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The positive nitrogen peroxide ion is discussed as an ionic constituent of the lower ionosphere in the light of recently observed concentrations at altitudes between 87.8 and 93.2 km. Photoionization and charge exchange reactions appear to be insufficient to account for the positive nitrogen peroxide ion concentration observed at 90 km. A possible alternative reaction is proposed, and its implications are briefly reviewed.
On the basis of these background data, metabolic studies were performed on humans involved in space flight. These studies included the Skylab experiences. The primary purpose of the investigations was to study red cells for: (1) evidences of lipid peroxidation, or (2) changes at various points in the glycolytic pathway. The Skylab missions were an opportunity to study blood samples before, during, and after flight and to compare results with simultaneous controls. No direct evidence that lipid peroxidation had occurred in the red blood cells was apparent in the studies.
Afterbody drag predictions for jet aircraft are usually made experimentally with the jet exhaust flow simulated. The physical gas properties of the fluid used for the model jet exhaust can affect the accuracy of simulation of the airplane's jet exhaust plume. The effect of the accuracy of this simulation on afterbody drag was investigated by wind-tunnel tests with single engine model. In addition to unheated air as the exhaust gas, the decomposition products of three different concentrations of hydrogen peroxide were utilized. The air jet simulation consistently resulted in higher boattail drag than hydrogen peroxide simulation. The differences in drag for the various exhaust gases are attributed to different plume shapes and entrainment properties of the gases. The largest differences in drag due to exhaust gas properties were obtained for the combination of high transonic Mach numbers and high boattail angles. For these conditions, the current data indicate that the use of air to simulate a nonafterburning turbojet exhaust can result in an increase in afterbody amounting to 20 percent of the nonafterburning turbojet value.
Two methods for eliminating luminol interference materials are described. One method eliminates interference from organic material by pre-reacting a sample with dilute hydrogen peroxide. The reaction rate resolution method for eliminating inorganic forms of interference is also described. The combination of the two methods makes the luminol system more specific for bacteria. Flow system designs for both the firefly luciferase and luminol bacteria detection systems are described. The firefly luciferase flow system incorporating nitric acid extraction and optimal dilutions has a functional sensitivity of 3 x 100,000 E. coli/ml. The luminol flow system incorporates the hydrogen peroxide pretreatment and the reaction rate resolution techniques for eliminating interference. The functional sensitivity of the luminol flow system is 1 x 10,000 E. coli/ml.
Blood samples from Spacelab crewmembers were studied for possible environment effects on red cell components. Analysis involved peroxidation of red cell lipids, enzymes of red cell metabolism, and levels of 2,3-diphosphoglyceric acid and adenosine triphosphate. Results show that there is no evidence of lipid peroxidation, that biochemical effect known to be associated with irreversible red cell damage. Changes observed in glycolytic intermediates and enzymes cannot be directly implicated as indicating evidence of red cell damage.
The extent to which fluvial processes occurred in Mars is considered with reference to the oxidation of soil organics by the gamma-Fe2O3/H2O2 system. Data from the Viking biology experiments suggest that the acidity of gamma-Fe2O3 controls the ionization of hydrogen peroxide - that is, in acid conditions and in the presence of large concentrations of formate, gamma-Fe2O3 reacts efficiently with peroxide to oxidize formate to CO2 and H2O. Fe3O4, alpha-Fe2O3, and calcite are basic and block the oxidation of formate. The properties of this system are consistent with the hypothesis that Mars has been under a severe regime of dryness.
A method and apparatus for removing porphyrins from a fluid sample which are unrelated to the number of bacteria present in the sample and prior to combining the sample with luminol reagent to produce a light reaction is disclosed. The method involves a pre-incubation of the sample with a dilute concentration of hydrogen peroxide which inactivates the interfering soluble porphyrins. Further, by delaying taking a light measurement for a predetermined time period after combining the hydrogen peroxide-treated water sample with a luminol reagent, the luminescence produced by the reaction of the luminol reagent with ions present in the solution, being short lived, will have died out so that only porphyrins within the bacteria which have been released by rupturing the cells with the sodium hydroxide in the luminol reagent, will be measured. The measurement thus obtained can then be related to the concentration of live and dead bacteria in the fluid sample.
The experimental studies on the mitochondria of insect and mammalian cells are examined with a view to an analysis of intrinsic mitochondrial senescence, and its relation to the age-related changes in other cell organelles. The fine structural and biochemical data support the concept that the mitochondria of fixed postmitotic cells may be the site of intrinsic aging because of the attack by free radicals and lipid peroxides originating in the organelles as a by-product of oxygen reduction during respiration. Although the cells have numerous mechanisms for counteracting lipid peroxidation injury, there is a slippage in the antioxidant protection. Intrinsic mitochondrial aging could thus be considered as a specific manifestation of oxygen toxicity. It is proposed that free radical injury renders an increasing number of the mitochondria unable to divide, probably because of damage to the lipids of the inner membrane and to mitochondrial DNA.
Research done on detecting the contaminants of p-dioxane that cause a positive response for highly reactive acyl groups is discussed. Attention is given to the fact that the positive hydroxamate response might indicate an unsuspected hazard. It is found that all acyl groups transferred are formyl groups, and the mono- and diformates of 1,2-ethanediol are identified as major sources of this activity. It is also found that the formate esters are formed by way of peroxide intermediates. Concentrations of the formate ester group as high as 1.8 M are found in partially consumed bottles of dioxane but not in other common ethers stored under similar conditions. Attention is called to the possibility that the exposure to the glycol formates is probably much wider than expected. It is noted that by purging containers of dioxane with nitrogen each time they are opened and storing them in the cold away from light can prevent both the economic loss and possible health hazard caused by contamination with peroxide and formate ester.
Free radicals were studied by electron spin resonance (ESR) using model compounds that are representative of constituents of jet fuels. Radical formation was initiated with peroxides and hydroperoxides by using UV photolysis at and near room temperature and thermal initiation at higher temperatures. Both oxygen free and air saturated systems were studied. N-Dodecane was frequently used as a solvent, and a mixture of n-dodecyl radicals was made with a peroxide initiator in n-dodecane (free of oxygen) thermally at 212 C and photolytically at room temperature. Hydrogen abstraction from the 3,4,5 and 6-positions gives radicals that are sufficiently alike that their spectra are essentially superimposed. The radical formed by abstract of hydrogen from the 2-position gives a different spectrum. ESR parameters for these radicals were measured. The radical formed by abstraction of a primary hydrogen was not observed. Similar radicals are formed from n-decane. A variety of exploratory experiments were carried out with systems that give free radical spectra to which was added small amounts of 2,5-dimethylpyrrole.
Research is described which is directed toward the preparation of chemical oxygen sources which exhibited improved O2 storage and reaction characteristics when compared to potassium superoxide (KO2). The initial focus of the research was the preparation of calcium superoxide (Ca(O2)2) by the disproportionation of calcium peroxide diperoxyhydrate. the Ca(O2)2 was characterized by chemical, thermal, and x ray analyses. Several methods for scaling up the Ca(O2)2 syntheis process were studied. The reactivity of Ca(O2)2 toward humidified carbon dioxide (CO2) was evaluated and was compared to that of KO2 under flow test conditions approximating those existing in portable breathing apparatus. The reactivities of mixtures of KO2 and Ca(O2)2 or lithium peroxide towards humidified CO2 were also studied. Finally, an analysis of two commercial, KO2-based, self contained self rescuers was conducted to determine the potential weight and volume savings which would be possible if Ca(O2)2 or a mixture of KO2 and Ca(O2)2 were used as a replacement for KO2.
Evaluation of the ethyl vinyl acetate (EVA) encapsulation system is presented. This work is part of the materials baseline needed to demonstrate a 30 year module lifetime capability. Process and compound variables are both being studied along with various module materials. Results have shown that EVA should be stored rolled up, and enclosed in a plastic bag to retard loss of peroxide curing agents. The TBEC curing agent has superior shelf life and processing than the earlier Lupersol-101 curing agent. Analytical methods were developed to test for peroxide content, and experimental methodologies were formalized.
Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.
The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.
Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.
The review of disinfectants for use on manned missions emphasizes the need for contamination control to prevent the detrimental effects of bacteria growth on crew health. Microbial control is possible by means of biocides, but the selected product has to meet stringent toxicity requirements for the small environments in spacecraft. The testing and evaluation is described of four biocide candidates: hydrogen peroxide, quaternary ammonium compounds, iodine, and glutaraldehyde. The effectiveness of the disinfectants are analyzed in terms of the ability to treat typical microbial counts from Skylab missions in a closed environment. It is shown that many biocide candidates are not compatible with the ECLSS, water-recovery management, and air-revitalization subsystems of the Space Station Freedom. The use of hydrogen peroxide is proposed with a secondary stronger agent for microbial spills from biological experiments.
In the fall of 1987 during a photoacoustic study of hydrogen peroxide's fourth vibrational overtone band, the remarkably clear and well resolved spectrum was observed. Its periodicity and K subband structure suggested that the spectrum was not of hydrogen peroxide but of a smaller near-prolate symmetric top molecule. Furthermore, the time dependent behavior of the signal indicated that chemical changes were taking place within the photoacoustic apparatus.
A new emissions control system for the oxidizer scrubbers that eliminates the current oxidizer liquor waste and lowers the NO(x) emissions is described. Since fueling and deservicing spacecraft constitute the primary operations in which environmental emissions occur, this will eliminate the second largest waste stream at KSC. This effort is in accord with Executive Order No. 12856 (Federal Compliance with Right-to-Know Laws and Pollution Prevention Requirements, data 6 Aug. 1993) and Executive Order No. 12873 (Federal Acquisition, Recycling, and Waste Prevention, dated 20 Oct. 1993). A recent study found that the efficiencies of the oxidizer scrubbers during normal operations ranged from 70 percent to 99 percent. The new scrubber liquor starts with 1% hydrogen peroxide at a pH of 7 and the process control system adds hydrogen peroxide and potassium hydroxide to the scrubber liquor to maintain those initial conditions. The result is the formation of a solution of potassium nitrate, which is sold as a fertilizer. This report describes the equipment and procedures used to monitor and control the conversion of the scrubber liquor to fertilizer, while reducing the scrubber emissions.