Engineering topics
Publications and source records attributed to Chameides, W. L..
Absorption cross section measurements and model calculations indicate that CS2 photooxidation may be an important tropospheric sink for the CS2, giving a lifetime on the order of a week or two. If background CS2 levels are 10-20 pptv, then CS2 photooxidation may be an important global source of OCS as well.
Increased understanding of the chemical phenomena occurring in the troposphere was the research goal. Emphasis was placed on tropospheric impact on environmental quality, including public health, agriculture, climate, and weather.
A detailed study of the photochemistry of iodine and its oxides indicates that iodine species may play an important role in the tropospheric photochemical system. Methyl iodide, often observed in the marine troposphere with an average concentration of 5-10 ppt, is photolyzed and thereby produces I atoms. Chemical interactions with O3, HxOy, and NOx cause I to be converted to other inorganic compounds such as IO, HOI, IONO2, and I2. The production of these species and their subsequent recycling back to I can lead to the catalytic removal of tropospheric O3, the enhancement of the NO2/NO ratio, the destruction of HxOy free radicals, and the conversion of HO2 to OH. Ultimately, tropospheric inorganic iodine is removed by heterogeneous processes. Calculations using a numerical model to simulate tropospheric photochemistry indicate that iodine may have a strong impact upon the atmospheric O3-NOx-HxOy system. The magnitude of these effects is dependent upon the value of several uncertain rate constants and the primary source distributions of CH3I and other organic and inorganic iodine compounds.
The present understanding of the physical and chemical behavior of methane, carbon monoxide and the chemical species involved in the conversion of CH4 to CO in the troposphere is reviewed. Following a brief summary of CO and CH4 emission and reactions in urban areas, attention is given to measurements of the spatial and temporal distributions of CO and CH4 in the rural atmosphere, the contribution of the oceans to atmospheric CO and CH4 concentrations, and interactions of CH4 and CO with soils and vegetation. Estimates of the transport of CH4 and CO from the troposphere to the stratosphere are discussed, and photochemical reactions of the constituents are examined. Two- and three-dimensional models for CH4 and CO transport are presented, and possible future variations in atmospheric abundances of the molecules are considered. Finally, present estimates of the global methane and carbon dioxide budgets are summarized, and it is pointed out that, despite the large contribution of anthropogenic sources, the budgets appear to be in balance.
The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.
Calculations of long-wave atmospheric heating and cooling rates using the rate equations of Rodgers and Walshaw (1966) with the Malkmus (1967) random band model are presented. A perturbation scheme is developed for the inclusion of aerosol scattering effects in the numerical calculation. Unlike the flux differencing method for calculating long-wave heating and cooling rates, this scheme allows aerosol effects to be included in a simple manner with only a small additional use of computer time. The calculations indicate good agreement with those of previous investigators and demonstrate the expected equivalence of the flux-differencing method and the flux-divergence equation of Rodgers and Walshaw (1966), even at stratospheric altitudes. It is found that aerosols lead to a net heating in the lower troposphere due to infrared scattering and absorption.
Enhanced levels of N2O and CO were measured in tropospheric air samples exposed to a 17,500-J laboratory discharge. These enhanced levels correspond to an N2O production rate of about 4 trillion molecules/J and a CO production rate of about 10 to the 14th molecules/J. The CO measurements suggest that the primary region of chemical production in the discharge is the shocked air surrounding the lightning channel, as opposed to the slower-cooling inner core. Additional experiments in a simulated Venus atmosphere (CO2 - 95%, N2 - 5%, at one atmosphere) indicate an enhancement of CO from less than 0.1 ppm prior to the laboratory discharge to more than 2000 ppm after the discharge. Comparison with theoretical calculations appears to confirm the ability of a shock-wave/thermochemical model to predict the rate of production of trace species by an electrical discharge.
The high temperature chemistry of the N-O-H-C system has been studied to determine the production of NO and CO by atmospheric lightning. The yield of NO is found to be equivalent to results obtained for a pure N2/O2 atmosphere. The CO yield is highly dependent upon the detailed cooling processes within the discharge and thus an experiment designed to measure the CO source in discharges could yield useful insights into the discharge itself. An upper limit of 3.5 x 10 to the 11th g CO per yr is estimated for the global CO source from lightning.
The reported analysis implies that the number of molecules of NO produced per joule of discharge varies with input energy. The calculations assume a cylindrical symmetry but the results are consistent with equivalent calculations using spherical symmetry. If NO yield does vary with input energy, extrapolation of laboratory experiments using small sparks is not as straightforward as has previously been assumed. Calculated curves for the yield of NO as a function of discharge energy are presented and are compared with experimental values and other theoretical values.
An investigation was conducted to determine whether nonmethane hydrocarbons (NMHC) are abundant enough to have a significant impact upon the ambient photochemistry. The vertical distribution of C2H6, C2H2, C3H8, C4H10, and C5H12 in the altitude range from 0 to 40 km was calculated in this connection. A one-dimensional steady state model with coupled photochemistry and vertical transport was employed in the investigation. The calculations imply that measurable quantities of relatively unreactive NMHC, especially C2H6 and C2H2, may be present in the upper troposphere and stratosphere. The results indicate, however, that NMHC are not likely to have a large impact on the background photochemistry of the troposphere, although local effects near source regions are probable. The findings support the current practice of many modelers who neglect NMHC in their calculations.
The role of nitrogen oxides in the tropospheric photochemical system is re-evaluated in the light of recent measurements of the rate constants for two key reactions. A model for nitrogen oxides is discussed which yields surface NO(x) (NO+NO2) levels approaching 1 ppb in NO(x) source regions but less than 0.1 ppb outside source regions. Applying the new rate coefficients implies increased radical concentrations and a more intense O3 and CO photochemistry. Even for densities of 0.1 ppb or less, NO(x) still leads to significant local O3 production and conversion of HO2 to OH. Unrealistic O3 profiles are obtained with the new rate coefficients for surface NO(x) densities of about 1 ppb, while reasonable agreement with observation is obtained with lower NO(x) densities. Feedback processes between CO, NO(x), OH, and CH4 are also discussed.
Photochemical model calculations indicate that significant perturbations in tropospheric OH, CH4, and related compounds may occur in the coming decades due to increased anthropogenic emissions of CO and NO(x). The magnitude and direction of the perturbation depends on future emission rates of CO and NO(x) and also on the efficiency with which urban NO(x) is transported to the ambient atmosphere. If CO and NO(x) emissions increase at comparable rates, the CO effect on OH will dominate and OH will decrease while CH4 increases. The effects of a variation in tropospheric OH, halocarbons, and other compounds include a perturbation to stratospheric ozone and the atmosphere's thermal equilibrium.
The terrestrial and marine nitrogen cycles are examined in an attempt to clarify how the atmospheric content of N2O is controlled. We review available data on the various reservoirs of fixed nitrogen, the transfer rates between the reservoirs, and estimate how the reservoir contents and transfer rates can change under man's influence. It is seen that sources, sinks and lifetime of atmospheric N2O are not understood well. Based on our limited knowledge of the stability of atmospheric N2O we conclude that future growth in the usage of industrial fixed nitrogen fertilizers could cause a 1% to 2% global ozone reduction in the next 50 years. However, centuries from now the ozone layer could be reduced by as much as 10% if soils are the major source of atmospheric N2O.
The budget of tropospheric ozone is re-examined in the light of lower observed nitrogen oxide densities and revised reaction rates. To estimate the relative importance of transport and photochemistry, model calculations are presented which determine one-dimensional vertical ozone profiles at midlatitudes for equinoctial conditions. These calculations imply that both photochemistry and transport are important in controlling the abundance of tropospheric ozone. It is estimated that photochemical processes produce about 0.6 times 10 to the eleventh and destroy about 1.4 times 10 to the eleventh tropospheric ozone molecules per sq cm per sec, while mixing processes transport about 1.4 times 10 to the eleventh ozone molecules per sq cm per sec from the stratosphere into the troposphere and ground level fluxes destroy about 0.6 times 10 to the eleventh ozone molecules per sq cm per sec. The sensitivity of our model calculations to transport parameters, key rate coefficients, and nitrogen oxide densities are discussed.
A model coupling photochemistry and vertical transport in the troposphere has been used to investigate the magnitude of possible future perturbations to atmospheric CH4. The response of atmospheric CH4 to an increase in the concentration of CO or to a variation in stratospheric O3 is studied. Both of the above mechanisms, which could be caused by man's activities, arise because a change in the concentration of tropospheric OH will lead to a change in the CH4 abundance. The calculations imply that a perturbation of about 30-40% in atmospheric CH4 could occur if stratospheric O3 were perturbed by 10% or if man-made CO continued to increase. The possible consequences of a CH4 perturbation may entail a perturbation in stratospheric photochemistry or in the thermal balance of the atmosphere.
The rate of odd nitrogen (NOx) production by electrical discharge through air was theoretically and experimentally estimated to be about 60,000 trillion NOx molecules per joule. The theoretical treatment employed a cylindrical shock-wave solution to calculate the rate of NOx production in high temperature reactions. The limits obtained were experimentally verified by subjecting a regulated air flow to electrical discharges followed by a measurement of NOx production using chemiluminescence. These measurements also indicated that water vapor content has no detectable effect on the NOx production rate. The results imply that lightning is a significant source of NOx, producing about 30-40 megatons NOx-N per year and possibly accounting for as much as 50% of the total atmospheric NOx source.
The daytime electron temperature profile of the Jovian ionosphere was calculated, taking into account the effects of thermal conduction and heat inflow from the plasmasphere. The photoelectron fluxes and electron heating rates were determined by using the two-stream approach of Banks and Nagy (1970) and Nagy and Banks (1970). The calculated electron temperatures were found to follow the neutral temperature up to an altitude slightly above the electron density peak, while at higher altitudes they were significantly enhanced above the assumed neutral temperature value.
Results are presented for a self-consistent one-dimensional coupled flow calculation for Ox, NOx, HOx, ClX, H2O, H2, CH4, H2O2, and N2O densities between 10 and 120 km. The results agree well with observations for the normal midlatitude atmosphere over this altitude range. ClX, NOx, and H2O are varied independently in the model considered. It is shown that the effect of depletion of ozone by ClX is to remove ozone preferentially above 30 km and to lower the altitude of maximum ozone density. This leads to enhanced solar heating of the lower stratosphere and tropopause and suggests the possibility of an increased flux of water into the stratosphere. Increasing water vapor in the stratosphere greatly enhances the rate of destruction of O3 by ClX and also causes an increase in the rate of destruction of O3 in the NOx-perturbed atmosphere.