Intracellular relationships and cell theory
Existence limits of cells, isoprenes, genetic systems, E. coli, and cell membranes in intracellular relationships
Danielli, J. F.↗
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Study of the synthesis of block copolymers Final report, 18 Oct. 1966 - 18 Aug. 1970
Chemical and mechanical properties and synthesis of 4-vinylbiphenyl-isoprene ABA block copolymers for permeation and propellant binder studies
Heller, J.↗
Hydrocarbon polymeric binder for advanced solid propellant
A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.
Potts, J. E.↗
Estimates on the production of CO and H2 from the oxidation of hydrocarbon emissions from vegetation
Extrapolating from extensive field measurements on foliar emissions in the U.S. approximate global inputs of isoprene and terpenes of 3.5 times 10 to the 14th power and 4.8 times 10 to the 14th power g(C)/yr, respectively, are obtained. The oxidation of these hydrocarbons could contribute in an important way to the atmospheric sources of CO (4.2-13.3 times 10 to the 14th power g/yr) and H2 (10-35 times 10 to the 12th power g/yr), and to organic species soluble in rainwater
Zimmerman, P. R.↗
Membrane lipids and the origin of life
The current state of knowledge regarding the development of biological systems is briefly reviewed. At a crucial stage concerning the evolution of such systems, the mechanisms leading to more complex structures must have evolved within the confines of a protected microenvironment, similar to those provided by the contemporary cell membranes. The major components found normally in biomembranes are phospholipids. The structure of the biomembrane is examined, and attention is given to questions concerning the availability of the structural components which are necessary in the formation of primitive lipid membranes. Two approaches regarding the study of protomembranes are discussed. The probability of obtaining ether lipids under prebiotic conditions is considered, taking into account the formation of cyclic and acyclic isoprenoids by the irradiation of isoprene with UV.
Oro, J.↗
Enhancement of in vitro Guayule propagation
A method for stimulating in vitro propagation of Guayule from a nutrient medium containing Guayule tissue by adding a substituted trialkyl amine bioinducing agent to the nutrient medium is described. Selective or differentiated propagation of shoots or callus is obtained by varying the amounts of substituted trialky amine present in the nutrient medium. The luxuriant growth provided may be processed for its poly isoprene content or may be transferred to a rooting medium for production of whole plants as identical clones of the original tissue. The method also provides for the production of large numbers of Guayule plants having identical desirable properties such as high polyisoprene levels.
Dastoor, M. N.↗
The Amazon Boundary Layer Experiment (ABLE 2A) - Dry season 1985
The Amazon Boundary Layer Experiment (ABLE 2A) used data from aircraft, ground-based, and satellite platforms to characterize the chemistry and dynamics of the lower atmosphere over the Amazon Basin during the early-to-middle dry season, July and August 1985. This paper reports the conceptual framework and experimental approach used in ABLE 2A and serves as an introduction to the detailed papers which follow in this issue. The results of ABLE 2A demonstrate that isoprene, methane, carbon dioxide, nitric oxide, dimethylsulfide, and organic aerosol emissions from soils and vegetation play a major role in determining the chemical composition of the atmospheric mixed layer over undisturbed forest and wetland environments. As the dry season progresses, emissions from both local and distant biomass burning become an important source of carbon monoxide, nitric oxide and ozone in the atmosphere over the central Amazon Basin.
Harriss, R. C.↗
Sources and sinks of formic, acetic, and pyruvic acids over central Amazonia. II - Wet season
Potential sources and sinks of formic, acetic, and pyruvic acids over the Amazon forest were investigated using a photochemical model and data collected on gas phase concentrations of these acids in the forest canopy, boundary layer, and free troposphere over the central Amazon Basin during the 1987 wet season. It was found that the atmospheric reactions previously suggested in the literature as sources of carboxylic acids (i.e., the gas phase decomposition of isoprene, the reaction between CH3CO3 and a peroxide, and aqueous phase oxidation of CH2O) appear to be too slow to explain the observed concentrations, suggesting that other atmospheric reactions, so far unidentified, could make a major contribution to the carboxylic acid budgets.
Talbot, R. W.↗
Graphite intercalation compound with iodine as the major intercalant
Halogenated CBr(sub x)I(sub y) (1 less than y/x less than 10) was made by exposing graphite materials with interplanar spacing in the 3.35 to 3.41 A range to either pure Br2 or an I2-Br2 mixture, and then to iodine vapor containing a small amount of Br2. The electrical resistivity of this product is from 3 to 6.5 times the pristine value. The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine to bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to fluorine attack during subsequent fluorination to fabricate graphite fluoride fibers.
Hung, Ching-Cheh↗
Simulation of summertime ozone over North America
The concentrations of O3 and its precursors over North America are simulated for three summer months with a 3D, continental-scale photochemical model using meteorological input from the Goddard Institute for Space Studies (GISS) GCM. The model has 4 x 5 deg grid resolution and represents nonlinear chemistry in urban and industrial plumes with a subgrid nested scheme. Simulated median afternoon O3 concentrations at rural U.S. sites are within 5 ppb of observations in most cases, except in the south central U.S., where concentrations are overpredicted by 15-20 ppb. The model captures successfully the development of regional high-O3 episodes over the northeastern United States on the back side of weak, warm, stagnant anticyclones. Simulated concentrations of CO and nonmethane hydrocarbons are generally in good agreement with observations, concentrations of NO(x) are underpredicted by 10-30 percent, and concentrations of PANs are overpredicted by a factor of 2 to 3. The overprediction of PANs is attributed to flaws in the photochemical mechanism, including excessive production from oxidation of isoprene, and may also reflect an underestimate of PANs deposition. Subgrid nonlinear chemistry as captured by the nested plumes scheme decreases the net O3 production computed in the U.S. boundary layer by 8 percent on average.
Jacob, Daniel J.↗
Ozone formation during an episode over Europe: A 3-D chemical/transport model simulation
A 3-D regional photochemical tracer/transport model for Europe and the Eastern Atlantic has been developed based on the NASA/GISS CTM. The model resolution is 4x5 degrees latitude and longitude with 9 layers in the vertical (7 in the troposphere). Advective winds, convection statistics and other meteorological data from the NASA/GISS GCM are used. An extensive gas-phase chemical scheme based on the scheme used in our global 2D model has been incorporated in the 3D model. In this work ozone formation in the troposphere is studied with the 3D model during a 5 day period starting June 30. Extensive local ozone production is found and the relationship between the source regions and the downwind areas are discussed. Variations in local ozone formation as a function of total emission rate, as well as the composition of the emissions (HC/NO(x)) ratio and isoprene emissions) are elucidated. An important vertical transport process in the troposphere is by convective clouds. The 3D model includes an explicit parameterization of this process. It is shown that this process has significant influence on the calculated surface ozone concentrations.
Berntsen, Terje↗
Acetone in the atmosphere: Distribution, sources, and sinks
Acetone (CH3COCH3) was found to be the dominant nonmethane organic species present in the atmosphere sampled primarily over eastern Canada (0-6 km, 35 deg-65 deg N) during ABLE3B (July to August 1990). A concentration range of 357 to 2310 ppt (= 10(exp -12) v/v) with a mean value of 1140 +/- 413 ppt was measured. Under extremely clean conditions, generally involving Arctic flows, lowest (background) mixing ratios of 550 +/- 100 ppt were present in much of the troposphere studied. Correlations between atmospheric mixing ratios of acetone and select species such as C2H2, CO, C3H8, C2Cl4 and isoprene provided important clues to its possible sources and to the causes of its atmospheric variability. Biomass burning as a source of acetone has been identified for the first time. By using atmospheric data and three-dimensional photochemical models, a global acetone source of 40-60 Tg (= 10(exp 12) g)/yr is estimated to be present. Secondary formation from the atmospheric oxidation of precursor hydrocarbons (principally propane, isobutane, and isobutene) provides the single largest source (51%). The remainder is attributable to biomass burning (26%), direct biogenic emissions (21%), and primary anthropogenic emissions (3%). Atmospheric removal of acetone is estimated to be due to photolysis (64%), reaction with OH radicals (24%), and deposition (12%). Model calculations also suggest that acetone photolysis contributed significantly to PAN formation (100-200 ppt) in the middle and upper troposphere of the sampled region and may be important globally. While the source-sink equation appears to be roughly balanced, much more atmospheric and source data, especially from the southern hemisphere, are needed to reliably quantify the atmospheric budget of acetone.
Singh, H. B.↗
Reactive nitrogen oxides and ozone above a taiga woodland
Measurements of reactive nitrogen oxides (NO(x) and NO(y)) and ozone (O3) were made in the planetary boundary layer (PBL) above a taiga woodland in northern Quebec, Canada, during June-August, 1990, as part of NASA Artic Boundary Layer Expedition (ABLE) 3B. Levels of nitrogen oxides and O3 were strongly modulated by the synoptic scale meteorology that brought air from various source regions to the site. Industrial pollution from the Great Lakes region of the U.S. and Canada appears to be a major source for periodic elevation of NO(x), and NO(y) and O3. We find that NO/NO2 ratios at this site at midday were approximately 50% those expected from a simple photochemical steady state between NO(x) and O3, in contrast to our earlier results from the ABLE 3A tundra site. The difference between the taiga and tundra sites is likely due to much larger emissions of biogenic hydrocarbons (particularly isoprene) from the taiga vegetation. Hydrocarbon photooxidation leads to relatively rapid production of peroxy radicals, which convert NO to NO2, at the taiga site. Ratios of NO(x) to NO(y) were typically 2-3 times higher in the PBL during ABLE 3B than during ABLE 3A. This is probably the result of high PAN levels and suppressed formation of HNO3 from NO2 due to high levels of biogenic hydrocarbons at the ABLE 3B site.
Bakwin, Peter S.↗
Convective transport over the central United States and its role in regional CO and ozone budgets
We have constructed a regional budget for boundary layer carbon monoxide over the central United States (32.5 deg - 50 deg N, 90 deg - 105 deg W), emphasizing a detailed evaluation of deep convective vertical fluxes appropriate for the month of June. Deep convective venting of the boundary layer (upward) dominates other components of the CO budget, e.g., downward convective transport, loss of CO by oxidation, anthropogenic emissions, and CO produced from oxidation of methane, isoprene, and anthropogenic nonmethane hydrocarbons (NMHCs). Calculations of deep convective venting are based on the method pf Pickering et al.(1992a) which uses a satellite-derived deep convective cloud climatology along with transport statistics from convective cloud model simulations of observed prototype squall line events. This study uses analyses of convective episodes in 1985 and 1989 and CO measurements taken during several midwestern field campaigns. Deep convective venting of the boundary layer over this moderately polluted region provides a net (upward minus downward) flux of 18.1 x 10(exp 8) kg CO/month to the free troposphere during early summer. Shallow cumulus and synoptic-scale weather systems together make a comparable contribution (total net flux 16.2 x 10(exp 8) kg CO/month). Boundary layer venting of CO with other O3 precursors leads to efficient free troposheric O3 formation. We estimate that deep convective transport of CO and other precursors over the central United States in early summer leads to a gross production of 0.66 - 1.1 Gmol O3/d in good agreement with estimates of O3 production from boundary layer venting in a continental-scale model (Jacob et al., 1993a, b). On this respect the central U.S. region acts as s `chimney' for the country, and presumably this O3 contributes to high background levels of O3 in the eastern United States and O3 export to the North Atlantic.
Thompson, Anne M.↗
Graphite intercalation compound with iodine as the major intercalate
Halogenated graphite CBr(x)I(y) (I less than y/x less than 10) was made by exposing graphite materials to either pure Br2 or an I2/Br2/HBr mixture to initiate the reaction, and then to iodine vapor containing a small amount of Br2/HBr/IBr to complete the intercalation reaction. Wetting of the graphite materials by the I2/Br2/HBr mixture is needed to start the reaction, and a small amount of Br2/HBr/IBr is needed to complete the charge transfer between iodine and carbon. The interplanar spacings for the graphite materials need to be in the 3.35 to 3.41 A range. The X-ray diffraction data obtained from the halogenated HOPG indicate that the distance between the two carbon layers containing intercalate is 7.25 A. Electrical resistivity of the fiber product is from 3 to 6.5 times the pristine value, The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine-to-bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 percent to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to structural damage during subsequent fluorination to fabricate graphite fluoride fibers.
Hung, Ching-Cheh↗
Simulation of Tropical Biomass Burning
The research objectives that were achieved during the course of our studies include the following: (1) Over the last few years, a model has been developed in the Atmospheric Chemistry and Dynamics Branch at Ames Research Center in collaboration with the Physics Department at San Jose State University. It is referred to as the Global/Regional Atmospheric Chemistry Event Simulator (GRACES). Currently, the GRACES model system combines an atmospheric chemistry and transport model, and a regional mesoscale meteorological model. Therefore this system is suitable for simulating the conditions observed by the tropical observation missions, such as the Pacific Exploratory Mission in the 'Tropics (PEM-Tropics), Study of Ozone and Nitrogen oxides Experiment (SONEX), and other periods. Specifically, the research carried out included the evaluation of the behavior of several components of the MM5 (I.e., Meteorological Model 5, version 2) and the GRACES combined modeling system. We initiated research on (a) the ability of the MM5 model to assimilate downward vertical velocities at least as high as the analyses, (b) the ability of the Graces model to incorporate the vertical velocities from MM5, and (c) other factors related to transport patterns required to transport CO in the observed manner. We carried out improved calculations of the transport of tracers for both NASA airborne missions, SONEX and PEM-Tropics. We also made improved source strength estimates fopr isoprene dust, and similar emissions from the Earths surface. This required the use of newly available databases on the Earth's surface and vegetation. We completed atmospheric chemistry simulations of radicals and nitrogen oxide species. We have greatly improved the handling of cumulonimnbus convection by modifing an existing scheme.
Hamill, Patrick↗
Simulation of Tropical Biomass Burning
The work proposed was carried out as planned. The work described in this final report formed the basis for a follow-on research grant research grant from NASA Ames Research Center. The research objectives that were achieved during the course of our studies include the following: (1) the evaluation of several components of MM5 (Meteorological Model 5 version 2) and the Global/Regional Atmospheric Chemistry Event Simulator (GRACES) combined modeling system; (2) improved calculations of the transport of tracers for both NASA airborne missions, Study of Ozone and Nitrogen oxides experiment (SONEX) and Pacific Exploratory MIssion in the Tropics (PEM-Tropics); (3) improved source strength estimates for isoprene, dust and similar emissions from the Earth's surface. This required the use of newly available databases on the Earth's surface and vegetation; (4) completed atmospheric chemistry simulations of radicals and nitrogen oxide species; (5)improved the handling of cumulonimbus convection by modifying the existing scheme; (6) identified the role of the African Intertropical Front, using MM5's nesting capability to refine model resolution in crucial areas; modified the MM5 trajectory program to allow it to work much better for a parcel crossing the west/east boundaries.
Hamill, Patrick↗
Ecosystem Modeling of Biological Processes to Global Budgets
From an ecological perspective, the search for life on distant planets begins from several key assumptions. The first of these is that, viewed from a remote location in space, the signature of life on a distant planet will be the result of net gas exchange of organisms with their environment. On the basis of extensive biogeochemical measurements and biogenic trace gas fluxes in modem Earth environments, it is probable that certain groups of organisms both produce and consume the same trace gas(es) within a single bioprofile of Solid (porous) substrate or surface water. The net gas exchange rate with the atmosphere measured at the living surface is frequently the result of competing metabolic reactions, which may carried out by different functional groups of organisms located at dissimilar 'climatic' or chemical microsites within the same bioprofile. Biogenic gases produced at one (deep) level of a bioprofile may be consumed by another functional group of organisms located closer to the level of surface exchange with the atmosphere. A second key assumption is that the net biogenic fluxes of atmospheric gases on Earth can be used to infer relative abundance and functional composition of the major organisms on a distant planet. Examples of this principle include the presence of methanogenic microorganisms abundant today in freshwater ecosystems worldwide, which are major source of atmospheric methane and its seasonal variability in Earth's atmosphere. A third assumption is that scaling up biogenic gas fluxes from a single biological community to the planetary level requires flux measurements at the whole ecosystem level. This implies that measurements of biogenic gas exchange with the global atmosphere cannot be easily inferred from measurements of gas production rates of single organisms, which may have been isolated in some manner from the setting of their native ecosystem. Hence, the unit of biological organization used in modern Earth Science for scaling up to biosphere effects on atmospheric composition is the ecosystem level. These assumptions are the foundation for developing modern emission budgets for biogenic gases such as carbon dioxide, methane, carbon monoxide, isoprene, nitrous and nitric oxide, and ammonia. Such emission budgets commonly include information on seasonal flux patterns, typical diurnal profiles, and spatial resolution of at least one degree latitude/longitude for the globe. On the basis of these budgets, it is possible to compute 'base emission rates' for the major biogenic trace gases from both terrestrial and ocean sources, which may be useful benchmarks for defining the gas production rates of organisms, especially those from early Earth history, which are required to generate a detectable signal on a global atmosphere. This type of analysis is also the starting point for evaluation of the 'biological processes to global gas budget' extrapolation procedure described above for early Earth ecosystems.
Christopher, Potter S.↗