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Indicator Devices for Detection of Trace Gaseous Hydrazines

The relatively recent decrease in the acceptable time-weighted-average for hydrazines from 100 parts-per-billion (ppb) to 10 ppb rendered many trace hydrazine detectors either insensitive or inaccurate. Development of a rapid detection method for hydrazines at the new 10-ppb concentration was necessary so that test area personnel could reliably assess airborne hydrazines concentrations of a potentially contaminated area prior to entry. The reduction of Au(III) to Au(0) by hydrazines is a well characterized reaction and application of the corresponding yellow to purple color change was selected as a potentially useful means for detection of trace hydrazines in air. Tests with small quantities of KAuCl4 deposited on a variety of substrates were conducted using verified sources of 1,1-dimethylhydrazine, methylhydrazine, and hydrazine at approximately 10 ppb in air. Substrates tested were glass fiber filter paper, glass beads, anion exchange resin (AuCl4- form), and diatomaceous earth. The most successful of these substrates were glass fiber filter paper and diatomaceous earth. The KAuC14 impregnated glass fiber filter paper appeared to be somewhat light sensitive so further tests were conducted using the diatomaceous earth substrate. KAuCl4 concentration, substrate particle size, and sampler configuration were evaluated. Based on these tests, the device selected for further evaluation was a 5mm OD by 50mm glass tube containing 0.02-0.03g of 45/60 mesh diatomaceous earth coated with 2 percent KAuCl4. When connected to a sampling pump, response of the device to changes in relative humidity, ambient light, and high levels of other fluids, which might also be found in a propellant test area, was evaluated. False positive responses were not detected for exposures to relative humidity changes from 10 to 80 percent, sunlight for greater than 10 minutes, or percent levels of ammonia, isopropyl alcohol, nitrogen dioxide, and hydrogen. In addition, body emissions did not produce a false positive response in view of potential application for use inside protective clothing. The device was shown to reliably detect less than 10 ppb of the hydrazines tested using a 10 to 20L sample followed by a 2 to 5 minute color development time. Some field tests were conducted in parallel with conventional acidic firebrick sorbent tubes. There was generally very good agreement between the devices and firebrick sorbent tubes when greater than 10 ppb of a hydrazine was present.

Dee, Lou A.↗

Pressure Dome for High-Pressure Electrolyzer

A high-strength, low-weight pressure vessel dome was designed specifically to house a high-pressure [2,000 psi (approx. = 13.8 MPa)] electrolyzer. In operation, the dome is filled with an inert gas pressurized to roughly 100 psi (approx. = 690 kPa) above the high, balanced pressure product oxygen and hydrogen gas streams. The inert gas acts to reduce the clamping load on electrolyzer stack tie bolts since the dome pressure acting axially inward helps offset the outward axial forces from the stack gas pressure. Likewise, radial and circumferential stresses on electrolyzer frames are minimized. Because the dome is operated at a higher pressure than the electrolyzer product gas, any external electrolyzer leak prevents oxygen or hydrogen from leaking into the dome. Instead the affected stack gas stream pressure rises detectably, thereby enabling a system shutdown. All electrical and fluid connections to the stack are made inside the pressure dome and require special plumbing and electrical dome interfaces for this to be accomplished. Further benefits of the dome are that it can act as a containment shield in the unlikely event of a catastrophic failure. Studies indicate that, for a given active area (and hence, cell ID), frame outside diameter must become ever larger to support stresses at higher operating pressures. This can lead to a large footprint and increased costs associated with thicker and/or larger diameter end-plates, tie-rods, and the frames themselves. One solution is to employ rings that fit snugly around the frame. This complicates stack assembly and is sometimes difficult to achieve in practice, as its success is strongly dependent on frame and ring tolerances, gas pressure, and operating temperature. A pressure dome permits an otherwise low-pressure stack to operate at higher pressures without growing the electrolyzer hardware. The pressure dome consists of two machined segments. An O-ring is placed in an O-ring groove in the flange of the bottom segment and is trapped by the flange on the top dome segment when these components are bolted together with high-strength bolts. The pressure dome has several unique features. It is made (to ASME Pressure Vessel guidelines) in a high-strength aluminum alloy with the strength of stainless steel and the weight benefits of aluminum. The flange of the upper dome portion contains specially machined flats for mounting the dome, and other flats dedicated to the special feedthroughs for electrical connections. A pressure dome can be increased in length to house larger stacks (more cells) of the same diameter with the simple addition of a cylindrical segment. To aid in dome assembly, two stainless steel rings are employed. One is used beneath the heads of the high-strength bolts in lieu of individual hardened washers, and another is used instead of individual nuts. Like electrolyzers could be operated at low or high pressures simply by operating the electrolyzer outside or inside a pressurized dome.

Norman, Timothy↗

Detection of Reduced Nitrogen Compounds at Rocknest Using the Sample Analysis At Mars (SAM) Instrument on the Mars Science Laboratory (MSL)

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected nitrogen-bearing compounds during the pyrolysis of Rocknest material at Gale Crater. Hydrogen cyanide and acetonitrile were identified by the quadrupole mass spectrometer (QMS) both in direct evolved gas analysis (EGA). SAM carried out four separate analyses from Rocknest Scoop 5. A significant low temperature release was present in Rocknest runs 1-4, while a smaller high temperature release was also seen in Rocknest runs 1-3. Here we evaluate whether these compounds are indigenous to Mars or a pyrolysis product resulting from known terrestrial materials that are part of the SAM derivatization.

Sample Analysis at Mars↗

Volatile Detections in Gale Crater Sediment and Sedimentary Rock: Results from the Mars Science Laboratory's Sample Analysis at Mars Instrument

This chapter discusses the detection of evolved gases from Gale crater sedimentary rock and eolian sediment by the Mars Science Laboratory rover's Sample Analysis at Mars (SAM) instrument. An overview is presented of the SAM instrument along with summary of key results from previous evolved gas analyses conducted at the Viking and Phoenix landing sites. The SAM measurements of evolved water, sulfur dioxide, carbon dioxide, carbon monoxide, oxygen, and nitrous oxide from Gale crater samples are presented. The phases responsible for the evolved gas detections and the implications for their presence are then evaluated. The water deuterium to hydrogen (D/H) ratio is discussed in context of understanding the degree of water loss from Mars. In the introduction of this book, we briefly explored the history of the exploration of Mars, where we discussed a major shift in the scientific thinking and public perception of the nature of the surface of Mars as new missions explored the Red Planet. The first observations of the surface sparked speculations of Mars being inhabited by intelligent beings, inspiring fantasy, science fiction, and, of course, further exploration. The turn came when Mariner 4 returned images of a lunar-like landscape, a monotonous basaltic world with many impact craters but no water, and therefore no prospects for life to find a habitable niche. The authors of the chapters of this book show how different our understanding of Mars is today from the historical Mariner 4 perspective!

Sutter, Brad↗

Oxygen and sulfur interactions with a clean iron surface and the effect of rubbing contact on these interactions

An investigation was conducted to determine the nature of the chemical interactions of oxygen and sulfur with iron when surfaces are stationary and also during sliding in a vacuum environment. Various gases that contained sulfur, oxygen, or both were adsorbed to iron at 23 C. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Friction experiments were conducted with a hemispherical rider sliding on a rotating disk. An Auger cylindrical mirror analyzer was used to monitor the iron surface chemistry. The results of this study indicate that oxygen will completely displace sulfide films from iron surfaces. Organic thiols containing sulfur, such as methyl mercaptan, adsorb to an iron surface dissociatively. Only sulfur is detected on the iron surface. Sliding inhibits the formation of sulfide films on iron with the adsorption of hydrogen sulfide and methyl mercaptan. With oxygen and sulfur dioxide, the sliding process does not affect adsorption behavior.

Buckley, D. H.↗

A comparison of Doppler lidar wind sensors for Earth-orbit global measurement applications

Now, there are four Doppler lidar configurations which are being promoted for the measurement of tropospheric winds: (1) the coherent CO2 Lidar, operating in the 9 micrometer region using a pulsed, atmospheric pressure CO2 gas discharge laser transmitter, and heterodyne detection; (2) the coherent Neodymium doped YAG or Glass Lidar, operating at 1.06 micrometers, using flashlamp or diode laser optical pumping of the solid state laser medium, and heterodyne detection; (3) the Neodymium doped YAG/Glass Lidar, operating at the doubled frequency (at 530 nm wavelength), again using flashlamp or diode laser pumping of the laser transmitter, and using a high resolution tandem Fabry-Perot filter and direct detection; and (4) the Raman shifted Xenon Chloride Lidar, operating at 350 nm wavelength, using a pulsed, atmospheric pressure XeCl gas discharge laser transmitter at 308 nm, Raman shifted in a high pressure hydrogen cell to 350 nm in order to avoid strong stratospheric ozone absorption, also using a high resolution tandem Fabry-Perot filter and direct detection. Comparisons of these four systems can include many factors and tradeoffs. The major portion of this comparison is devoted to efficiency. Efficiency comparisons are made by estimating the number of transmitted photons required for a single pulse wind velocity estimate of + or - 1 m/s accuracy in the middle troposphere, from an altitude of 800 km, which is assured to be reasonable for a polar orbiting platform.

Menzies, Robert T.↗

Lyman-Alpha Comes of Age

The Lyman-alpha (Lyα) line is the strongest recombination line of hydrogen, which constitutes the dominant share of normal matter in the Universe. Fifty-one years ago, it was predicted that Lyα emission should appear prominently in the spectra of young primordial galaxies. For the next 30 years, this prediction was tested by many surveys, but none found the predicted galaxies at the predicted luminosities. The blame for these non-detections was squarely cast on the resonant nature of the Lyα line, which requires Lyα photons to scatter off many hydrogen atoms before escaping from a galaxy. This can hugely increase the path that they traverse, and consequently also the probability that they will be absorbed by dust. This remained the dominant explanation of the missing high-redshift lines for decades, despite some dissenting opinions about the effect of dust. The spectra of nearby galaxies from the International Ultraviolet Explorer are inconclusive about what allows galaxies to be Lyα emitters. The ‘missing’ lines were finally detected 20 years ago, at flux levels much below the original predictions - a difference that we understand to be predominantly due to the hierarchical growth of galaxies, such that star-forming objects at high redshift are much less massive than anticipated in the original prediction. The discovery and study of Lyα galaxies has blossomed into an invaluable method for understanding the youngest stages of galaxy formation, the circumgalactic medium, and ultimately the epoch of reionization. The high equivalent widths of Lyα galaxies from the earliest high-redshift surveys show that they are low-mass galaxies dominated by young stellar populations. The Sakura CLAW workshop (which used the Twitter hashtag #SakuraCLAW) gathered more than 110 participants (Fig. 1) who showcased progress that pushed the frontiers of Lyα galaxy science in sample size, sensitivity, redshifts and physical understanding..

Malhotra, Sangeeta↗

Development of Microfabricated Chemical Gas Sensors and Sensor Arrays for Aerospace Applications

Aerospace applications require the development of chemical sensors with capabilities beyond those of commercially available sensors. In particular, factors such as minimal sensor size, weight, and power consumption are particularly important. Development areas which have potential aerospace applications include launch vehicle leak detection, engine health monitoring, fire detection, and environmental monitoring. Sensor development for these applications is based on progress in three types of technology: 1) Micromachining and microfabrication (Microsystem) technology to fabricate miniaturized sensors. 2) The use of nanocrystalline materials to develop sensors with improved stability combined with higher sensitivity. 3) The development of high temperature semiconductors, especially silicon carbide. However, due to issues of selectivity and cross-sensitivity, individual sensors are limited in the amount of information that they can provide in environments that contain multiple chemical species. Thus, sensor arrays are being developed to address detection needs in such multi-species environments. This paper discusses the needs of space applications as well as the point-contact sensor technology and sensor arrays being developed to address these needs. Sensors to measure hydrogen, hydrocarbons, hydrazine, nitrogen oxides (NO,), carbon monoxide, oxygen, and carbon dioxide are being developed as well as arrays for leak, fire, and emissions detection. Demonstrations of the technology will also be discussed. It is concluded that microfabricated sensor technology has significant potential for use in a range of aerospace applications.

Hunter, G. W.↗

Catalysts for initiating the hydrogen-oxygen reaction at 78 K.

Catalysts for initiating reaction of hydrogen with oxygen in gas mixtures at temperatures down to 78 K (-195 C) were sought. A rising-temperature reactor was used for detecting onset of reaction. The platinum metals, especially iridium, platinum, and ruthenium, were the most active. With high concentrations of iridium on an alumina support, reaction initiation was observed at -195 C for a helium stream containing 3% hydrogen and 1% oxygen. Best results were obtained when the catalyst had been preheated in hydrogen and cooled in a hydrogen environment before being contacted with oxygen-containing gas. The initiation is interpreted to be the result of transient phenomena which occur when a hydrogen-oxygen mixture contacts an active catalyst. Chemisorption of oxygen and formation of some water, along with water adsorption on the support, serve to raise the temperature to a point where true catalysis can proceed.

Jennings, T. J.↗

Gravitational waves and red shifts - A space experiment for testing relativistic gravity using multiple time-correlated radio signals

A two-step satellite mission for improving the accuracy of gravitational wave detection and for observing actual gravity waveforms is proposed. The spacecraft would carry both a highly stable hydrogen maser, which would control a transmitter sending signals to earth, and a Doppler transponder operating in the two-way mode. The use of simultaneous one- and two-way Doppler transmissions offers four time records of frequency pulsations, which can reveal gravitational radiation at 1-10 MHz with an amplitude accuracy of a factor of six. The first mission phase would consist of a Shuttle launch into a highly eccentric orbit to obtain measurements of the gravitational redshift using gravitational potentials of different earth regions to establish that gravity is describable by a metric theory. Then, after a boost into a heliocentric orbit at 6 AU, the earth-satellite system could detect gravitational waves in the solar system, as well as bursts emitted by the collisions of supermassive black holes.

Smarr, L. L.↗

Possible sources of the diffuse soft X-ray flux

A review is presented of recent arguments concerning the origin of the cosmic X-ray background in the energy region below 1 keV. Observational limitations on a possible hot intergalactic medium are discussed. Reanalysis of the Small Magellatic Cloud shadowing experiment of McCammon et al. (1971) using refined neutral hydrogen maps have confirmed the conclusion that at least 75% of the 1/4 keV flux detected from that direction must originate from regions closer than the SMC. Recent rocket observations have located three galactic soft X-ray emitting regions of large angular extent. Arguments are reviewed that the emission mechanism for this diffuse galactic flux must be thermal. It is suggested that a component of the interstellar medium is very hot and is responsible for both the soft X-ray background and the oxygen VI ions seen as interstellar absorption lines in the ultraviolet spectra of some early-type stars observed by the Copernicus satellite.

Bunner, A. N.↗

Applications of chemiluminescence to bacterial analysis

Luminol chemiluminescence method for detecting bacteria was based on microbial activation of the oxidation of the luminol monoanion by hydrogen peroxide. Elimination of the prior lysing step, previously used in the chemiluminescence technique, was shown to improve considerably the reproducibility and accuracy of the method in addition to simplifying it. An inexpensive, portable photomultiplier detector was used to measure the maximum light intensity produced when the sample is added to the reagent. Studies of cooling tower water show that the luminol chemiluminescence technique can be used to monitor changes in viable cell population both under normal conditions and during chlorine treatment. Good correlation between chemiluminescence and plate counts was also obtained in the analysis of process water used in paper mills. This method showed good potential for monitoring the viable bacteria populations in activated sludge used in waste treatment plants to digest organic matter.

Searle, N. D.↗

Electrochemical incineration of wastes

A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.

Kaba, L.↗

He I absorption by Lyman-alpha clouds and low-redshift Lyman-alpha clouds

Sources and sinks of radiation are used to model the evolution of the metagalactic ionizing background radiation field. It is shown that, if the comoving number density of quasars approached constancy at high redshift, as suggested by some recent observations, the observed ionizing background might possibly have been produced by the observed quasars alone. Consideration is also given to the UV radiation from decaying neutrons proposed by Sciama (1990), as an extra possible source. If is found that, if the background spectrum were as soft as in the Sciama scenario, the observed Ly-alpha clouds would contain detectable amounts of neutral helium, producing an 'He I forest' almost as dense as the hydrogen forest, due to the 584-A transition 1s-squared-1s2p. It is argued that observations of the Ly-alpha forest contradict the Sciama hypothesis.

Miralda-Escude, Jordi↗

TRACE-P OH and HO2 Measurements with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) on the DC-8

The Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) measures OH and HO2 from the NASA DC-8. This instrument detects OH by laser induced fluorescence (LIF) in detection chambers at low pressure and detects HO2 by chemical conversion with NO followed by LIF detection. The demonstrated detection limit (S/N=2, 5 min.) for OH is about 0.005 pptv (1x10(exp 6)/cu cm at 2 km altitude) and for HO2 is 0.05 pptv (1x10(exp 6)/cu cm at 2 km altitude). We will use ATHOS to measure OH, HO2, and HO2/OH during TRACE- P, analyze these results by comparing them against fundamental relationships and computer models, and publish the analyses. TRACE-P HO(x), measurements will help develop a clearer picture of the atmospheric oxidation and 0 3 production that occur as Asian pollution spreads across the Pacific Ocean.

Brune, William H.↗

PillCam(TradeMark), a Noninvasive Endoscopic Device for the Measurement of Gastrointestinal Motility Changes

Introduction: Bioavailability and effectiveness of drugs given by mouth are governed in part by gastrointestinal (GI) motility and function. Microgravity has been shown to decrease GI motility as indicated by a 3 fold increase in gastrointestinal transit time (GITT). The PillCam(TradeMark), an endoscopic camera embedded in a capsule, is a novel noninvasive and unobtrusive device that is used for the diagnosis of GI pathology. The purpose of this study is to evaluate the usefulness of PillCam(TradeMark) as an alternative to the Lactulose Breath Hydrogen Test (LBHT) for estimating GI motility. The sensitivity and applicability of this device for detection and estimation of the effect of promethazine, a deterrent, and caffeine, a prokinetic, on GI motility were also examined. Method: In this semi-randomized cross-over design study, six male and six female subjects were administered the following 4 treatments: PillCam(TradeMark) alone, PillCam(TradeMark)+Lactulose (10g), PillCam(TradeMark)+caffeine (200mg), and PillCam(TradeMark)+Promethazine (50mg). Results: GITT ranged between 1:24 and 7:52 hr:min. Lactulose did not alter GITT. A significant increase in GITT was noticed after administration of PMZ when compared to values from PillCam(TradeMark) treatment alone or PillCam(TradeMark)+Lactulose treatment. No difference in GITT after caffeine treatment was noticed. While there were no gender related differences in GITT after administration of PillCam(TradeMark) or with lactulose, a significant difference (p<.05) between genders was observed after promethazine administration with mean GITT higher in males (5:50 hr:min) than females (4:15 hr:min). Conclusion: The PillCam(TradeMark) capsule is applicable for the determination of GITT using time stamped GI images. It can be successfully used for the assessment of drug induced changes in GI motility and therefore, may be applicable for microgravity and analog environment studies on GI motility and function.

Vaksman, Zahman↗

Chemical sensors using coated or doped carbon nanotube networks

Methods for using modified single wall carbon nanotubes ("SWCNTs") to detect presence and/or concentration of a gas component, such as a halogen (e.g., Cl.sub.2), hydrogen halides (e.g., HCl), a hydrocarbon (e.g., C.sub.nH.sub.2n+2), an alcohol, an aldehyde or a ketone, to which an unmodified SWCNT is substantially non-reactive. In a first embodiment, a connected network of SWCNTs is coated with a selected polymer, such as chlorosulfonated polyethylene, hydroxypropyl cellulose, polystyrene and/or polyvinylalcohol, and change in an electrical parameter or response value (e.g., conductance, current, voltage difference or resistance) of the coated versus uncoated SWCNT networks is analyzed. In a second embodiment, the network is doped with a transition element, such as Pd, Pt, Rh, Ir, Ru, Os and/or Au, and change in an electrical parameter value is again analyzed. The parameter change value depends monotonically, not necessarily linearly, upon concentration of the gas component. Two general algorithms are presented for estimating concentration value(s), or upper or lower concentration bounds on such values, from measured differences of response values.

Li, Jing↗