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Cofer, W. R., III

Publications and source records attributed to Cofer, W. R., III.

At least 19 records

Solid propellant exhausted aluminum oxide and hydrogen chloride - Environmental considerations

Measurements of gaseous hydrogen chloride (HCl) and particulate aluminum oxide (Al2O3) were made during penetrations of five Space Shuttle exhaust clouds and one static ground test firing of a shuttle booster. Instrumented aircraft were used to penetrate exhaust clouds and to measure and/or collect samples of exhaust for subsequent analyses. The focus was on the primary solid rocket motor exhaust products, HCl and Al2O3, from the Space Shuttle's solid boosters. Time-dependent behavior of HCl was determined for the exhaust clouds. Composition, morphology, surface chemistry, and particle size distributions were determined for the exhausted Al2O3. Results determined for the exhaust cloud from the static test firing were complicated by having large amounts of entrained alkaline ground debris (soil) in the lofted cloud. The entrained debris may have contributed to neutralization of in-cloud HCl.

Cofer, W. R., III

Space Shuttle exhausted aluminum oxide - A measured particle size distribution

Aluminum oxide (A2O3) particles were collected from the Space Shuttle exhaust plume immediately following the launch of STS-34 on October 18, 1989. A2O3 samples were obtained at 2.4, 3.0, 3.2, and 7.4 km in altitude. The samples were analyzed using SEM to develope particle size distributions. There were no indications that the particle size distribution changed as a function of altitude. The particle number concentrations per cubic meter of air sampled for the four collections was found to fit an exponential expression.

Cofer, W. R., III

New estimates of nitrous oxide emissions from biomass burning

The recent discovery of an artifact producing increased levels of N2O in combustion gas samples collected and stored in grab bottles before chemical analysis has resulted in the downgrading of fossil-fuel combustion and the questioning of biomass burning as important sources of N2O. As almost all reported analyses of N2O produced from biomass burning have involved essentially the same collection and analysis protocols as used in the fossil-fuel studies, this source of N2O must also be reexamined. Here, measurements of N2O made over a large prescribed fire using a near real-time in situ measurement technique are reported and compared with measurements of N2O from simultaneously collected grab-bottle samples. The results from 27 small laboratory biomass test fires are also used to help clarify the validity of earlier assessments. It is concluded that biomass burning contributes about seven percent of atmospheric N2O, as opposed to earlier estimates of several times this value.

Cofer, W. R., III

Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

The first simultaneous measurements of gaseous nitric acid and ammonia in the smoke plume of a wetlands biomass burn were obtained. The measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn on November 9, 1987, at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 0.00012. Ammonia, however, dit not correlate well with CO2, suggesting a more complex relationship between combustion and production/release of NH3.

Lebel, P. J.

Nebulization reflux concentrator

A nebulization reflux concentrator for removing trace gas contaminants from a sample gas is described. Sample gas from a gas supply is drawn by a suction source into a vessel. The gas enters the vessel through an atomizing nozzle, thereby atomizing and entraining a scrubbing liquid solvent drawn through a siphon tube from a scrubbing liquid reservoir. The gas and entrained liquid rise through a concentrator and impinge upon a solvent phobic filter, whereby purified gas exits through the filter housing and contaminated liquid coalesces on the solvent phobic filter and falls into the reservoir.

Collins, V. G.

A new technique for collection, concentration and determination of gaseous tropospheric formaldehyde

This article describes an improved technique for making in situ measurements of gaseous tropospheric formaldehyde (CH2O). The new technique is based on nebulization/reflux principles that have proved very effective in quantitatively scrubbing water soluble trace gases (e.g., CH2O) into aqueous mediums, which are subsequently analyzed. Atmospheric formaldehyde extractions and analyses have been performed with the nebulization/reflux concentrator using an acidified dinitrophenylhydrazine solution that indicate that quantitative analysis of CH2O at global background levels (about 0.1 ppbv) is feasible with 20-min extractions. Analysis of CH2O, once concentrated, is accomplished using high performance liquid chromatography with ultraviolet photometric detection. The CH2O-hydrazone derivative, produced by the reaction of 2,4-dinitrophenylhydrazine in H2SO4 acidified aqueous solution, is detected as CH2O.

Cofer, W. R., III

A general, cryogenically-based analytical technique for the determination of trace quantities of volatile organic compounds in the atmosphere

An analytical technique for the determination of trace (sub-ppbv) quantities of volatile organic compounds in air was developed. A liquid nitrogen-cooled trap operated at reduced pressures in series with a Dupont Nafion-based drying tube and a gas chromatograph was utilized. The technique is capable of analyzing a variety of organic compounds, from simple alkanes to alcohols, while offering a high level of precision, peak sharpness, and sensitivity.

Coleman, R. A.

Influence of meteorological conditions on aerosol vertical distribution and composition off the northeast American coastline

The size distribution and composition of lower tropospheric aerosols were measured off the northeast American coastline under clear air and disturbed meteorological conditions. Under the clear air conditions observed on 5 August 1982, with air flow from west to east, sulfate-rich stratified layers are the dominant feature of aerosol distribution in the lowest 3000 m of the troposphere. The encroachment of a warm frontal system over the study area on 9 August 1982 resulted in dramatic changes in aerosol distribution and composition prior to any precipitation, probably due to increased vertical mixing and dilution of pollutant aerosols. Chloride becomes the dominant water soluble anion in the lower 3000 m, primarily due to a several fold decrease in sulfate. Although these results are limited to only two sets of measurements, the data indicate the variability which can occur in the tropospheric vertical aerosol distributions at remote locations. A knowledge of the structure and stability of these stratified layers is of particular importance to studies of the ocean-troposphere chemistry problem.

Sebacher, D. I.

Improved aqueous scrubber for collection of soluble atmospheric trace gases

A new concentration technique for the extraction and enrichment of water-soluble atmospheric trace gases has been developed. The gas scrubbing technique efficiently extracts soluble gases from a large volume flow rate of air sample into a small volume of refluxed trapping solution. The gas scrubber utilizes a small nebulizing nozzle that mixes the incoming air with an aqueous extracting solution to form an air/droplet mist. The mist provides excellent interfacial surface areas for mass transfer. The resulting mist sprays upward through the reaction chamber until it impinges upon a hydrophobic membrane that virtually blocks the passage of droplets but offers little resistance to the existing gas flow. Droplets containing the scrubbed gases coalesce on the membrane and drip back into the reservoir for further refluxing. After a suitable concentration period, the extracting solution containing the analyte can be withdrawn for analysis. The nebulization-reflex concentration technique is more efficient (maximum flow of gas through the minimum volume of extractant) than conventional bubbler/impinger gas extraction techniques and is offered as an alternative method.

Cofer, W. R., III

Surface chloride salt formation on Space Shuttle exhaust alumina

Aluminum oxide samples from the exhaust of Space Shuttle launches STS-1, STS-4, STS-5, and STS-6 were collected from surfaces on or around the launch pad complex and chemically analyzed. The results indicate that the particulate solid-propellant rocket motor (SRM) alumina was heavily chlorided. Concentrations of water-soluble aluminum (III) ion were large, suggesting that the surface of the SRM alumina particles was rendered soluble by prior reactions with HCl and H2O in the SRM exhaust cloud. These results suggest that Space Shuttle exhaust alumina particles are good sites for nucleation and condensation of atmospheric water. Laboratory experiments conducted at 220 C suggest that partial surface chloriding of alumina may occur in hot Space Shuttle exhaust plumes.

Cofer, W. R., III

Aluminum chloride formation on Space Shuttle aluminum oxide

Samples of particulates collected from the exhaust of Space Shuttle launches STS-1, -4, -5, -6, and -7 were analyzed. Scanning electron microscopy and X-ray diffractometry of these samples indicated that the particulates were spherical and predominantly composed of aluminum oxide. The water-soluble weight fraction, pH, acid-soluble weight fraction, and insoluble weight fraction were determined for each sample. Water-soluble weight fractions averaged about 7 percent of the total sample weight, were generally very acidic, and contained significantly elevated concentrations of chloride and aluminum (III) ion. The high concentrations of soluble aluminum (III) and chloride ions observed suggested that aluminum chlorides and/or oxychlorides had formed on the surface of the alumina particulates. More than 72 percent by weight of each sample was insoluble in either water or strong mineral acid, and was identified as alpha-Al2O3. The results from these analyses suggest that the surface of Space Shuttle exhaust alumina particulates will be highly acidic and heavily chlorided, and that a substantial amount of the surface chloride may be chemically associated with aluminum (III) ions rather than just physically adsorbed as HCl.

Cofer, W. R., III

Oxidation of SO2 by NO2 and O3 on carbon - Implications to tropospheric chemistry

The oxidation of SO2 to sulfate in air at 65 percent relative humidity on carbon particles was investigated gravimetrically in the presence of NO2 and O3. Approximately 1 mg samples of carbon black were exposed to continuously flowing ppbv mixtures of SO2, SO2 + NO2 and SO2 + O3 for prescribed periods of time before desorption into dry N2. Wet chemical analysis of the particles followed desorption. NO2 and O3 were found to have little, if any, effect relative to air on sulfate yields at the concentrations studied.

Cofer, W. R., III

Hydrogen chloride and aerosol ground cloud characteristics resulting from Space Shuttle launches

Airborne measurements of gaseous HCl, gaseous and aerosol HCl, particulates, relative humidity and temperature were obtained in ground clouds produced during three Space Shuttle launches. Partitioning of HCl between HCl aerosol and gaseous HCl was investigated as the solid rocket exhaust cloud diluted with ambient air to evaluate the conditions under which aerosol formation occurs in the troposphere in the presence of hygroscopic HCl vapor. Equilibrium predictions for aqueous HCl aerosol formation generally agree with the measured HCl partitioning over HCl concentrations from 0.5 to 36 ppm. HCl concentration dispersion within four cloud segments at time t (min) was evaluated using the expression C = C(0) (t to the alpha power) where C(0) varied from 145 to 2250 ppm and alpha varied from -1.14 to -1.73. Aerosol fallout from the exhaust clouds was measured with time by monitoring HCl concentrations and aerosol distributions 100 m below the cloud as it drifted away from the launch site. Significant amounts of HCl were found to be removed by fallout of particles in the 80-220 micron diameter range up to 30 min after launch.

Sebacher, D. I.

Carbon catalysis in the aqueous oxidation of SO2 by NO2 and air

Sulfur dioxide and an oxidant gas (air or NO2) were bubbled through aqueous suspensions of both washed and unwashed carbon black as well as through samples of wash water, which contained whatever soluble species were originally present on the carbon, and high-purity water. The sulfate yields obtained showed the washed and unwashed carbon to be equally catalytic for the oxidation of SO2 to sulfate by both oxidants, whereas little sulfate was generated in either the wash water or high-purity water in the absence of carbon. These results indicate that the sulfate yields produced in aqueous suspensions of the carbon studied are due to catalysis by the carbon particles rather than by soluble species dissolved from them.

Schryer, D. R.

Airborne measurements of Space Shuttle exhaust constituents

Airborne measurements of hydrogen chloride (HCl) and particulates made during penetrations into and flights under Space Shuttle exhaust clouds from launches STS-1, -2, and -5 are presented to permit comparison with dispersion model predictions for Space Shuttle exhaust clouds, and with previous measurements made in Titan III exhaust clouds. Analytical techniques employed for the Shuttle measurements were developed and refined during earlier Titan III exhaust cloud measurements and include the measurements of particulate concentrations, size distributions, and the partitioning of HCl between the gaseous and aerosol phases. The results are useful in understanding the dynamics of ground cloud development, atmospheric dispersion, and potential environmental effects of Shuttle effluents.

Cofer, W. R., III

Methane and nonmethane hydrocarbon concentrations in the North and South Atlantic marine boundary layer

Methane and nonmethane hydrocarbon (NMHC) data were collected in the Atlantic marine boundary layer from 40 N to 32 S latitude during October and November 1980. Average volume mixing ratios for CH4 of 1.69 + or - 0.02 ppmv were obtained north of the intertropical convergence zone (ITCZ) and 1.60 + or - 0.02 ppmv south of the ITCZ. The hemispheric CH4 gradient was very sharp, decreasing rapidly between 14 N and 10 N latitude. Gaseous NMHC concentrations (based on response as CH4) were measured simultaneously and found to lie consistently within the standard error for the individual measurements + or - 0.02 ppmv) after correction for water vapor interference. The correction for water vapor response was large, frequently as much as 80% of the raw NMHC signal. Application of the student's t distribution test to the NMHC data set established that the mean northern and southern hemispheric NMHC mixing ratios measured, 0.016 and 0.010 ppmv, respectively, were statistically different at the 95% confidence level. These results indicate volatile NMHC mixing ratios average less than 0.02 ppmv over the Atlantic and represent the first set of semicontinuous NMHC measurements spanning the North and South Atlantic marine boundary layer.

Cofer, W. R., III