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NASA NTRS1985

Seasonal C-13 variations of methane from an anoxic marine sediment

Recent analyses of glacial ice suggest that the atmospheric concentration of methane has doubled in the last several hundred years, presumably due to anthropogenic perturbations of the relevant biogeochemical cycles. In principal, carbon isotopic measurements of atmospheric methane would provide information concerning changes in the sources and sinks of methane. The isotopic composition of methane is dependent on the source of the methane carbon, the mechanism of methane synthesis, and the degree and mode of oxidation which the methane has experienced. Unfortunately, few carbon isotopic measurements of atmospheric variations have been reported, so conclusions about temporal isotopic variations cannot be made. Also, before isotopic measurements of atmospheric methane can be used to identify changes in methane isotopic composition from different sources must be obtained. Methane bubbles from the anoxic sediments of Cape Lookout Bight, NC exhibit seasonal C-13 variations. The C-13 values ranged from -58 in August to -64 in the winter months with the evolution of the C-13 enriched gas occurring during periods of peak methane production. Even though a few intramolecular C-13 measurements of the pore water acetate have been made (methyl group, -26 per mil; carbonyl, -6 per mil), it is not clear how the acetate fermentation pathway affects the methane C-13/C-12 composition.

Blair, Neal↗

NASA NTRS1992

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗

NASA NTRS1992

Emissions of biogenic sulfur gases from Alaskan tundra

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol/m(sup -2)H(sup -1) (1.5-10) occurred in the water-saturated wet meadow areas inhabited by grasses, sedges, and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/m(sup -2)h(sup -1) (0-8.3) and lowest fluxes were from lichen-dominated areas at 0.9 nmol/m(sup -2)h(sup -1). Sulfur emissions from a lake surface were also low at 0.8 nmol/m(sup -2)h(sup -1). Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfure emissions from the marine sites were up to 20-fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150-250 nmol/m(sup -2)h(sup -1)). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfure emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2-3 x 10(exp 8) g/yr. This represents less than 0.001 percent of the estimated annual global flux (approximately 50 Tg) of biogenic sulfur and less than 0.01 percent of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Hines, Mark E.↗

NASA NTRS1992

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades: Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of greater than 500 nmol/m(sup -2)h(sup -1) occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of approximately 60 nmol/m(sup -2)h(sup -1) which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat thematic mapper were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emission were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities (42 percent) accounted for approximately 24 percent of the total S emissions.

Hines, Mark E.↗

NASA NTRS1992

Emissions of sulfur gases from wetlands

Data on the emissions of sulfur gases from marine and freshwater wetlands are summarized with respect to wetland vegetation type and possible formation mechanisms. The current data base is largest for salt marshes inhabited by Spartina alterniflora. Both dimethyl sulfide (DMS) and hydrogen sulfide (H2S) dominate emissions from salt marshes, with lesser quantities of methyl mercaptan (MeSH), carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl disulfide (DMDS) being emitted. High emission rates of DMS are associated with vegetation that produces the DMS precursor dimethylsulfonionpropionate (DMSP). Although large quantities of H2S are produced in marshes, only a small percentage escapes to the atmosphere. High latitude marshes emit less sulfur gases than temperate ones, but DMS still dominates. Mangrove-inhabited wetlands also emit less sulfur than temperate S. alterniflora marshes. Few data are available on sulfur gas emissions from freshwater wetlands. In most instances, sulfur emissions from temperate freshwater sites are low. However, some temperate and subtropical freshwater sites are similar in magnitude to those from marine wetlands which do not contain vegetation that produces DMSP. Emissions are low in Alaskan tundra but may be considerably higher in some bogs and fens.

Hines, Mark E.↗

NASA NTRS1992

Factors controlling sulfur gas exchange in Sphagnum-dominated wetlands

Atmosphere-peatland exchange of reduced sulfur gases was determined seasonally in fen in NH, and in an artificially-acidified fen at the Experimental Lakes Area (ELA) in Canada. Dimethyl sulfide (DMS) dominated gas fluxes at rates as high as 400 nmol/m(sup -2)hr(sup -1). DMS fluxes measured using enclosures were much higher than those calculated using a stagnant-film model, suggesting that Sphagnum regulated efflux. Temperature controlled diel and seasonal variability in DMS emissions. Use of differing enclosure techniques indicated that vegetated peatlands consume atmospheric carbonyl sulfide. Sulfate amendments caused DMS and methane thiol concentrations in near-surface pore waters to increase rapidly, but fluxes of these gases to the atmosphere were not affected. However, emission data from sites experiencing large differences in rates of sulfate deposition from the atmosphere suggested that chronic elevated sulfate inputs enhance DMS emissions from northern wetlands.

Demello, William Zamboni↗

NASA NTRS1992

Gas exchange in wetlands: Controls and remote sensing

This project was directed toward the quantification of fluxes of gaseous biogenic sulfur compounds from freshwater wetlands. These compounds (primarily hydrogen sulfide (H2S), dimethyl sulfide (DMS), and carbonyl sulfide (OCS)) have been implicated in the regulation of planetary albedo by the formation of microscopic atmospheric aerosols when they oxidize, and the further role of these aerosols as cloud condensation nuclei (CCN). The role of continental sources and sinks for these compounds is poorly understood. The present study was undertaken to quantify the source and sink strength of high latitude wetlands, and to delineate factors that regulate this flux.

Hines, Mark E.↗

NASA NTRS1995

Analysis of gas absorption to a thin liquid film in the presence of a zero-order chemical reaction

The paper presents a detailed theoretical analysis of the process of gas absorption to a thin liquid film adjacent to a horizontal rotating disk. The film is formed by the impingement of a controlled liquid jet at the center of the disk and subsequent radial spreading of liquid along the disk. The chemical reaction between the gas and the liquid film can be expressed as a zero-order homogeneous reaction. The process was modeled by establishing equations for the conservation of mass, momentum, and species concentration and solving them analytically. A scaling analysis was used to determine dominant transport processes. Appropriate boundary conditions were used to solve these equations to develop expressions for the local concentration of gas across the thickness of the film and distributions of film height, bulk concentration, and Sherwood number along the radius of the disk. The partial differential equation for species concentration was solved using the separation of variables technique along with the Duhamel's theorem and the final analytical solution was expressed using confluent hypergeometric functions. Tables for eigenvalues and eigenfunctions are presented for a number of reaction rate constants. A parametric study was performed using Reynolds number, Ekman number, and dimensionless reaction rate as parameters. At all radial locations, Sherwood number increased with Reynolds number (flow rate) as well as Ekman number (rate of rotation). The enhancement of mass transfer due to chemical reaction was found to be small when compared to the case of no reaction (pure absorption), but the enhancement factor was very significant when compared to pure absorption in a stagnant liquid film. The zero-order reaction processes considered in the present investigation included the absorption of oxygen in aqueous alkaline solutions of sodiumdithionite and rhodium complex catalyzed carbonylation of methanol. Present analytical results were compared to previous theoretical results for limiting conditions, and were found to have very good agreement.

Rajagopalan, S.↗

NASA NTRS1995

Origin of condensation nuclei in the springtime polar stratosphere

An enhanced sulfate aerosol layer has been observed near 25 km accompanying springtime ozone depletion in the Antarctic stratosphere. We use a one-dimensional aerosol model that includes photochemistry, particle nucleation, condensational growth, coagulation, and sedimentation to study the origin of the layer. Annual cycles of sunlight, temperature, and ozone are incorporated into the model. Our results indicate that binary homogeneous nucleation leads to the formation of very small droplets of sulfuric acid and water under conditions of low temperature and production of H2SO4 following polar sunrise. Photodissociation of carbonyl sulfide (OCS) alone, however, cannot provide sufficient SO2 to create the observed condensation nuclei (CN) layer. When subsidence of SO2 from very high altitudes in the polar night vortex is incorporated into the model, the CN layer is reasonably reproduced. The model predictions, based on the subsidence in polar vortex, agree with in situ measurements of particle concentration, vertical distribution, and persistence during polar spring.

Zhao, Jingxia↗

NASA NTRS1993

An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide

As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.

Gregory, Gerald L.↗

NASA NTRS1993

Carbon disulfide measurements in the atmosphere of the western North Atlantic and the northwestern South Atlantic Oceans

Carbon disulfide (CS2) measurements were made over the western and equatorial North Atlantic Ocean and the northwestern and equatorial South Atlantic Ocean. Carbon disulfide was in the range 0.4-50 pptrv in the atmosphere of the western North Atlantic Ocean. Emissions from anthropogenic sources and wet lands were found to be important although anthropogenic sources were 4-6 times larger than biogenic sources. The flux of CS2 from eastern North America between 30 and 39 deg latitude was estimated to be 2 x 10(exp 8)g/yr or sulfur. The anthropogenic contribution was 1.8 x 10(exp 8)g/yr of sulfur whereas the contribution of marshes was 0.2 x 10(exp 8)g/yr of sulfur. Sources of CS2 at high latitudes in the northern hemisphere were comparatively weak. Carbon disulfide levels in the western South Atlantic Ocean between -5 and 1 deg latitude were in the range 0.2-6 pptrv. Most of the CS2 appeared to come from biomass burning in Africa. Carbon disulfide was much higher close to shore suggesting that the South American continent was a significant source although too few data were available to quantify it. On ferry lights from Wallops, Virginia to Natal, Brazil, CS2 levels at the ferry altitude of about 6 km averaged 1.2 pptrv. This background CS2 was adequate to account for all the carbonyl sulfide (OCS) in the atmosphere.

Bandy, Alan R.↗

NASA NTRS1995

Origin of Condensation Nuclei in the Springtime Polar Stratosphere

Zhao, Jingxia↗

NASA NTRS1998

Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO, required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production Of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about I part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

Wennberg, P. O.↗

NASA NTRS1998

Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(sub x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.

Wennberg, P. O.↗

NASA NTRS1978

NMR and Infrared Study of Thermal Oxidation of cis-1, 4-Polybutadiene

A study of the microstructural changes occuring in CB during thermal, uncatalyzed oxidation was carried out. Although the oxidation of CB is accompanied by extensive crosslinking with attendant insolubilization, it was found possible to follow the oxidation of solid CB directly with C-13 NMR spectroscopy. The predominant products appearing in the C-13 NMR spectra of oxidized CB are epoxides. The presence of lesser amounts of alcohols, peroxides, and carbonyl structures was adduced from complementary infrared and NMR spectra of soluble extracts obtained from the oxidized, crosslinked CB. This distribution of functional groups contrasts with that previously reported for the autooxidation of 1,4-polyisoprene. The difference was rationalized in terms of the relative stabilities of intermediate radical species involved in the autoxidation of CB and 1,4-polyisoprene.

Gemmer, Robert V.↗

NASA NTRS1998

Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3, in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of 03 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day.This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

Wennberg, P. O.↗

NASA NTRS1999

Quantification and Characterization of Volatiles Evolved During Extrusion of Rice and Soy Flours

NASA Johnson Space Center is designing and building a habitat (Bioregenerative Planetary Life Support Systems Test Complex, BIO-Plex) intended for evaluating advanced life support systems developed for long duration missions to the Moon or Mars where all consumables will be recycled and reused. A food system based on raw products obtained from higher plants (such as soybeans, rice and wheat) may be a central feature of a biological ly-based Advanced Life Support System (ALSS). In order to convert raw crops to edible ingredients or food items, multipurpose processing equipment such as an extruder is ideal. Volatile compounds evolved during the manufacturing of these food products may accumulate reaching toxic levels. Additionally, off-odors often dissipated in open-air environments without consequence, may cause significant discomfort in the BIO-Plex. Rice and defatted soy flours were adjusted to 16% moisture and triplicate samples were extruded using a table top single-screw extruder. The extrudate was collected in specially designed Tedlar bags from which air samples could be extracted. The samples were analyzed by GC-MS with special emphasis on compounds with Spacecraft Maximum Allowable Concentrations (SMAC). Results showed a combination of alcohols, aldehydes, ketones and carbonyl compounds in the different flours. Each compound and its SMAC value as well as its impact on the air revitalization system was discussed.

Zasypkin, D.↗

NASA NTRS2000

R6 Hexameric Insulin Complexed with m-Cresol or Rescorcinol

The structures of three R6 human insulin hexamers have been determined. Crystals of monoclinic m-cresol/insulin, monoclinic resorcinol/insulin, and rhombohedral m-cresol/insulin crystals diffracted to 1.9, 1.9 and 1,78 Angstroms, respectively, and have been refined to residuals of 0.195, 0.179, and 0.200, respectively. In all three structures, a phenolic derivative is found to occupy the phenolic binding site where it forms hydrogen bonds to the carbonyl oxygen of A6 Cys and the nitrogen of A11 Cys. Two additional phenolic derivative binding sites were identified within or between hexamers. The structures of all three hexamers are nearly identical although a large displacement of the N-terminus of one B-chain in both monoclinic structures results from coordination to a sodium ion which is located between symmetry related hexamers. Other minor differences in structure are a consequence of differences in packing in the monoclinic cell as compared to the rhombohedral cell. Based upon the differences in conformation of the B13 Glu side chains in T6, T3R3, and R6 hexamers, the deprotonation of these side chains appears to be associated with the T (right arrow) R conformational transition.

Smith, G. David↗