understand the complexities of the tropical atmosphere.

Hlavka, Dennis↗

Spectral Profiler Probe for In Situ Snow Grain Size and Composition Stratigraphy

An ultimate goal of the climate change, snow science, and hydrology communities is to measure snow water equivalent (SWE) from satellite measurements. Seasonal SWE is highly sensitive to climate change and provides fresh water for much of the world population. Snowmelt from mountainous regions represents the dominant water source for 60 million people in the United States and over one billion people globally. Determination of snow grain sizes comprising mountain snowpack is critical for predicting snow meltwater runoff, understanding physical properties and radiation balance, and providing necessary input for interpreting satellite measurements. Both microwave emission and radar backscatter from the snow are dominated by the snow grain size stratigraphy. As a result, retrieval algorithms for measuring snow water equivalents from orbiting satellites is largely hindered by inadequate knowledge of grain size.

Berisford, Daniel F.↗

Influence of Benzene on the Optical Properties of Titan Haze Laboratory Analogs in the Mid-Visible

The Cassini Ion and Neutral Mass Spectrometer (Waite, Jr., et al., 2007) and the Composite Infrared Spectrometer (Coustenis, A., et al., 2007) have detected benzene in the upper atmosphere and stratosphere of Titan. Photochemical reactions involving benzene in Titan's atmosphere may influence polycyclic aromatic hydrocarbon formation, aerosol formation, and the radiative balance of Titan's atmosphere. We measure the effect of benzene on the optical properties of Titan analog particles in the laboratory. Using cavity ring-down aerosol extinction spectroscopy, we determine the real and imaginary refractive index at 532 nm of particles formed by benzene photolysis and Titan analog particles formed with ppm-levels of benzene. These studies are compared to the previous study by Hasenkopf, et a1. (2010) of Titan analog particles formed by methane photolysis.

Yoon, Y. Heidi↗