Engineering topics

Chameides, W. L.

Publications and source records attributed to Chameides, W. L..

At least 19 records

NASA NTRS1995

The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl4, C2Cl4, C2HCL3, CH3CCl3, and CHCl3

A study of the tropospheric and stratospheric cycles of phosgene is carried out to determine its fate and ultimate role in controlling the ozone depletion potentials of its parent compounds. Tropospheric phosgene is produced from the OH-initiated oxidation of C2Cl4, CH3CCl3, CHCl3, and C2HCl3. Simulations using a two-dimensional model indicate that these processes produce about 90 pptv/yr of tropospheric phosgene with an average concentration of about 18 pptv, in reasonable agreement with observations. We estimate a residence time of about 70 days for tropospheric phosgene, with the vast majority being removed by hydrolysis in cloudwater. Only about 0.4% of the phosgene produced in the troposphere avoids wet removal and is transported to the stratosphere, where its chlorine can be released to participate in the catalytic destruction of ozone. Stratospheric phosgene is produced from the photochemical degradation of CCl4, C2Cl4, CHCl3, and CH3CCl3 and is removed by photolysis and downward transport to the troposphere. Model calculations, in good agreement with observations, indicate that these processes produce a peak stratospheric concentration of about 25-30 pptv at an altitude of about 25 km. In contrast to tropospheric phosgene, stratospheric phosgene is found to have a lifetime against photochemical removal of the order of years. As a result, a significant portion of the phosgene that is produced in the stratosphere is ultimately returned to the troposphere, where it is rapidly removed by clouds. This phenomenon effectively decreases the amount of reactive chlorine injected into the stratosphere and available for ozone depletion from phosgene's parent compounds. A similar phenomenon due to the downward transport of stratospheric COFCl produced from CFC-11 is estimated to cause a 7% decrease in the amount of reactive chlorine injected into the stratosphere from this compound. Our results are potentially sensitive to a variety of parameters, most notably the rate of reaction of phosgene with sulfate aerosols. However, on the basis of the observed vertical distribution of COCl2, we estimate that the reaction of COCl2 with sulfate aerosol most likely has a gamma less than 5 x 10(exp -5) and, as a result, has a negligible impact on the stratospheric chlorine loadings of the phosgene parent compounds.

Kindler, T. P.↗

NASA NTRS1990

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.↗

NASA NTRS1990

Natural hydrocarbons, urbanization, and urban ozone

The combined effects of emission control and urbanization, with its concomitant intensification of the urban heat island, on urban ozone concentrations are studied. The effect of temperature on ozone is considered, and attention is given to the temperature effect on ozone photochemistry. Model calculations suggest that ozone concentration enhancements are caused by the effect of temperature on the atmospheric chemistry of peroxyacetyl nitrate, as well as the temperature dependence of natural and anthropogenic hydrocarbon emissions. It is pointed out that, because of the sensitivity of urban ozone to local climatic conditions and the ability of trees to moderate summertime temperatures, the inadvertent removal of trees from urbanization can have an adverse effect on urban ozone concentration, while a temperature increase in the urban heat island caused by urbanization can essentially cancel out the ozone-reducing benefits obtained from a 50-percent reduction in anthropogenic hydrocarbon emissions.

Cardelino, C. A.↗

NASA NTRS1990

Observed and model-calculated NO2/NO ratios in tropospheric air sampled during the NASA GTE/CITE-2 field study

Airborne measurements of NO2/NO ratios in the free troposphere, obtained using two-photon LIF (TP-LIF) and chemiluminescence (CL) detectors during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986, are analyzed and compared with the predictions of a photochemical model. The derivation of the model is outlined, with an emphasis on the role of peroxy radicals in the fast photochemical cycling of NO and NO2 and the production of O3; the CITE 2 instruments and flight protocols are described; and the results are presented in extensive tables and graphs and discussed in detail. It was found that on three CITE 2 flights the CL data were systematically greater than the TP-LIF data; when these data were removed, the averaged values of the two instruments agreed to within 1 percent. The NO2/NO ratios predicted by the model are shown to be consistent with the measurements, although usually 20-25 percent lower.

Chameides, W. L.↗

NASA NTRS1990

Possible atmospheric lifetimes and chemical reaction mechanisms for selected HCFCs, HFCs, CH3CCl3, and their degradation products against dissolution and/or degradation in seawater and cloudwater

For a wide variety of atmospheric species including CO2, HNO3, and SO2, dissolution in seawater or cloudwater followed by hydrolysis or chemical reaction represents a primary pathway for removal from the atmosphere. In order to determine if this mechanism can also remove significant amounts of atmospheric chlorofluorocarbons (HCFC's), fluorocarbons (HFC's), and their degradation products, an investigation was undertaken as part of the Alternative Fluorocarbons Environmental Acceptability Study (AFEAS). In this investigation, the rates at which CHCl2CF3 (HCFC-123), CCl2FCH3 (HCFC-141b), CClF2CH3 (HCFC-142b), CHClF2 (HCFC-22), CHClFCF3 (HCFC-124) CH2FCF3 (HFC-134a) CHF2CH3 (HFC-152a), CHF2CF3 (HFC-125), and CH3CCl3 can be dissolved in the oceans and in cloudwater were estimated from the species' thermodynamic and chemical properties using simple mathematical formulations to simulate the transfer of gases from the atmosphere to the ocean or cloudwater. The ability of cloudwater and rainwater to remove gas phase degradation products of these compounds was also considered as was the aqueous phase chemistry of the degradation products. The results of this investigation are described.

Wine, P. H.↗

NASA NTRS1989

Ozone precursors and ozone photochemistry over eastern North Pacific during the spring of 1984 based on the NASA GTE/CITE 1 airborne observations

Simultaneous high-resolution measurements of O3, NO, CO, dew point temperature, and UV flux obtained during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation (GTE/CITE 1) spring 1984 airborne field exercise over the eastern North Pacific Ocean are analyzed. Mid-tropospheric CO, O3, and NO mixing ratios averaged about 120 parts per billion by volume (ppbv), 50 ppbv, and 10 parts per trillion by volume (pptv), respectively. Statistical analysis of the high-resolution data indicates the existence of two ozone sources, one related to the downward transport of ozone-rich air from the upper troposphere and stratosphere, and the other to the transport of ozone-rich air from the continents. Modeling calculations based on these average levels imply that, from the surface to about 8 km, photochemical reactions probably supplied a net sink of ozone to the region overlying the eastern North Pacific Ocean during the sampling period. However, because the NO levels measured during the flights were frequently at or near the detection limit of the instruments and because the results are very sensitive to the absolute NO levels and their temporal variability, the conclusion must be considered provisional.

Chameides, W. L.↗

NASA NTRS1987

Net ozone photochemical production over the eastern and central North Pacific as inferred from GTE/CITE 1 observations during fall 1983

The role of photochemistry in the budget of tropospheric ozone is studied. Measurements of O3, NO, CO, H2O vapor, and temperature obtained during the fall of 1983 during the GTE/CITE project over the eastern and central North Pacific Ocean are analyzed. The effect of altitude on the measurements is discussed. The analysis reveals a correlation between ozone and NO levels; both increase in concentration and variability with altitude. It is observed that an additional source of secondary importance associated wih CO-rich air parcels exists. A photochemical model is utilized to calculate the net rate of ozone production by photochemical reactions. A net photochemical source of ozone in the free troposphere and a net sink in the boundary layer are detected. The relation between the ozone source in the free troposphere and NO is examined. It is estimated that photochemistry provides a net ozone source to the free troposphere overlying the eastern and central North Pacific Ocean of about 5 x 10 to the 10th molecules/sq cm sec and a net sink of ozone to the boundary layer overlying this region of about 3 x 10 to the 10th molecules/sq cm sec.

Chameides, W. L.↗

NASA NTRS1987

An estimate of the NO(x) production rate in electrified clouds based on NO observations from the GTE/CITE 1 fall 1983 field operation

During the NASA GTE/CITE 1 fall 1983 airborne field operation the NASA Convair 990 penetrated the anvils of two active cumulonimbus clouds. While NO levels outside the anvils averaged about 20 parts per trillion per volume (pptv), the average NO inside the anvils was about 440 pptv. Extrapolation of this observation along with data on the amount of air typically advected out of cumulonimbus clouds and the total number of thunderclouds occurring over the globe at any moment, implies a rate of nitrogen fixation in electrified clouds of about 7 x 10 to the 6th trillion/yr. Although the data base used to make this estimate is quite limited, the approach differs from that used in previous studies of the global production of nitrogen oxides by lightning, and thus represents an independent assessment of the role of electrified clouds in the atmospheric nitrogen oxide budget.

Chameides, W. L.↗

NASA NTRS1986

The removal of soluble species by warm stratiform clouds

The development of a one-dimensional, time-dependent model to study the removal of soluble gases from a warm, precipitating stratiform cloud is reported. The model calculates the distributions of water vapor and condensed water, in the form of cloud drops and raindrops, as well as the in-cloud concentration of a soluble species in the gas and aqueous phases for a specified profile of pressure and temperature and an assumed updraft velocity. Highly soluble gases are found to be rapidly dissolved into cloud droplets and then slowly incorporated into raindrops as cloudwater is converted to rainwater. The rainout rate for highly soluble species is found to be ultimately limited by the rate at which new gaseous material can be transferred from the cloud-free air into the cloud. The model calculations indicate that turbulence represents an important mechanism by which highly soluble gases are transported into stratiform clouds.

Qin, YU↗

NASA NTRS1986

Possible role of NO3 in the nighttime chemistry of a cloud

The NO3 radical in the aqueous phase is a strong oxidizing agent which reacts rapidly with a wide variety of inorganic and organic species. Within nighttime clouds the production of gaseous NO3 from the reaction of NO2 with O3 followed by heterogeneous scavenging of NO3 by cloud droplets can represent a significant source of these reactive radicals to cloud water. Model calculations indicate that in addition to leading to the production of NO3(-) in cloud water, this aqueous-phase source of NO3 can, under the appropriate conditions and depending upon the values for a number of uncertain rate constants, have a significant impact upon the rate of conversion of SO2 to H2SO4.

Chameides, W. L.↗

NASA NTRS1985

The rainout parameterization in a photochemical model

Photochemical models of tropospheric trace species typically simulate the effects of wet removal of soluble species from the atmosphere through a first-order rainout parameterization, which is independent of the species solubility and constant in time. In this work a modified first-order rainout parameterization is proposed that is a function of the species' solubility and takes into account the intermittent nature of atmospheric wet removal. In the case of a highly soluble species, such as HNO3, the inclusion of the effects of intermittent rainout in the parameterization leads to averaged rainout lifetimes considerably higher than ones used in most photochemical models. For illustrative purposes this parameterization is applied to a one-dimensional steady state model with parameterized eddy diffusion, although in principle it can be used in more sophisticated multidimensional models. The model results are compared to analagous calculations obtained with a 3-D tracer transport model.

Giorgi, F.↗

NASA NTRS1984

Lightning - Estimates of the rates of energy dissipation and nitrogen fixation

The nitrogen needed by plants can normally not be directly obtained from the nitrogen present in molecular form in the atmosphere. The reason for this situation is related to the great energy required to break the N-N bond. Only a few organisms, such as algae and certain bacteria, can 'fix' nitrogen. An abiological process for breaking the N-N bond is provided by lightning. The present investigation is concerned with this possibility. It is found that lightning produces approximately 2.6 x 10 to the 9th kg N per year. There are, however, uncertainties, which are mainly related to the energy of a lightning flash.

Borucki, W. J.↗

NASA NTRS1984

The photochemistry of a remote marine stratiform cloud

The coupled gas- and aqueous-phase photochemistry of a stratiform cloud in a remote region of the marine atmosphere is investigated with a time-dependent box model. Both scavenging of ambient acidic aerosols and gases as well as aqueous-phase chemical reactions within droplets are found to be important sources of acidity to cloud water and can lead to pH levels in cloud water in the remote marine atmosphere well below 5.6. The major sources of acidity via aqueous-phase chemical reactions are the generation of sulfuric acid from dissolved SO2 and the generation of formic acid from dissolved formaldehyde. In both cases, aqueous-phase free radicals can play a significant role either directly by oxidizing dissolved SO2 and HCHO or indirectly by producing the aqueous-phase oxidant H2O2. The rate of SO2 conversion to sulfuric acid is sensitive to a variety of parameters including the accommodation or sticking coefficient for SO2, H2O2, HO2, and OH, the liquid water content, and the ambient levels of SO2, HNO3, and other acidic or basic gases. Because high levels of SO2 tend to deplete cloud water of H2O3, the possibility exists that the pH of precipitation in polluted regions will respond nonlinearly to reduced SO2 emissions.

Chameides, W. L.↗

NASA NTRS1983

Aqueous-phase source of formic acid in clouds

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

Chameides, W. L.↗

NASA NTRS1982

The free radical chemistry of cloud droplets and its impact upon the composition of rain

Calculations are presented that simulate the free radical chemistries of the gas phase and aqueous phase within a warm cloud during midday. It is demonstrated that in the presence of midday solar fluxes, the heterogeneous scavenging of OH and HO2 from the gas phase by cloud droplets can represent a major source of free radicals to cloud water, provided the accommodation or sticking coefficient for these species impinging upon water droplets is not less than 0.0001. The aqueous-phase of HO2 radicals are found to be converted to H2O2 by aqueous-phase chemical reactions at a rate that suggests that this mechanism could produce a significant fraction of the H2O2 found in cloud droplets. The rapid oxidation of sulfur species dissolved in cloudwater by this free-radical-produced H2O2 as well as by aqueous-phase OH radicals could conceivably have a significant impact upon the chemical composition of rain.

Chameides, W. L.↗

NASA NTRS1982

H2O2 levels in rainwater collected in south Florida and the Bahama Islands

Measurements of H2O2 in rainwater collected in Miami, Florida, and the Bahama Islands area indicate the presence of H2O2 concentration levels ranging from 100,000 to 700,000 M. No systematic trends in H2O2 concentration were observed during an individual storm, in marked contrast to the behavior of other anions for example, NO3(-), SO4(-2), and Cl(-). The data suggest that a substantial fraction of the H2O2 found in precipitation is generated by aqueous-phase reactions within the cloudwater rather than via rainout and washout of gaseous H2O2.

Zika, R.↗

NASA NTRS1981

Rates of fixation by lightning of carbon and nitrogen in possible primitive atmospheres

A thermochemical-hydrodynamic model of the production of trace species by electrical discharges has been used to estimate the rates of fixation of C and N by lightning in the primitive atmosphere. Calculations for various possible mixtures of CH4, CO2, CO, N2, H2, and H2O reveal that the prime species produced were probably HCN and NO and that the key parameter determining the rates of fixation was the ratio of C atoms to O atoms in the atmosphere. Atmospheres with C more abundant than O have large HCN fixation rates, in excess of 10 to the 17th molecules/J, but small NO yields. However, when O is more abundant than C, the NO fixation rate approaches 10 to the 17th molecules/J while the HCN yield is small. The implications for the evolution of life are discussed.

Chameides, W. L.↗

NASA NTRS1981

The two-dimensional diagnostic model for tropospheric OH - An uncertainty analysis

Tropospheric OH is believed to play a major role in atmospheric photochemistry, and, via its chemical interactions OH ultimately may affect the climate, stratospheric ozone levels, and the pH of rain. A valuable tool for predicting the global OH abundance as a function of latitude and altitude is the two-dimensional diagnostic model for tropospheric OH. This model can also be applied to budget studies of species which interact with OH, such as CH4, CO, and O3. In addition to laboratory-obtained kinetic data, important variables include the rate constants for several reactions, the rate of heterogeneous removal of soluble species, and the global abundance and spatial variability in H2O, O3, CO, and NOx. The uncertainties in these parameters imply over a factor of 3 variability in the calculated global OH concentration as well as significant uncertainties in the latitudinal and vertical OH distribution.

Chameides, W. L.↗