[Show abstract][Hide abstract] ABSTRACT: Scores of compounds are found in the International Space Station (ISS) atmospheric samples that are returned to the Johnson Space Center Toxicology Laboratory for analysis. Spacecraft Maximum Allowable Concentrations (SMACs) are set with the view that each compound is present as if there were no other compounds present. In order to apply SMACs to the interpretation of the analytical data, the toxicologist must employ some method of combining the potential effects of the aggregate of compounds found in the atmospheric samples. The simplest approach is to assume that each quantifiable compound has the potential for some effect in proportion to the applicable SMAC, and then add all the proportions. This simple paradigm disregards the fact that most compounds have potential to adversely affect only a few physiological systems, and their effects would be independent rather than additive. An improved approach to dealing with exposure to mixtures is to add the proportions only for compounds that adversely affect the same physiological system. For example, toxicants that cause respiratory irritation are separated from those that cause neurotoxicity or cardiotoxicity. Herein we analyze ISS air quality data according to toxicological groups with a view that this could be used for understanding any crew symptoms occurring at the time of the sample acquisition or when an on-board air quality monitor indicates high pollution. In addition, this approach could be useful in post-flight longitudinal surveys in which the flight surgeon may need to identify post-flight, follow-up medical studies because of on-orbit exposures that target specific physiological systems.
[Show abstract][Hide abstract] ABSTRACT: A combustion products analyzer (CPA) was built for use on Shuttle in response to several thermodegradation incidents that had occurred during early flights. The CPA contained sensors that measured carbon monoxide, hydrogen chloride, hydrogen cyanide, and hydrogen fluoride. These marker compounds, monitored by the CPA, were selected based upon the likely products to be released in a spacecraft fire. When the Toxicology Laboratory group at Johnson Space Center (JSC) began to assess the air quality monitoring needs for the International Space Station (ISS), the CPA was the starting point for design of an instrument to monitor the atmosphere following a thermodegradation event. The final product was significantly different from the CPA and was named the compound specific analyzer-combustion products (CSA-CP). The major change from the CPA that will be the focus of this paper was the replacement of an unreliable hydrogen fluoride (HF) sensor with an oxygen sensor. A reliable HF sensor was not commercially available, but as the toxicology group reviewed the overall monitoring strategy for ISS, it appeared that a portable oxygen sensor to backup the major constituent analyzer was needed. Therefore, an oxygen sensor replaced the HF sensor in the new instrument. This paper will describe the development, deployment, and performance of the CSA-CP oxygen sensor on both Shuttle and ISS. Also, data for CSA-CP oxygen sensor accuracy at nominal and reduced pressures will be presented.
[Show abstract][Hide abstract] ABSTRACT: The goal of toxicological risk assessment of human space flight is to identify and quantify significant risks to astronaut health from air pollution inside the vehicle or habitat, and to develop a strategy for control of those risks. The approach to completing a toxicological risk assessment involves data and experience on the frequency and severity of toxicological incidents that have occurred during space flight. Control of these incidents depends on being able to understand their cause from in-flight and ground-based analysis of air samples, crew reports of air quality, and known failures in containment of toxic chemicals. Toxicological risk assessment in exploration missions must be based on an evaluation of the unique toxic hazards presented by the habitat location. For example, lunar and Martian dust must be toxicologically evaluated to determine the appropriate control measures for exploration missions. Experience with near-earth flights has shown that the toxic products from fires present the highest risk to crew health from air pollution. Systems and payload leaks also present a significant hazard. The health risk from toxicity associated with materials offgassing or accumulation of human metabolites is generally well controlled. Early tests of lunar and Martian dust simulants have shown that each posses the potential to cause fibrosis in the lung in a murine model. Toxicological risks from air pollutants in space habitats originate from many sources. A number of risks have been identified through near-earth operations; however, the evaluation of additional new risks present during exploration missions will be a challenge.
[Show abstract][Hide abstract] ABSTRACT: Space-faring crews must have safe breathing air throughout their missions to ensure adequate performance and good health. Toxicological assessment of air quality depends on the standards that define acceptable air quality, measurements of pollutant levels during the flight, and reports from the crew on their in-flight perceptions of air quality. Air samples from ISS flight 2A showed that contaminants in the Zarya module were at higher concentrations than the Unity module. At the crew's first entry, the amount of non-methane volatile organic compounds (NMVOCs) in Zarya was 23 Mg/cubic meter, whereas in the amount of NMVOCs in Unity was 5.3 mg/cubic meter. Approximately 26 hours later at egress from the modules, the NMVOCs were comparable indicating good mixing of the atmospheres. The 2A crew reported no adverse health effects related to air pollution during their flight. Ingress air samples from 2A.1, which was flown more than 5 months after 2A, again showed that the Zarya had accumulated more unscrubbed pollutants than Unity. The NMVOCs in Unity were 3.5 mg/cubic meter, whereas the were 20 mg/cubic meter in Zarya. After almost 80 hours of ISS operations, the NMVOCs were 7.5 and 12 mg/cubic meter in Unity and Zarya, respectively. This suggests that the atmospheres in the modules were not mixing very well. The 2A.1 crew felt that the air quality in Zarya deteriorated when they were working in a group at close quarters, when the panels had been removed, and after they had worked in an area for some time. The weight of evidence suggests that human metabolic products (carbon dioxide, water vapor, heat) were not being effectively removed from the crew's work area, and these caused their symptoms. Additional local measurements of pollutants are planned for the 2A.2 mission to the ISS.
[Show abstract][Hide abstract] ABSTRACT: The sampling capability of Tenax-TA tubes, used in the National Aeronautics and Space Administration's solid sorbent air sampler to trap and concentrate contaminants from air aboard spacecraft, was improved by incorporating two sorbents within the tubes. Existing tubes containing only Tenax-TA allowed highly volatile compounds to "break through" during collection of a 1.5 L air sample. First the carbon molecular sieve-type sorbents Carboxen 569 and Carbosieve S-III were tested for their ability to quantitatively trap the highly volatile compounds. Breakthrough volumes were determined with the direct method, whereby low ppm levels of methanol or Freon 12 in nitrogen were flowed through the sorbent tubes at 30 mL/min, and breakthrough was detected by gas chromatography. Breakthrough volumes for methanol were about 9 L/g on Carboxen 569 and 11 L/g on Carbosieve S-III; breakthrough volumes for Freon 12 were about 7 L/g on Carboxen 569 and > 26 L/g on Carbosieve S-III. Next, dual-bed tubes containing either Tenax-TA/Carbosieve S-III, Tenax-TA/Carboxen 569, or Carbotrap/Carboxen 569 to a 10-component gas mixture were exposed, in dry and in humidified air (50% relative humidity), and percentage recoveries of each compound were determined. The Tenax-TA/Carboxen 569 combination gave the best overall recoveries (75-114% for the 10 compounds). Acetaldehyde had the lowest recovery (75%) of the 10 compounds, but this value was still an improvement over either the other two sorbent combinations or the original single-sorbent tubes.
AIHAJ - American Industrial Hygiene Association 01/2000; 61(1):69-75. DOI:10.1080/778879055
[Show abstract][Hide abstract] ABSTRACT: The Toxicology Laboratory at Johnson Space Center (JSC) has pioneered the use of gas chromatography-ion mobility spectrometry (GC/IMS) for measuring target volatile organic compounds (VOCs) aboard spacecraft. Graseby Dynamics, under contract to NASA/Wyle, has built several volatile organic analyzers (VOA) based on GC/IMS. Foremost among these have been the volatile organic analyzer-risk mitigation unit and the two flight VOA units for International Space Station (ISS). The development and evaluation of these instruments has been chronicled through presentations at the International Conference on Ion Mobility Spectrometry over the past three years. As the flight VOA from Graseby is prepared for operation on ISS at JSC, it is time to begin evaluations of technologies for the next generation VOA, Although the desired instrument characteristics for the next generation unit are the same as the current unit, the requirements are much more stringent. As NASA looks toward future missions beyond Earth environs, a premium will be placed upon small, light, reliable, autonomous hardware. It is with these visions in mind that the JSC Toxicology Laboratory began a search for the next generation VOA. One technology that is a candidate for the next generation VOA is GC/IMS. The recent miniaturization of IMS technology permits it to compete with other, inherently small, technologies such as chip-sized sensor arrays. This paper will discuss the lessons learned from the VOA experience and how that has shaped the design of a potential second generation VOA based upon GC/IMS technology. Data will be presented from preliminary evaluations of GC technology and the mini-IMS when exposed to VOCs likely to be detected aboard spacecraft. Results from the evaluation of an integrated GC/mini-IMS system will be shown if available.
[Show abstract][Hide abstract] ABSTRACT: Early in the development of the Crew Health Care System (CHECS) for the International Space Station (ISS), it was recognized that detection of target volatile organic compounds would be a key component of the air monitoring strategy. Experiences during the NASA/Mir program supported the decision to include a real-time volatile organic analyzer (VOA) aboard ISS to help assess the impact of air quality events on crew health and determine the effectiveness of decontamination efforts. Toward this end, a joint development by the Toxicology Laboratory at Johnson Space Center and Graseby Dynamics produced a VOA that has been delivered and is ready for the first 5 years of ISS operation. The first-generation VOA selection criteria included minimizing size, weight, and power consumption while maintaining analytical performance. Measuring available technologies against these criteria, a VOA system based upon gas chromatography/ion mobility spectrometry (GC/IMS) was selected in the mid-90's. However, as NASA looks forward to later-stage ISS operations and to new frontiers such as human exploration of Mars, the ISS VOA (weighing 43 kg and consuming 160 watts) must be replaced by a smaller, less resource-intensive device. This paper will present a possible second-gene ration VOA based upon the same technology as the first-generation unit. Utilizing GC/IMS technology again will permit the instrumental data and experience gained during the initial phase of ISS to be applied to later ISS phases and advanced spacecraft missions. During the past 3 years, efforts to reduce the size of ion mobility spectrometers have been pursued by Graseby Dynamics, the manufacturer of the first-generation VOA. The concept of operation, expected analytical performance, and estimated size of a fully functional second-generation VOA based upon GC/mini-IMS technology will be presented. Furthermore, results of initial laboratory evaluations will be shown.
[Show abstract][Hide abstract] ABSTRACT: From the earliest manned missions, the volatile organic compound (VOC) content of spacecraft air has been a concern because of a much greater potential for contamination than air in most terrestrial settings. First, the volume of air is small compared to the mass of man- made materials comprising the interior furnishings of the spacecraft. These man-made materials offgas VOCs trapped during manufacture. Second, the nitrogen fraction of the air is recycled. Any VOCs not scrubbed out with charcoal filters or aqueous condensate (mainly water expired by the crew) will accumulate in the air. Third, the crew emits metabolic VOCs. Fourth, experimental payloads can also offgas or accidentally release a VOC; in fact a major organic constituent of the atmosphere is the disinfectant isopropanol released from swabs used in medical experiments.
[Show abstract][Hide abstract] ABSTRACT: Biological particulates collected on air filters during shuttle missions (STS-40 and STS-42) were identified using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). A method was developed for identifying the atmospheric particles and their sources through the analysis of standard materials and the selection of "marker" compounds specific to the particle type. Pyrolysis spectra of biological standards were compared with those of airborne particles collected during two space shuttle missions; marker compounds present in the shuttle particle spectra were matched with those of the standards to identify the source of particles. Particles of 0,5--1-mm diameter and weighing as little as 40 micrograms could be identified using this technique. The Py-GC/MS method identified rat food and soilless plant-growth media as two sources of particles collected from the shuttle atmosphere during flight.
[Show abstract][Hide abstract] ABSTRACT: Hydrazine (HZ) and monomethylhydrazine (MMH) in air were monitored continuously using a hand-held ion mobility spectrometer equipped with membrane inlet, 63Ni ion source, acetone reagent gas, and ambient temperature drift tube. Response characteristics included detection limit, 6 ppb; linear range, 10-600 ppb; saturated response, >2 ppm; and stable response after 15-30 min. Ammonia interfered in hydrazines detection through a product ion with the same drift time as that for MMH and HZ. Acetone reagent gas was replaced with 5-nonanone to alter drift times of product ions and separate ammonia from MMH and HZ. Patterns in mobility spectra, ion identifications from mass spectra, and fragmentation cross-sections from collisional-induced dissociations suggest that drift times are governed by ion-cluster equilibria in the drift region of the mobility spectrometer. Practical aspects including calibration, stability, and reproducibility are reported from the use of a hand-held mobility spectrometer on the space shuttle Atlantis during mission STS-37.
[Show abstract][Hide abstract] ABSTRACT: Since the early years of the manned space program, NASA has developed and used exposure limits called Spacecraft Maximum Allowable Concentrations (SMACs) to help protect astronauts from airborne toxicants. Most of these SMACS are based on an exposure duration of 7 days, since this is the duration of a 'typical' mission. A set of 'contingency SMACs' is also being developed for scenarios involving brief (1-hour or 24- hour) exposures to relatively high levels of airborne toxicants from event-related 'contingency' releases of contaminants. The emergency nature of contingency exposures dictates the use of different criteria for setting exposure limits. The NASA JSC Toxicology Group recently began a program to document the rationales used to set new SMACs and plans to review the older, 7-day SMACs. In cooperation with the National Research Council's Committee on Toxicology, a standard procedure has been developed for researching, setting, and documenting SMAC values.
[Show abstract][Hide abstract] ABSTRACT: This paper will describe the Combustion Products Analyzer (CPA), which is being developed under the direction of the Toxicology Laboratory at Johnson Space Center to provide necessary data on air quality in the Shuttle following a thermodegradation incident. Using separate electrochemical sensors, the CPA monitors four gases (hydrogen fluoride/carbonyl fluoride, hydrogen chloride, hydrogen cyanide, and carbon monoxide), which were selected as the most hazardous compounds likely to be released during thermodegradation of synthetic materials. Electrochemical sensors have been available for several years; the CPA sensors, which are unique because of their small size and zero-gravity compatibility, will be described in detail.
[Show abstract][Hide abstract] ABSTRACT: The development of hand-held, ambient-temperature instruments that utilize ion mobility spectrometry (IMS) in the detection of hydrazine and monomethylhydrazine is reviewed. A development effort to eliminate ammonia interference through altering the ionization chemistry, based on adding 5-nonanone as dopant in the ionization region of the IMS, is presented. Calibration of this instrument conducted before and after STS-37 revealed no more than a 5 percent difference between calibration curves, without any appreciable loss of equipment function.
[Show abstract][Hide abstract] ABSTRACT: The Space Station Freedom (SSF), with a 30-year projected lifetime and a completely closed-loop Environmental Control and Life Support System (ECLSS), is perhaps the ultimate 'tight building'. Recognizing the potential for the development of 'tight building syndrome' (TBS), and initiating actions to minimize possible TBS occurrences on SSF, requires a multidisciplinary approach that begins with appropriate design concerns and ends with detection and control measures on board SSF. This paper presents a brief summary of current experience with TBS on earth. Air contamination, including volatile organic compounds and microorganisms, is the focus of the discussion. Preventive steps to avoid TBS, control of environmental factors that may lead to TBS, and use of real-time instrumentation for the detection of potential causes of TBS are also outlined.
[Show abstract][Hide abstract] ABSTRACT: SUMMARY Air pollutants were quantified during the Phase II (30 day), Phase IIa (60 day), and Phase III (90 day) tests. Measurements from the Phase II test demon- strated a generally stable and safe atmosphere; however, measurements of ammonia and formaldehyde were incomplete. Near day 10 a large amount of methane entered the atmosphere and Freon ® 113 was unusually high most of the time. There were peri- odic "bursts" of ethanol and isopropanol imposed on a steady state level of methanol. The Phase IIa test, which was the first opportunity to measure formaldehyde, was plagued with excess formaldehyde offgassing from various materials in the test cham- ber. This led to mucosal irritation in one crewmember. Methanol was unusually high, and at one point carbon monoxide had accumulated nearly to its long-term spacecraft maximum allowable concentration (SMAC). In contrast to the Phase II test where an accidental release of methane occurred, methane accumulated steadily throughout the Phase IIa test. Ammonia levels in the Phase IIa test quickly reached a low, steady-state concentration. Except for formaldehyde, all contaminants met standards for acceptable air quality. The Phase III test demonstrated much improved control of formaldehyde even though it exceeded its long-term SMAC late in the test. Ammonia accumulated steadily during the 90 days, reaching approximately 1/8 of its long-term SMAC. During the final days of the test, the air was characterized by rather rapid rises in irritant compounds and methylcyclosiloxanes. The trace contaminant control system (TCCS) suffered degraded performance during this time, and this is the likely cause of the increases in concentrations. Even though air quality standards were exceeded for irritants late in the test, there were no reports from the crew that the air was causing symptoms.