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At least 235 records · Page 13

Modified HNO3 seasonality in volcanic layers of a polar ice core - Snow-pack effect or photochemical perturbation?

Changes in atmospheric HNO3 chemistry following the Laki (1783), Tambora (1815), and Katmai (1912) volcanic eruptions are presently investigated in view of a central Greenland ice core's chemical composition. Attention is given to the concentration of several cations and anions, using ion chromatography. Following the eruptions, the ratio of winter to summer depositions of NO3(-) was significantly higher than during nonvolcanic periods. While this may be due to ice pack effects, it is proposed that large concentrations of the stratospheric H2SO4 particles ejected by the volcanoes favored HNO3 removal during Arctic winter.

Laj, Paolo↗

Diagnostic studies of the HxOy-NxOy-O3 photochemical system using data from NASA GTE field expeditions

The research effort supported in part by the subject grant focused on three related topics. Our major effort was concentrated on the analysis of data gathered during GTE field expeditions. Ancillary efforts were directed at: the development and application of a Global Chemical Transport Model for the study of the atmospheric reactive nitrogen budget; the development and application of a one-dimensional, time dependent cloud model for the study of the impact of in-cloud aqueous phase chemistry on the atmospheric sulfur budget; and mechanistic studies of the chemical processes involved in dry deposition of ozone to vegetative surfaces. In the sections below, we briefly summarize the central conclusions of each of these efforts. These discussions are followed by a listing of the papers completed during the granting period and the graduate students supported by funds from the grant. Reprints and preprints of all papers completed with support from the grant are attached as appendices.

Chameides, W. L.↗

Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

Zahniser, Mark S.↗

Escape of Mars atmospheric carbon through time by photochemical means

Luhmann et al. recently suggested that sputtering of the Martian atmosphere by re-entering O(+) pickup ions could have provided a significant route of escape for CO2 and its products throughout Mars' history. They estimated that the equivalent of C in an approximately 140-mbar CO2 atmosphere should have been lost this way if the Sun and solar wind evolved according to available models. Another source of escaping C (and O) that is potentially important is the dissociative recombination of ionospheric CO(+) near the exobase. We have evaluated the loss rates due to this process for 'ancient' solar EUV radiation fluxes of 1, 3, and 6 times the present flux in order to calculate the possible cumulative loss over the last 3.5 Gyr.

Luhmann, J. G.↗

Uniqueness of a solution of a steady state photochemical problem: Applications to Mars

Based on the conservation of chemical elements in chemical reactions, a rule is proved that the number of boundary conditions given by densities and/or non-zero velocities should not be less than the number of chemical elements in the system, and the components given by densities and velocities should include all elements in the system. Applications of this rule to Mars are considered. It is proved that a problem of CO2-H2O chemistry in the lower and middle atmosphere of Mars, say, in the range of 0-80 km does not have an unique solution, if only CO2 and H2O densities are given at the lower boundary, while all other boundary conditions are fluxes. Two models of this type are discussed. These models fit the same boundary conditions, are balanced with a relative uncertainty of 10(exp -4) for H2, and predict the O2, CO, and H2 mixing ratios which differ by order of magnitude. One more species density, e.g. that of O2, should be specified at the boundary to obtain the unique solution. The situation is better if the upper boundary is extended to the exobase where thermal escape velocities of H and H2 can be specified. However, in this case, either oxygen nonthermal escape rate or the O2 density at the surface should be given as the boundary condition. Two models of Mars' photochemistry, with and without nitrogen chemistry, are considered. The oxygen nonthermal escape rate of 1.2 x 10(exp 8) cm(exp -2) s(exp -1) is given at 240 km and is balanced with the total hydrogen escape rate within uncertainty of 1 percent for both models. Both models fit the measured O2 and CO mixing ratios, the O3 line absorption at 9.6 microns, and the O2 1.27 microns dayglow within the uncertainties of the measured values; although, the model without nitrogen chemistry fits better.

Krasnopolsky, V. A.↗

Changes in photochemically significant solar UV spectral irradiance as estimated by the composite Mg II index and scale factors

Quantitative assessment of the impact of solar ultraviolet irradiance variations on stratospheric ozone abundances currently requires the use of proxy indicators. The Mg II core-to-wing index has been developed as an indicator of solar UV activity between 175-400 nm that is independent of most instrument artifacts, and measures solar variability on both rotational and solar cycle time scales. Linear regression fits have been used to merge the individual Mg II index data sets from the Nimbus-7, NOAA-9, and NOAA-11 instruments onto a single reference scale. The change in 27-dayrunning average of the composite Mg II index from solar maximum to solar minimum is approximately 8 percent for solar cycle 21, and approximately 9 percent for solar cycle 22 through January 1992. Scaling factors based on the short-term variations in the Mg II index and solar irradiance data sets have been developed to estimate solar variability at mid-UV and near-UV wavelengths. Near 205 nm, where solar irradiance variations are important for stratospheric photo-chemistry and dynamics, the estimated change in irradiance during solar cycle 22 is approximately 10 percent using the composite Mg II index and scale factors.

Deland, Matthew T.↗

In situ measurements of the NO2/NO ratio for testing atmospheric photochemical models

Simultaneous in situ measurements of NO2, NO, O3, ClO, pressure and temperature have been made for the first time, presenting a unique opportunity to test our current understanding of the photochemistry of the lower stratospere. Data were collected from several flights of the ER-2 aircraft at mid-latitudes in May 1993 during NASA's Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE). The daytime ratio of NO2/NO remains fairly constant at 19 km with a typical value of 0.68 and standard deviation of +/- 17. The ratio observations are compared with simple steady-state calculations based on laboratory-measured reaction rates and modeled NO2 photolysis rates. At each measurement point the daytime NO2/NO with its measurements uncertainty overlap the results of steady-state caculations and associated uncertainty. Possible sources of error are examined in both model and measurements. It is shown that more accurate laboratory determinations of the NO + 03 reaction rate and of the NO2 cross-sections in the 200-220 K temperature range characteristic of the lower stratosphere would allow for a more robust test of our knowledge of NO(X) phtochemistry by reducing significant sources if uncertainties in the interpretation of statospheric measurements.

Jaegle, L.↗

Uniqueness of a solution of a steady state photochemical problem: Applications to Mars

Based on the conservation of chemical elements in chemical reactions, a rule is proved that the number of boundary conditions given by densities and/or nonzero velocities should not be less than the number of chemical elements in the system, and the boundary conditions for species given by densities and velocities should include all elements in the system. Applications of this rule to Mars are considered. It is shown that the problem of the CO2-H2O chemistry in the lower and middle atmosphere of Mars, say, in the range of 0-80 km does not have a unique solution, if only CO2 and H2O densities are given at the lower boundary, and the remaining boundary conditions are fluxes. Two examples of models of this type are discussed. Two models of the photochemistry of the Martian atmosphere, with and without nitrogen chemistry, are considered. The oxygen nonthermal escape ratio of 1.2 x 10(exp 8)/cu cm/s is given at 240 km and is balanced with the total hydrogen escape rate within an uncertainty of 1% for both models. Both models fit the measured O2 and CO mixing ratios, the O3 abundance, and the O2 1.27-micrometer dayglow almost within the uncertainties of the measured values, though the model without nitrogen chemistry fits better. The importance of nitrogen chemistry in the lower and middle atmosphere of Mars depends on a fine balance between production of NO and N in the upper atmosphere which is not known within the required accuracy.

Krasnopolsky, Vladimir A.↗

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HOx and NOx species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences.

Zahniser, Mark S.↗

Interpretation of lidar and satellite data sets using a global photochemical model

The status in the beginning of the report period was that the existing General Circulation Model (GCM) was running with a chemistry module compiled for stratospheric simulation studies. The chemistry simulation was not working sufficiently in the troposphere and any tropospheric trace gas sources or dry deposition sinks were not yet incorporated. The current status concerning the chemistry module is that the chemistry simulation has been modified to also simulate the chemistry in the troposphere with resulting mixing ratios close to other model simulations as described in Olson et al. (1996). The mechanism to incorporate trace gas source and dry deposition sinks, testing for H202, CH300H, 03, HCHO, HN03, and N02, are incorporated and is currently being tested. Existing model and development versions include: the full GCM model, currently still running with the original stratospheric chemistry module; an off-line version of the GCM, i.e. wind and photolysis rates are pre-calculated and prescribed in read-in arrays; a box model version of the modified chemistry module for developments and first tests of new modifications; and a box model with the same chemistry simulated but flexible partitioning and integration methods for test purposes of those. The grantee's work focused mainly on three areas: trace gas sources and dry deposition; method to introduce a NO source instead of a NO(x) source; and investigating integration methods.

Chyba, Thomas↗

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanism in Stratospheric Models

The global three-dimensional measurement of long- and short-lived species from Upper Atmospheric Research Satellite (UARS) provides a unique opportunity to validate chemistry and dynamics mechanisms in the middle atmosphere. During the past three months, we focused on expanding our study of data-model comparisons to whole time periods when Cryogenic Limb Array Etalon Spectrometer (CLAES) instrument were operating.

Rodriquez, Jose M.↗

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanism in Stratospheric Models

We proposed model-data intercomparison studies for UARS data. In the past three months, we have been working on constructing analysis tools to diagnose the UARS data. The 'Trajectory mapping' technique, which was developed by Morris (1994), is adaptable to generate synoptic maps of trace gas data from asynoptic observations. An in-house trajectory model (kinematic methods following Merrill et al., 1986 and Pickering et al., 1994) has been developed in AER under contract with NASA/ACMAP and the trajectory mapping tool has been applied to analyze UARS measurement.

Rodriquez, Jose M.↗

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanism in Stratospheric Models

UARS data sets provide global coverage for the distributions of trace gases, which gives us an excellent chance to utilize the data set for model-data intercomparison studies. In the past three months, we have been working on the comparisons of the UARS data between 1992 (a half year after the Pinatubo eruption) and 1993 (one and a half year after the eruption) in an attempt to see how the Pinatubo volcanic eruption may have impacted stratospheric chemistry.

Rodriquez, Jose M.↗

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(x) and NO(x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. The second year's effort has focussed the design and construction of the proposed high pressure flow reactor on three separate areas: (1) the construction of the high pressure flow reactor; (2) characterization of the turbulent flow profile; and (3) demonstration of the instrument by measuring HO2 + NO2 and HO2 + NO reaction rate coefficients.

Villalta, Peter W.↗

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

This is the final report for this project. Its purpose is to reduce the uncertainty in rate coefficients for key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring the rate coefficients for the reactions of HO2 + O3, and HO2 + NO2 in the temperature range (200-240 K) relevant to the lower stratosphere. In order to accomplish this, a high pressure turbulent flow tube reactor was built and its flow characteristics were quantified. The instrument was coupled with tunable diode laser spectroscopy for HO2 detection. Room temperature measurements of the HO2 + NO2 rate coefficients over the pressure range of 50-300 torr agree well with previous measurements. Preliminary measurements of the HO2 + O, rate coefficients at 50 - 300 Torr over the temperature range of 208-294 K agree with the NASA evaluation from 294-225 K but deviate significantly (50 % higher) at approximately 210 K.

Villalta, P. W.↗

Tropospheric Diagnostic Modeling Studies of PEM-Tropics Field Data: Investigation of the HO(x)/NO(x)/O3 Photochemical System and Its Coupling to Sulfur and Halogen Chemistry

Over the time period of this NASA grant the PI has helped plan and execute in the PEM-Tropics A field program. He has also helped organize and co-chair three data workshops which have focused on the detailed analysis of PEM-Tropics A data. His direct participation in these analyses has led to his major involvement in 10 manuscripts, 5 of which are in print, 3 in press, and 2 submitted. A complete list of papers is included in the report.

Davis, Douglas D.↗

Interpretation of Lidar and Satellite Data Sets Using a Global Photochemical Model

A primary goal of the NASA Tropospheric Chemistry Program (TCP) is to "contribute substantially to scientific understanding of human impacts on the global troposphere". In order to analyze global or regional trends and factors of the troposphere chemistry, for example, its oxidation capacity or composition, a continuous global/regional data coverage as well as model simulations are needed. The Global Tropospheric Experiment (GTE), a major component of the TCP, provides data vital to these questions via aircraft measurement of key trace chemical species in various remote regions of the world. Another component in NASA's effort are satellite projects for exploration of tropospheric chemistry and dynamics. A unique data product is the Tropospheric Ozone Residual (TOR) utilizing global tropospheric ozone data. Another key research tool are simulation studies of atmospheric chemistry and dynamics for the theoretical understanding of the atmosphere, the extrapolation of observed trends, and for sensitivity studies assessing a changing anthropogenic impact to air chemistry and climate. In the context with model simulations, field data derived from satellites or (airborne) field missions are needed for two purposes: 1. To initialize and validate model simulations, and 2., to interpret field data by comparison to model simulation results in order to analyze global or regional trends and deviations from standard tropospheric chemistry and transport conditions as defined by the simulations. Currently, there is neither a sufficient global data coverage available nor are existing well established global circulation models. The NASA LARC CTM model is currently not yet in a state to accomplish a sufficient tropospheric chemistry simulation, so that the current research under this cooperative agreement focuses on utilizing field data products for direct interpretation. They will be also available for model testing and a later interpretation with a finally utilized model.

Zenker, Thomas↗

In Situ Measurements of the NO2/NO Ratio for Testing Atmospheric Photochemical Models

Simultaneous in situ measurements of NO2, NO, O3, ClO, pressure and temperature have been made for the first time, presenting a unique opportunity to test our current understanding of the photochemistry of the lower stratosphere. Data were collected from several flights of the ER-2 aircraft at mid-latitudes in May 1993 during NASA's Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE). The daytime ratio of NO2/NO remains fairly constant at 19 km with a typical value of 0.68 and standard deviation of +/- 0.17. The ratio observations are compared with simple steady-state calculations based on laboratory-measured reaction rates and modeled NO2 photolysis rates. At each measurement point the daytime NO2/NO with its measurement uncertainty overlap the results of steady-state calculations and associated uncertainty. However, over all the ER-2 flights examined, the model systematically overestimates the ratio by 40% on average. Possible sources of error are examined in both model and measurements. It is shown that more accurate laboratory determinations of the NO + O3 reaction rate and of the NO2 cross-sections in the 200-220 K temperature range characteristic of the lower stratosphere would allow for a more robust test of our knowledge of NO(x) photochemistry by reducing significant sources of uncertainties in the interpretation of stratospheric measurements. The present measurements are compared with earlier observations of the ratio at higher altitudes.

Jaegle, L.↗