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Optical remote measurement of toxic gases

Enactment of the Clean Air Act Amendments (CAAA) of 1990 has resulted in increased ambient air monitoring needs for industry, some of which may be met efficiently using open-path optical remote sensing techniques. These techniques include Fourier transform spectroscopy, differential optical absorption spectroscopy, laser long-path absorption, differential absorption lidar, and gas cell correlation spectroscopy. With this regulatory impetus, it is an opportune time to consider applying these technologies to the remote and/or path-averaged measurement and monitoring of toxic gases covered by the CAAA. This article reviews the optical remote sensing technology and literature for that application.

Review↗

The Situational Awareness Sensor Suite for the ISS (SASSI): A Mission Concept to Investigate ISS Charging and Wake Effects

The complex interaction between the International Space Station (ISS) and the surrounding plasma environment often generates unpredictable environmental situations that affect operations. Examples of affected systems include extravehicular activity (EVA) safety, solar panel efficiency, and scientific instrument integrity. Models and heuristically‐derived best practices are well‐suited for routine operations, but when it comes to unusual or anomalous events or situations, especially those driven by space weather, there is no substitute for real‐time monitoring. Space environment data collected in real‐time (or near‐real time) can be used operationally for both real‐time alarms and data sources in assimilative models to predict environmental conditions important for operational planning. Fixed space weather instruments mounted to the ISS can be used for monitoring the ambient space environment, but knowing whether or not (or to what extent) the ISS affects the measurements themselves requires adequate space situational awareness (SSA) local to the ISS. This paper presents a mission concept to use a suite of plasma instruments mounted at the end of the ISS robotic arm to systematically explore the interaction between the Space Station structure and its surrounding environment. The Situational Awareness Sensor Suite for the ISS (SASSI) would be deployed and operated on the ISS Express Logistics Carrier (ELC) for long‐term "survey mode" observations and the Space Station Remote Manipulator System (SSRMS) for short‐term "campaign mode" observations. Specific areas of investigation include: 1) ISS frame and surface charging during perturbations of the local ISS space environment, 2) calibration of the ISS Floating Point Measurement Unit (FPMU), 3) long baseline measurements of ambient ionospheric electric potential structures, 4) electromotive force-induced currents within large structures moving through a magnetized plasma, and 5) wake‐induced ion waves in both electrostatic (i.e. particles) and electromagnetic modes. SASSI will advance the understanding of plasma‐boundary interaction phenomena, demonstrate a suite a sensors acting in concert to provide effective SSA, and validate and/or calibrate existing ISS space environment instruments and models.

Krause, L. Habash↗

Effects of Ambient Alcohol Levels on the Real-time Monitoring of the Atmosphere of the International Space Station

Effects of Ambient Alcohol Levels on the Real-time Monitoring of the Atmosphere of the International Space StationWilliam T. Wallace,1 Thomas F. Limero,1 Kenneth W. Clark,2 and Daniel B. Gazda31KBR, 2400 NASA Pkwy., Houston, TX 770582JES Tech, 16870 Royal Crest Dr., Houston, TX 770583NASA Lyndon B. Johnson Space Center, 2101 NASA Pkwy., Houston, TX 77058Monitoring of the spacecraft environment is required to ensure the safety of the crew and the health of the vehicle systems. For the ISS atmosphere, routine monitoring has been performed for many years by the Major Constituent Analyzer (MCA) and two Air Quality Monitors (AQMs), which, together, are used to monitor for trace (ppb) levels of 22 volatile organic compounds (VOCs). The target compounds measured by the AQMs include three types of chemicals: 1) those compounds that would be harmful to crew, 2) those compounds that have been detected regularly in archival samples, and 3) compounds that, while not necessarily harmful to crew health, could present problems for Environmental Control and Life Support Systems (ECLSS).In March 2019, following the docking of SpaceX-Demo1 (SpX-DM1), the on-board AQMs began to report extremely high levels of isopropyl alcohol (IPA). While elevated IPA is not abnormal following the docking of visiting vehicles (due to cleaning of the cargo prior to flight), the level measured by the AQM, and its continued presence following multiple days of scrubbing, caused concerns regarding the U.S. Water Recovery System. Following the departure of SpX-DM1, the IPA levels decreased to nominal levels, allowing the team to investigate the cause of the elevated measurements. Initially, based on the changes in the shape of the gas chromatograph (GC) traces in the IPA region during docked operations, it appeared that some unknown coeluting species was causing problems with quantification. However, with the docking of Northrup-Grumman-11 (NG-11), the elevated IPA concentrations returned, as well as the changes in GC traces. In contrast to the SpX-DM1 results, though, the AQM IPA results did not return to nominal levels following the departure of NG-11, suggesting that the changes could not be tied directly to the visiting vehicle.In this paper, we will discuss a number of potential causes for both the genuine (measured in archival samples) increases in IPA as well as the much higher levels measured by the AQM. Additionally, we will discuss methods being explored to decrease the potential for a reoccurrence in the future.

William T Wallace↗

multiplex gas chromatography: A novel analytical technique for future planetary studies

Determination of molecular species comprised of the biogenic elements in the atmospheres of planets and moons of the solar system is one the foremost requirements of the exobiologist studying chemical evolution and the origin of life. Multiplex chromatography is a technique where many samples are pseudo-randomly introduced to the chromatograph without regard to elution of preceding components. The resulting data are then reduced using mathematical techniques such as cross correlation or Fourier Transforms. To demonstrate the utility of this technique for future solar system exploration, chemical modulators were developed. Several advantages were realized from this technique in combination with these modulators: improvement in detection limits of several orders of magnitude, improvement in the analysis of complex mixtures by selectively modulating some of the components present in the sample, increase in the number of analyses that can be conducted in a given period of time, and reduction in the amount of expendables needed to run an analysis. In order to apply this technique in a real application, methane in ambient air was monitored continuously over a period of one week. By using ambient air as its own carrier all expendables beyond power were eliminated.

Valentin, J. R.↗

A Description of the Philips SO2 Monitor

Strict standards for ambient sulfur dioxide requirements in the San Francisco Bay Area result in strict criteria for monitor operations by private industry. Of nine different monitors tested, three are acceptable. One, the Phillips PW 9700, senses sulfur dioxide by coulometric reaction with bromine in a potassium bromide solution. The monitor has a high degree of sensitivity, rapid response, and stable attendance or maintenance is aided by quality construction, internal reagent supply, and elimination of reagent pump. Options include automatic zeroing and calibration, probe filter and heater, and telemetering output.

Potter, L. B.↗

Beta Absorption Mass Monitoring of Particulates - A Review

The theory and application of beta-radiation absorption for the measurement and monitoring of airborne particulates are discussed. The use of this technique, both for source testing and for ambient air quality monitoring is reviewed. Various particle collection methods used in conjunction with beta absorption sensing configurations are considered. State of the art and current developments of instrumentation approaches for the automated measurement of mass concentration and size distribution of aerosols by beta absorption are discussed. Methods for electronic signal processing and recording are presented. The Beta absorption technique appears as a powerful tool for the unattended measurement of the mass of particulate pollution, compatible with telemetry and central data processing methods.

Lilienfeld, Pedro↗

Application of Commercial Non-Dispersive Infrared Spectroscopy Sensors for Sub-Ambient Carbon Dioxide Detection

Monitoring carbon dioxide (CO2) concentration within a spacecraft or spacesuit is critically important to ensuring the safety of the crew. Carbon dioxide uniquely absorbs light at wavelengths of 3.95 micrometers and 4.26 micrometers. As a result, non-dispersive infrared (NDIR) spectroscopy can be employed as a reliable and inexpensive method for the quantification of CO2 within the atmosphere. A multitude of commercial-off-the-shelf (COTS) NDIR sensors exist for CO2 quantification. The COTS sensors provide reasonable accuracy so long as the measurements are attained under conditions close to the calibration conditions of the sensor (typically 21.1 C and 1 atm). However, as pressure deviates from atmospheric to the pressures associated with a spacecraft (8.0-10.2 PSIA) or spacesuit (4.1-8.0 PSIA), the error in the measurement grows increasingly large. In addition to pressure and temperature dependencies, the infrared transmissivity through a volume of gas also depends on the composition of the gas. As the composition is not known a priori, accurate sub-ambient detection must rely on iterative sensor compensation techniques. This manuscript describes the development of recursive compensation algorithms for sub-ambient detection of CO2 with COTS NDIR sensors. In addition, the basis of the exponential loss in accuracy is developed theoretically considering thermal, Doppler, and Lorentz broadening effects which arise as a result of the temperature, pressure, and composition of the gas mixture under analysis. As a result, this manuscript provides an approach to employing COTS sensors at sub-ambient conditions and may also lend insight into designing future NDIR sensors for aerospace application.

Swickrath, Michael J.↗

Application of Commercial Non-Dispersive Infrared Spectroscopy Sensors for Sub-Ambient Carbon Dioxide Detection

Monitoring carbon dioxide (CO2) concentration within a spacecraft or spacesuit is critically important to ensuring the safety of the crew. Carbon dioxide uniquely absorbs light at wavelengths of 3.95 micrometers and 4.26 micrometers. As a result, non-dispersive infrared (NDIR) spectroscopy can be employed as a reliable and inexpensive method for the quantification of CO2 within the atmosphere. A multitude of commercial off-the-shelf (COTS) NDIR sensors exist for CO2 quantification. The COTS sensors provide reasonable accuracy as long as the measurements are attained under conditions close to the calibration conditions of the sensor (typically 21.1 C (70.0 F) and 1 atmosphere). However, as pressure deviates from atmospheric to the pressures associated with a spacecraft (8.0{10.2 pounds per square inch absolute (psia)) or spacesuit (4.1{8.0 psia), the error in the measurement grows increasingly large. In addition to pressure and temperature dependencies, the infrared transmissivity through a volume of gas also depends on the composition of the gas. As the composition is not known a priori, accurate sub-ambient detection must rely on iterative sensor compensation techniques. This manuscript describes the development of recursive compensation algorithms for sub-ambient detection of CO2 with COTS NDIR sensors. In addition, the source of the exponential loss in accuracy is developed theoretically. The basis of the loss can be explained through thermal, Doppler, and Lorentz broadening effects that arise as a result of the temperature, pressure, and composition of the gas mixture under analysis. This manuscript provides an approach to employing COTS sensors at sub-ambient conditions and may also lend insight into designing future NDIR sensors for aerospace application.

Swickrath, Michael J.↗

The active titration method for measuring local hydroxyl radical concentration

We are developing a method for measuring ambient OH by monitoring its rate of reaction with a chemical species. Our technique involves the local, instantaneous release of a mixture of saturated cyclic hydrocarbons (titrants) and perfluorocarbons (dispersants). These species must not normally be present in ambient air above the part per trillion concentration. We then track the mixture downwind using a real-time portable ECD tracer instrument. We collect air samples in canisters every few minutes for roughly one hour. We then return to the laboratory and analyze our air samples to determine the ratios of the titrant to dispersant concentrations. The trends in these ratios give us the ambient OH concentration from the relation: dlnR/dt = -k(OH). A successful measurement of OH requires that the trends in these ratios be measureable. We must not perturb ambient OH concentrations. The titrant to dispersant ratio must be spatially invariant. Finally, heterogeneous reactions of our titrant and dispersant species must be negligible relative to the titrant reaction with OH. We have conducted laboratory studies of our ability to measure the titrant to dispersant ratios as a function of concentration down to the few part per trillion concentration. We have subsequently used these results in a gaussian puff model to estimate our expected uncertainty in a field measurement of OH. Our results indicate that under a range of atmospheric conditions we expect to be able to measure OH with a sensitivity of 3x10(exp 5) cm(exp -3). In our most optimistic scenarios, we obtain a sensitivity of 1x10(exp 5) cm(exp -3). These sensitivity values reflect our anticipated ability to measure the ratio trends. However, because we are also using a rate constant to obtain our (OH) from this ratio trend, our accuracy cannot be better than that of the rate constant, which we expect to be about 20 percent.

Sprengnether, Michele↗

Thermoregulatory responses of rats to varying environmental temperatures

The peripheral (tail) circulatory responses of six male albino rats were measured at ambient temperatures between 5 and 40 C, using impedance plethysmography. Each animal was anesthetized, instrumented, and placed in a thermal environmental chamber to reach equilibrium. Tail blood flow, respiration rate, heart rate, core temperature, and tail skin temperature were then monitored at each ambient temperature. The mean tail blood flow was significantly higher (p less than 0.05) at 5 C than at 10 C. The mean blood flow increased significantly (p less than 0.01) at each of the temperatures above 10 C. Tail skin temperature and internal body (core) temperature increased significantly with increasing ambient temperature.

Berry, J. J.↗

Moisture-Induced Delayed Alumina Scale Spallation on a Ni(Pt)Al Coating

Delayed interfacial scale failure takes place after cooling for samples of a Ni(Pt)Al-coated CMSX4 single crystal superalloy, cycled at 1150 C for up to 2000 hr. One sample exhibited premature coating grain boundary wrinkling, alumina scale spallation to bare metal, and a final weight loss of 3.3 mg/cm2 . Spallation under ambient conditions was monitored with time after cooldown and was found to continue for 24 hr. This produced up to 0.05 mg/cm2 additional loss for each hold, accumulating 0.7 mg/cm 2 (20 percent of the total) over the course of the test. After test termination, water immersion produced an additional 0.15 mg/cm2 loss. (A duplicate sample produced much less wrinkling and time dependent spalling, maintaining a net weight gain.) The results are consistent with the general phenomena of moisture-induced delayed spallation (MIDS) of mature, distressed alumina scales formed on oxidation resistant M-Al alloys. Relative ambient humidity is discussed as the factor controlling adsorbed moisture, reaction with the substrate, and hydrogen effects on interface strength.

Smialek, James L.↗

A gas chromatographic air analyzer fabricated on a silicon wafer

A miniature gas analysis system has been built based on the principles of gas chromatography (GC). The major components are fabricated in silicon using photolithography and chemical etching techniques, which allows size reductions of nearly three orders of magnitude compared to conventional laboratory instruments. The chromatography system consists of a sample injection valve and a 1.5-m-long separating capillary column, which are fabricated on a substrate silicon wafer. The output thermal conductivity detector is separately batch fabricated and integrably mounted on the substrate wafer. The theory of gas chromatography has been used to optimize the performance of the sensor so that separations of gaseous hydrocarbon mixtures are performed in less than 10 s. The system is expected to find application in the areas of portable ambient air quality monitors, implanted biological experiments, and planetary probes.

Terry, S. C.↗

Experiments on a round turbulent buoyant plume

This paper reports a comprehensive set of hot-wire measurements of a round buoyant plume which was generated by forcing a jet of hot air vertically up into quiescent environment. The boundary conditions of the experiment were measured, and are documented in the present paper in an attempt to sort out the contradictory mean flow results from the earlier studies. The ambient temperature was monitored to insure that the facility was not stratified and that the experiment was conducted in a neutral environment. The axisymmetry of the flow was checked by using a planar array of sixteen thermocouples and the mean temperature measurements from these are used to supplement the hot-wire measurements. The source flow conditions were measured so as to ascertain the rate at which the buoyancy was added to the flow. The measurements conserve buoyancy within 10 percent. The results are used to carry out the balances of the mean energy and momentum differential equations. In the mean energy equation it is found that the vertical advection of the energy is primarily balanced by the radial turbulent transport. In the mean momentum equation the vertical advection of momentum and the buoyancy force balance the radial turbulent transport. The buoyancy force is the second largest term in this balance and is responsible for the wider (and higher) velocity profiles in plumes as compared to jets. Budgets of the temperature variance and turbulence kinetic energy are also carried out in which thermal and mechanical dissipation rates are obtained as the closing terms. Similarities and differences between the two balances are discussed. It is found that even though the direct affect of buoyancy on turbulence, as evidenced by the buoyancy production term, is substantial, most of the turbulence is produced by shear. This is in contrast to the mean velocity field where the affect of buoyancy force is quite strong. Therefore, it is concluded that in a buoyant plume the primary affect of buoyancy on turbulence is indirect, and enters through the mean velocity field (giving larger shear production).

Shabbir, Aamir↗

The orbital debris detector consortium: Suppliers of instruments for in-situ measurements of small-particles in the space environment

Industry and university participants have joined together to form the IMPA:Ct consortium (In-situ Monitors of the Particulate Ambient: Circumterrestrial) which offers a broad range of flight qualified instruments for monitoring the small particle (0.1 micron to 10 cm) environment in space. Instruments are available in 12 months or less at costs ranging from 0.5 to 1.5 million dollars (US) for the total program. Detector technologies represented by these groups are: impact-induced capacitor-discharge (MOS, metal-oxide-silicon), cratering or penetration of electroactive thin film (polyvinylidene fluoride (PVDF)), impact-plasma detection, acoustic detection, CCD tracking of optical scatter of sunlight, and photodiode detection of optical scatter of laser light. The operational characteristics, general spacecraft interface and resource requirements (mass/power/telemetry), cost and delivery schedules, and points of contact for seven different instruments are presented.

Simon, C. G.↗

Effects of Ambient Alcohol Levels on the Real-time Monitoring of the Atmosphere of the International Space Station

Monitoring of the spacecraft environment is required to ensure the health of the crew and the vehicle systems. For the ISS atmosphere, routine volatile organic compound (VOC) monitoring has been performed for almost a decade by Air Quality Monitors (AQMs). The target compounds measured by the AQMs include three types of chemicals: 1) those compounds that would be harmful to crew, 2) those compounds that have been detected regularly in archival samples, and 3) compounds that, while not necessarily harmful to crew health, could present problems for Environmental Control and Life Support Systems (ECLSS). Following the docking of SpaceX-Demo1 (SpX-DM1), the AQMs began to report high levels of isopropanol (IPA). While elevated IPA is routinely observed with visiting vehicles, the level measured by the AQM, and its continued presence following multiple days of scrubbing, caused concerns regarding the U.S. Water Recovery System. Following the departure of SpX-DM1, the IPA levels decreased to nominal levels, allowing the team to investigate the cause of the elevated measurements. Based on the changes in the shape of the gas chromatograph (GC) traces in the IPA region during docked operations, it appeared that an unknown coeluting species was causing problems with quantification. However, with the docking of Northrup-Grumman-11 (NG-11), the elevated IPA returned, as well as the changes in GC traces. In contrast to the SpX-DM1 results, the AQM IPA results did not return to nominal levels following the departure of NG-11, suggesting that the changes could not be tied directly to the visiting vehicle. In this paper, we will discuss a number of potential causes for both the genuine (measured in archival samples) increases in IPA as well as the much higher levels measured by the AQM. Additionally, we will discuss methods being explored to decrease the potential for a reoccurrence in the future.

William T. Wallace↗

Non-thermal distribution of O(1D) atoms in the night-time thermosphere

The 6300 A O(1D-3P) emission has been used for many years to remotely monitor the thermospheric temperature from the Doppler width of its line profile. The O(1D) atoms in the nighttime thermosphere are initially produced by the dissociative recombination of O2(+) ions with kinetic energy much greater than the thermal energy of the ambient neutrals. The validity of the technique to monitor neutral ambient temperature by measuring O(1D) 6300 A emission depends on the degree of thermalization of the O(1D) atoms. The object of this study is to calculate the velocity distribution of the O(1D) atoms and to examine the effect of nonthermal distribution on the nighttime thermospheric neutral temperature determined.

Yee, Jeng-Hwa↗

Stability of PMR-polyimide monomer solutions

The stability of alcohol solutions of norborneyl capped PMR-polyimide resins was monitored during storage at ambient and subambient temperatures. Chemical changes during storage were determined spectroscopically using nuclear magnetic resonance. Resin processability and cured resin quality were determined by fabrication of unidirectional, graphite fiber composites using aged solutions and testing of selected composite properties. PMR-15 solutions exhibit nominally two weeks of useful life and PMR-2 solutions exhibit nominally two days of useful life at ambient conditions. The limiting factor is precipitation of imide reaction produces from the monomer solutions. Both solutions exhibit substantially longer useful lifetimes in subambient storage. PMR-15 shows no precipitation after several months storage at subambient temperatures. PMR-2 solutions do exhibit precipitates after extended subambient storage, however, the precipitates formed under these conditions can be redissolved. The chemical implications of these observations are discussed.

Lauver, R. W.↗

Stability of PMR-polyimide monomer solutions

The stability of alcohol solutions of norbornenyl capped PMR-polyimide resins (both PMR-15 and PMR-II) has been monitored during storage at ambient and subambient (5 C and -18 C) temperatures. PMR-15 solutions exhibit nominally two weeks of useful life and PMR-II solutions exhibit nominally two days of useful life at ambient conditions. The limiting factor is precipitation of imide reaction products from the monomer solutions. Both solutions exhibit substantially longer useful lifetimes in subambient storage. PMR-15 shows no precipitation after several months storage at subambient temperatures. PMR-II solutions do exhibit precipitates after extended subambient storage (nominally three months at -18 C), however, the precipitates formed under these conditions can be redissolved. The chemical implications of these observations are discussed.

Lauver, R. W.↗