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Mcelroy, M. B.

Publications and source records attributed to Mcelroy, M. B..

At least 19 records

Absorption of solar radiation by O2 - Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2

An accurate line-by-line model is used to evaluate effects of absorption in the Schumann-Runge bands of O2 on transmission of UV radiation. The model is used to evaluate rates of photolysis for N2O, CFCl3, and CF2Cl2, and to infer global loss rates and instantaneous lifetimes appropriate for 1980. A parameterized version of the line-by-line model enabling rapid evaluation of transmission in the Schumann-Runge region is described. Photochemical calculations employing the parameterization and constrained by data from the Atmospheric Trace Molecule Spectroscopy experiment are used to examine the budget of odd oxygen. Consistent with previous studies, it is shown that photochemical loss of odd oxygen exceeds production by photolysis of O2 for altitudes above 40 km. The imbalance between production and loss is shown to be consistent with a source of odd oxygen proportional to the product of the mixing ratio and photolysis rate of ozone, which suggests that processes involving vibrationally excited O2 may play an important role in production of odd oxygen.

Minschwaner, K.

Tropospheric OH in a three-dimensional chemical tracer model - An assessment based on observations of CH3CCl3

The paper introduces the representation of tropospheric chemistry allowing for calculation of chemical reaction rates within a chemical tracer model (CTM) simulation with the accuracy comparable to that of a detailed chemical model. The global distribution of tropospheric OH is calculated as a function of time, atmospheric composition, temperature, and solar irradiance. The globally integrated OH concentration weighted by frequency of reaction with CH3CCl3 is evaluated, along with the feasibility of using the observed latitudinal distribution of CH3CCl3 as a test for computed concentrations of OH. Seasonal variations of CH3CCl3 are also considered as a potential test for computed concentrations of OH. It is demonstrated that annual cycles of CH3CCl3 are controlled, or strongly influenced, by dynamical processes at latitudes northward of 25 deg South.

Spivakovsky, C. M.

Condensation of HNO3 on falling ice particles - Mechanism for denitrification of the polar stratosphere

Ice particles created in polar stratospheric cooling events are predicted to descend into Type I PSCs and accrete a coating of nitric acid trihydrate (NAT) that inhibits evaporation. Coated particles efficiently strip HNO3 from the atmosphere, providing a mechanism for denitrification without significant dehydration. Coatings that disintegrate may release large particles of NAT that influence subsequent particle growth.

Wofsy, S. C.

Denitrification in the Antarctic stratosphere

Rapid loss of ozone over Antarctica in spring requires that the abundance of gaseous nitric acid be very low. Precipitation of particulate nitric acid has been assumed to occur in association with large ice crystals, requiring significant removal of H2O and temperatures well below the frost point. However, stratospheric clouds exhibit a bimodal size distribution in the Antarctic atmosphere, with most of the nitrate concentrated in particles with radii of 1 micron or greater. It is argued here that the bimodal size distribution sets the stage for efficient denitrification, with nitrate particles either falling on their own or serving as nuclei for the condensation of ice. Denitrification can therefore occur without significant dehydration, and it is unnecessary for temperatures to drop significantly below the frost point.

Salawitch, R. J.

The chemistry of Antarctic ozone 1960-1987

The factors that influence Antarctic ozone are examined with a view to understanding the observed historical trend. Researchers show that reduced ambient temperatures can dramatically enhance the efficiency of chemical removal processes. Attention is focused on positive feedback between levels of ozone, temperature, and rates of heterogeneous chemical reactions. ClO and its dimer, and high levels of these gases are maintained until the clouds evaporate, on 15 September for the simulation shown here.

Salawitch, R. J.

Interactions between HCl, NO(x), and H2O ice in the Antarctic stratosphere - Implications for ozone

The role of PSC particles in determining the distributions of HCl and chlorine radicals is studied. The thermodynamics of HCl in ice is discussed, showing that significant quantities of HCl may be dissolved in ice when PSCs form. It is argued that HCl and HNO3 will be removed from the gas phase early in the condensation process, when only small quantities of H2O have been condensed, reflecting the thermodynamic properties of the solid phases of HCl, HNO3, and H2O. Rapid heterogeneous chemical reactions then volatilize reactive chlorine gases and convert NO(x) to solid-phase nitrates, which can be removed by gravitational settling. Analysis of the suite of heterogeneous chemical processes in the polar stratosphere implies a threshold for HCl concentrations, above which chemical loss rates for ozone increase dramatically.

Wofsy, S. C.

Sources of atmospheric nitrous oxide from combustion

Emissions of nitrous oxide (N2O) have been analyzed from industrial boilers and from a large experimental combustor burning natural gas, oil, or coal. Production of N2O and production of NO(x) were observed to be correlated, with an average molar ratio of 0.58:1 (N2O-N:NO). In conventional single-stage combustors, about 14 percent of fuel nitrogen is converted to N2O and 24 percent is converted to NO(x). Conversion of fuel nitrogen to N2O was much less efficient in a two-stage experimental combustor and in wood fires. A model is presented describing emissions of N2O globally, from the beginning of the industrial revolution to the present. It is expected that concentrations of N2O should rise more than 20 percent to about 367 ppb by the year 2050, based on conservative projections of world energy consumption.

Hao, W. M.

Photodissociation of metastable O2(a 1 Delta g): Implications for stratospheric O3

The potential energy curves of Saxon and Liu (1977) are used to calculate nuclear radial wave functions for O2 in the a 1 Delta g and C 3 Delta u states. Franck-Condon factors are evaluated for both bound-bound and bound-free transitions. Observational values for the radiative lifetimes of discrete vibrational levels of the C 3 Delta u state are used to place constraints on the cross section for photodissociaation of a 1 Delta g. It is argued that the cross section for the dissociation of O2(a 1 Delta g) through the C 3 Delta u state is smaller by four orders of magnitude than values required by Frederick and Cicerone (1985) to resolve the apparent discrepancy between computed and measured concentrations for O3 in the upper atmosphere.

Dalgarno, A.

Reductions of Antarctic ozone due to synergistic interactions of chlorine and bromine

The vertical column density of ozone observed in October over Antarctica has fallen precipitously over the past 10 yr. The concentration at Halley Bay (76 deg S, 27 deg W), expressed conventionally in Dobson units (DU), has dropped from about 300 DU in 1975 to less than 200 DU in 1984. Values in 1985 were even lower, comparable with the lowest values recorded anywhere on earth. It is suggested here that the loss of O3 in Antarctica may be attributed to catalysis of O3 recombination by a scheme in which the rate-limiting step is defined by the reaction of ClO + BrO - Cl + Br + O2. Concentrations of NO2 must be low and heterogeneous reactions involving particles in the polar stratospheric clouds must be an important element of the relevant chemistry. Industrial sources make important contributions to the contemporary budgets of both BrO and ClO and are likely to grow significantly in the future.

Mcelroy, M. B.

Changes in atmospheric CO2 - Factors regulating the glacial to interglacial transition

Observations of pCO2 and delta-C-13 for the deep sea, and delta-C-13 for shallow waters, furnish important constraints on the chemistry of the glacial ocean. The concentration of preformed nutrients in the model presented reflects the concentration of nitrogen at depth, the efficiency with which nitrogen is supplied to the cold surface water by exchange with the intermediate layer, the extent to which nutrients in the cold surface regime are diluted by low nutrient water from lower latitude, and the efficiency with which nutrients are used up by the local cold water biota.

Ennever, F. K.

Reductions in ozone at high concentrations of stratospheric halogens

An increase in the concentration of inorganic chlorine to levels comparable to that of oxidized reactive nitrogen could cause a significant change in the chemistry of the lower stratosphere leading to a reduction potentially larger than 15 percent in the column density of ozone. This could occur, for example by the middle of the next century, if emissions of man-made chlorocarbons were to grow at a rate of 3 percent per year. Ozone could be further depressed by release of industrial bromocarbon.

Prather, M. J.

Hydrogen on Venus - Exospheric distribution and escape

The spatial distribution of suprathermal H in the Venus atmosphere is calculated using an approximate numerical solution of the time-independent Boltzmann equation. Sources of suprathermal H are specified on the basis of Pioneer Venus measurements. Reactions involving H2 are neglected. The computed densities of suprathermal H are in satisfactory agreement with profiles derived from analysis of Lyman-alpha airglow by Mariners 5 and 10 and Veneras 11 and 12. The dayside emission at radial distances larger than 18,000 km is attributed to scattering of solar photons by fast H atoms produced primarily on the nightside near midnight. The nightside ionosphere, and consequently the source of suprathermal H, are both expected to vary in response to changes in the solar wind.

Rodriguez, J. M.

Changes in atmospheric CO2 - Influence of the marine biota at high latitude

Approximately half of the nitrogen and phosphorus entering deep waters of the contemporary ocean are transported from the surface in inorganic form as preformed nutrients. A simple model for ocean chemistry is presented and shown to account for the present level of atmospheric CO2. Fluctuations in preformed nutrients, modulated by changes in insolation and circulation at high latitudes, can result in significant variations in CO2. It is suggested that these changes may account for the apparent control on climate exercised by secular variations in the orbital parameters of the earth.

Knox, F.

Production of nitrous oxide and consumption of methane by forest soils

Soils in an Amazonian rainforest are observed to release N2O at a rate larger than the global mean by about a factor of 20. Emissions from a New England hardwood forest are approximately 30 times smaller then Brazilian values. Atmospheric methane is consumed by soils in both systems. Tropical forests would provide a major source of atmospheric N2O if the Brazilian results are representative.

Keller, M.

Atmospheric composition - Influence of biology

The variability of atmospheric constituents influenced by biological organisms over various time scales is examined, together with the human contribution to atmospheric sulfur. The biogeochemistry of nitrogen is discussed, with an emphasis on N2O, NO, and microbially mediated reactions in soil and water. Carbon species are bound up mainly in sediments and the deep ocean, but human activities involving combustion may cause a doubling of the atmospheric levels of CO2 in the near future, which could produce a general low-level atmospheric warming. Longer term measurements are required to assess the effects of CH4 augmentation in the atmosphere through fuel combustion. Coal burning effectively doubles the amount of SO2 produced by natural sources, and reduces the pH of rainwater, thus posing hazards to fish, plankton, and mollusc life.

Mcelroy, M. B.

Helium on Venus - Implications for uranium and thorium

Helium is removed at an average rate of 10 to the 6th atoms per square centimeter per second from Venus's atmosphere by the solar wind following ionization above the plasmapause. The surface source of helium-4 on Venus is similar to that on earth, suggesting comparable abundances of crustal uranium and thorium.

Prather, M. J.

Marine biological controls on atmospheric CO2 and climate

It is argued that the ocean is losing N gas faster than N is being returned to the ocean, and that replenishment of the N supply in the ocean usually occurs during ice ages. Available N from river and estruarine transport and from rainfall after formation by lightning are shown to be at a rate too low to compensate for the 10,000 yr oceanic lifetime of N. Ice sheets advance and transfer moraine N to the ocean, lower the sea levels, erode the ocean beds, promote greater biological productivity, and reduce CO2. Ice core samples have indicated a variability in the atmospheric N content that could be attributed to the ice age scenario.

Mcelroy, M. B.

A stratospheric chemical instability

The equations which determine partitioning of Cl(x) in steady state have multiple (three) solutions under conditions which might arise in the high-latitude winter stratosphere. Two of these solutions are stable, one is unstable, to infinitesimal perturbations. The relative stability of solutions is examined by subjecting the system to finite perturbations. The more stable solution is found to eliminate the less stable when semi-infinite volumes of the two solutions are placed in contact. The high-ClO, low NO2 solution is more stable under most conditions. Transitions from less to more stable states are slow in winter but may occur more rapidly when the seasonal variation of insolation is taken into account.

Fox, J. L.