Engineering topics
Publications and source records attributed to Pinto, Joseph P..
Biomass burning may be the overwhelming regional or continental-scale source of methane (CH4) as in tropical Africa and a significant global source of CH4. Our best estimate of present methane emissions from biomass burning is about 51.9 Tg/yr, or 10% of the annual methane emissions to the atmosphere. Increased frequency of fires that may result as the Earth warms up may result in increases in this source of atmospheric methane.
While the Kuwait oil-fire smoke plumes manifested a pronounced impact on solar radiation in the Gulf region (such as visibility and surface temperatures), smoke plume concentrations of combustion-generated pollutants suggest that the overall chemical impact on the atmosphere of the smoke from these fires was probably much less than anticipated. Combustion in the Kuwaiti oil fires was surprisingly efficient, releasing on average more than 93 percent of the combusted hydrocarbon fuels as CO2. Correspondingly, combustion-produced quantities of carbon monoxide (CO) and carbonaceous particles were low, each about 2 percent by weight. The fraction of CH4 produced by the fires was also relatively low (about 0.2 percent), but source emissions of nonmethane hydrocarbons were high (about 2 percent). Processes other than combustion (e.g., volatilization) probably contributed significantly to the measured in-plume hydrocarbon concentrations. Sulfur emissions (particulate and gaseous) measured at the source fires were lower (about 0.5 percent) than predicted based on average sulfur contents in the crude. N2O emissions from the Kuwaiti oil fires were very low and often could not be distinguished from background concentrations.
A novel mechanism for isotropic exchange between CO2 and O3 via O(1D) + CO2 - CO3(asterisk) followed by CO3(asterisk) - CO2 + O(3P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in O-18 in the stratospheric CO2 observed by Gamo et al. (1989), using the heavy O3 profile observed by Mauersberger (1981). The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO2 in the troposphere are briefly discussed.
The role photochemical reactions in the early earth's atmosphere played in the prebiotic synthesis of simple organic molecules was examined, extending an earlier calculation of formaldehyde production rates to more reduced carbon species, such as methanol, methane, and acetaldehyde. The experimental results of Bar-Nun and Chang (1983) are simulated as an aid in the construction of the photochemical scheme and as a way of validating the model. The results indicate that some fraction of CO2 and H2 present in the primitive atmosphere could have been converted to simple organic molecules. The exact amount is dependent on the partial pressure of CO2 and H2 in the atmosphere and on what assumptions are made concerning the shape of the absorption spectra of CO2 and H2O.
One-dimensional aerosol microphysical and photochemical models are used to study the chemistry of stratospheric volcanic clouds. The results indicate that the aerosol microphysical processes of condensation and coagulation produce larger particles as the SO2 injection rate is increased. Larger particles have a smaller optical depth per unit mass and settle out of the stratosphere at a faster rate than smaller ones, restricting the total number of particles in the stratosphere. The microphysical processes moderate the impact of volcanic clouds on the earth's radiation budget and climate, suggesting that volcanic effects may be self limiting. It is noted that the injection of HCl into the stratosphere, which could lead to large ozone changes, is limited by a cold trap effect in which HCl and water vapor condense on ash particles in the rising volcanic plume and fall out as ice.
A one-dimensional photochemical model is presently used to ascertain the nature of those chemical and physical processes of the Martian atmosphere responsible for the preferential escape of hydrogen over deuterium. A comparison of the present theoretical considerations with recent HDO observations indicates that Mars contains 0.2 m of (globally averaged) crustal water that is exchangeable with the atmosphere. This estimate, which is substantially lower than those obtained for Martian subsurface water on the basis of Viking image-derived geomorphological analyses, can be reconciled only if a small fration of the crustal water is exchangeable with the atmosphere.
It is suggested that photochemical enrichment processes driven by stellar UV emissions could result in a large deuterium fractionation of water and methane relative to H2 in the primitive solar nebula. These enrichment processes could have profoundly influenced the isotopic content of water in the terrestrial planets, if a large fraction of their volatiles had been added by impacts of meteorites and comets formed in the outer parts of the solar nebula. Efficient mixing could have exposed the material in the interior of the solar nebula to starlight.
Troe's (1977) approximate theory is presently used in conjunction with transition state theory to estimate the rate coefficient of the reaction by which CO is reduced to CH4; attention is given to the role that may be played in the reduction process by the formation of the CH3O radical from H + H2CO. Attention is given to the implications of such a reaction (1) for the CO chemistry on Jupiter and within the solar nebula, (2) for the interpretation of such experimental results as those of Bar-Nun and Shaviv (1975) and Bar-Nun and Chang (1983), and (3) for organic synthesis in the prebiotic terrestrial atmosphere.