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NASA NTRS1985

Seeding materials: Health and safety considerations

The choice of a proper seeding material for laser velocimeters must include health and safety considerations. Failure to do so can lead to catastrophic results. All materials are toxic, and laser velocimeter seeding materials are no exception. Toxicity may be considered an inherent property of a given material. The manifestation of that property or the physiological response to the material is dependent on dose and exposure conditions. An approximate physiological classification of toxicity is given in tablular form. Toxicity in some situations is not necessarily the most restrictive factor in selection of materials. It is also very important to consider how the material is used so that actual exposure to the material in a damaging form can result. For example, nickel and cadmium are both extremely toxic as systemic poisons and in the case of nickel as a carcinogen. Seeding materials are dispersed in air under conditions that favor personnel exposure. Dispersal equipment is frequently if not normally manned, and personnel are often required to make frequent adjustments to assure proper operations.

Brown, R. D.↗

NASA NTRS1992

Toxicological approach to setting spacecraft maximum allowable concentrations for carbon monoxide

The Spacecraft Maximum Allowable Concentrations (SMACs) are exposure limits for airborne chemicals used by NASA in spacecraft. The aim of these SMACs is to protect the spacecrew against adverse health effects and performance decrements that would interfere with mission objectives. Because of the 1 and 24 hr SMACs are set for contingencies, minor reversible toxic effects that do not affect mission objectives are acceptable. The 7, 30, or 180 day SMACs are aimed at nominal operations, so they are established at levels that would not cause noncarcinogenic toxic effects and more than one case of tumor per 1000 exposed individuals over the background. The process used to set the SMACs for carbon monoxide (CO) is described to illustrate the approach used by NASA. After the toxicological literature on CO was reviewed, the data were summarized and separated into acute, subchronic, and chronic toxicity data. CO's toxicity depends on the formation of carboxyhemoglobin (COHb) in the blood, reducing the blood's oxygen carrying capacity. The initial task was to estimate the COHb levels that would not produce toxic effects in the brain and heart.

Wong, K. L.↗

NASA NTRS1992

Human exposure limits to hypergolic fuels

Over the past four decades, many studies have been conducted on the toxicities of the rocket propellants hydrazine (HZ) and monomethylhydrazine (MH). Numerous technical challenges have made it difficult to unambiguously interpret the results of these studies, and there is considerable divergence between results obtained by different investigators on the inhalation concentrations (MAC's) for each toxic effect inducible by exposure to hypergolic fuels in spacecraft atmospheres, NASA undertook a critical review of published and unpublished investigations on the toxicities of these compounds. The current state of the art practices for similar studies. While many questions remain unanswered, MAC's were determined using the best available data for a variety of toxic endpoints for potential continuous exposure durations ranging from 1 hour to 180 days. Spacecraft MAC's (SMAC's) were set for each compound based on the most sensitive toxic endpoint at each exposure duration.

Garcia, H. D.↗

NASA NTRS1997

New Approaches to Waterproofing of Space Shuttle Insulating Materials

Future reusable space vehicles will be in service much more frequently than current space shuttles. Therefore, rapid reconditioning of spacecraft will be required. Currently, the waterproofing of space shuttles after each re-entry takes 72 hours and requires substantial labor. In addition, the currently used waterproofing reagent, DiMethylEthoxySilane (DMES), is considered toxic, and ethanol fumes are released during its hydrolytic activation. Consequently, a long time period, which is not acceptable for future operations, is needed to ensure that 0 the excess volatile compounds are removed before further maintenance of the space vehicle can be performed. The objective of this project was to assist NASA Ames in finding improved waterproofing systems by identifying suitable waterproofing agents that can be applied by vapor phase deposition and will be less toxic, bond more rapidly to the insulation material surface, and potentially have higher thermal stability than the DMES system. Several approaches to achieve faster waterproofing with less toxicity were assessed using the following alternatives: Reactive volatile compounds that are rapidly deposited by chemical bonding at the surface and leave no toxic volatiles. Reactive reagents that are the least toxic. Nonvolatile reagents that are very reactive and bond strongly to the insulating material surface. Three specific types of potential reagents were chosen for evaluation in this project: 1. Volatile reagents with Si-Cl functional groups for vapor deposition 2. Volatile reagents with Si-H functional groups for vapor deposition 3. Nonvolatile oligomeric or polymeric reactive siloxanes that are assumed to have higher thermal stability and/or strong bonding to the insulating material. The chemistry involved in the project was targeted at the generation of intermediates having reactive Si-OH bonds for the formation of either volatile species or polymeric species that bond rapidly to the surface and also cure rapidly. We focused on two chemical reactions@-hydrolysis of Si-Cl bonds and catalytic dehydrocoupling of Si-H bonds.

Blum, Yigal D.↗

NASA NTRS2000

Development and Application of Computational/In Vitro Toxicological Methods for Chemical Hazard Risk Reduction of New Materials for Advanced Weapon Systems

The development of quantitative structure-activity relationship (QSAR) is essential for reducing the chemical hazards of new weapon systems. The current collaboration between HEST (toxicology research and testing), MLPJ (computational chemistry) and PRS (computational chemistry, new propellant synthesis) is focusing R&D efforts on basic research goals that will rapidly transition to useful products for propellant development. Computational methods are being investigated that will assist in forecasting cellular toxicological end-points. Models developed from these chemical structure-toxicity relationships are useful for the prediction of the toxicological endpoints of new related compounds. Research is focusing on the evaluation tools to be used for the discovery of such relationships and the development of models of the mechanisms of action. Combinations of computational chemistry techniques, in vitro toxicity methods, and statistical correlations, will be employed to develop and explore potential predictive relationships; results for series of molecular systems that demonstrate the viability of this approach are reported. A number of hydrazine salts have been synthesized for evaluation. Computational chemistry methods are being used to elucidate the mechanism of action of these salts. Toxicity endpoints such as viability (LDH) and changes in enzyme activity (glutahoione peroxidase and catalase) are being experimentally measured as indicators of cellular damage. Extrapolation from computational/in vitro studies to human toxicity, is the ultimate goal. The product of this program will be a predictive tool to assist in the development of new, less toxic propellants.

Frazier, John M.↗

NASA NTRS2009

A History of Space Toxicology Mishaps: Lessons Learned and Risk Management

After several decades of human spaceflight, the community of space-faring nations has accumulated a diverse and sometimes harrowing history of toxicological events that have plagued human space endeavors almost from the very beginning. Lessons have been learned in ground-based test beds and others were discovered the hard way - when human lives were at stake in space. From such lessons one can build a risk-management framework for toxicological events to minimize the probability of a harmful exposure, while recognizing that we cannot foresee all events. Space toxicologists have learned that relatively harmless compounds can be converted by air revitalization systems into compounds that cause serious harm to the crew. Our toxic risk management strategy now includes an assessment of the fate of any compound that might be released into the atmosphere. Propellants are highly toxic compounds, yet we have not always been able to thoroughly isolate the crew from exposure to these toxicants. Leakage of fluids from systems has resulted in hazardous conditions at times, and the behavior of such compounds inside a spacecraft has taught us how to manage potentially harmful escapes should they occur. Potential combustion events are an ever-present threat to the wellbeing of the crew. Such events have been sufficiently common that we have learned that one cannot judge the health threat of a given fire by the magnitude of the event. Management of such risks demands monitoring of combustion products. In the category of unpredictable toxic events, if one assumes that fires are predictable, we can place experience with toxic microbial metabolites, upsets during repair operations, and discharges from filters that have accumulated a substantial load of pollutants in their absorption beds. Management of such events requires a broad-spectrum, real-time analytical capability to discern the identity and concentrations of pollutants if they enter the atmosphere. Adverse events are an integral part of any human activity, and the spacefaring community must learn as much as possible from mistakes and near misses.

James, John T.↗

NASA NTRS2010

Development of a Contingency Gas Analyzer for the Orion Crew Exploration Vehicle

NASA's experience with electrochemical sensors in a hand-held toxic gas monitor serves as a basis for the development of a fixed on-board instrument, the Contingency Gas Analyzer (CGA), for monitoring selected toxic combustion products as well as oxygen and carbon dioxide on the Orion Crew Exploration Vehicle (CEV). Oxygen and carbon dioxide are major components of the cabin environment and accurate measurement of these compounds is critical to maintaining a safe working environment for the crew. Fire or thermal degradation events may produce harmful levels of toxic products, including carbon monoxide (CO), hydrogen cyanide (HCN), and hydrogen chloride (HCl) in the environment. These three components, besides being toxic in their own right, can serve as surrogates for a panoply of hazardous combustion products. On orbit monitoring of these surrogates provides for crew health and safety by indicating the presence of toxic combustion products in the environment before, during and after combustion or thermal degradation events. Issues identified in previous NASA experiences mandate hardening the instrument and components to endure the mechanical and operational stresses of the CEV environment while maintaining high analytical fidelity. Specific functional challenges involve protecting the sensors from various anticipated events- such as rapid pressure changes, low cabin pressures, and extreme vibration/shock exposures- and extending the sensor lifetime and calibration periods far beyond the current state of the art to avoid the need for on-orbit calibration. This paper focuses on lessons learned from the earlier NASA hardware, current testing results, and engineering solutions to the identified problems. Of particular focus will be the means for protecting the sensors, addressing well known cross-sensitivity issues and the efficacy of a novel self monitoring mechanism for extending sensor calibration periods.

Niu, Bill↗

NASA NTRS2012

Martian and Asteroid Dusts as Toxicological Risks for Human Exploration Missions

As the lunar dust toxicity project winds down, our attention is drawn to the potential toxicity of dust present at the surface of more distant celestial objects. Lunar dust has proven to be surprisingly toxic to the respiratory systems of test animals, so one might expect dust from other celestial bodies to hold toxicological surprises for us. At this point all one can do is consider what should be known about these dusts to characterize their toxicity, and then ask to what extent that information is known. In an ideal world it might be possible to suggest an exposure standard based on the known properties of a celestial dust without direct testing of the dust in laboratory animals. Factors known to affect the toxicity of mineral dusts under some conditions include the following: particle size distribution, particle shape/porosity, mineralogical properties (crystalline vs. amorphous), chemical properties and composition, and surface reactivity. Data from a recent Japanese mission to the S-type asteroid Itokawa revealed some surprises about the dust found there, given that there is only a very week gravitational field to hold the dust on the surface. On Mars the reddish-brown dust is widely distributed by global dust storms and by local clusters of dust devils. Past surface probes have revealed some of the properties of dust found there. Contemporary data from Curiosity and other surface probes will be weighed against the data needed to set a defensible safe exposure limit. Gaps will emerge.

James, John T.↗

NASA NTRS2015

Risk of Adverse Health and Performance Effects of Celestial Dust Exposure

Crew members can be directly exposed to celestial dust in several ways. After crew members perform extravehicular activities (EVAs), they may introduce into the habitat dust that will have collected on spacesuits and boots. Cleaning of the suits between EVAs and changing of the Environmental Control Life Support System filters are other operations that could result in direct exposure to celestial dusts. In addition, if the spacesuits used in exploration missions abrade the skin, as current EVA suits have, then contact with these wounds would provide a source of exposure. Further, if celestial dusts gain access to a suit's interior, as was the case during the Apollo missions, the dust could serve as an additional source of abrasions or enhance suit-induced injuries. When a crew leaves the surface of a celestial body and returns to microgravity, the dust that is introduced into the return vehicle will "float," thus increasing the opportunity for ocular and respiratory injury. Because the features of the respirable fraction of lunar dusts indicate they could be toxic to humans, NASA conducted several studies utilizing lunar dust simulants and authentic lunar dust to determine the unique properties of lunar dust that affect physiology, assess the dermal and ocular irritancy of the dust, and establish a permissible exposure limit for episodic exposure to airborne lunar dust during missions that would involve no more than 6 months stay on the lunar surface. Studies, with authentic lunar soils from both highland (Apollo 16) and mare (Apollo17) regions demonstrated that the lunar soil is highly abrasive to a high fidelity model of human skin. Studies of lunar dust returned during the Apollo 14 mission from an area of the moon in which the soils were comprised of mineral constituents from both major geological regions (highlands and mares regions) demonstrated only minimal ocular irritancy, and pulmonary toxicity that was less than the highly toxic terrestrial crystalline silica (Permissible Exposure Limit [PEL] 0.05 mg/m3) but more toxic than the nuisance dust titanium dioxide (TiO2 [PEL 5.0 mg/m3]). A PEL for episodic exposure to airborne lunar dust during a six-month stay on the lunar surface was established, in consultation with an independent, extramural panel of expert pulmonary toxicologists, at 0.3 mg/m3. The PEL provided for lunar dust is limited to the conditions and exposure specified therefore additional research remains to be accomplished with lunar dust to further address the issues of activation, address other areas of more unique lunar geology (Glotch et al., 2010; Greenhagen et al., 2010), examine potential toxicological effects of inhaled or ingested dust upon other organ systems, such cardiovascular, nervous systems, and examine effects of acute exposure to massive doses of dust such as may occur during off-nominal situations. Work to support the establishment of PELs for Martian dust and dusts of asteroids remains to be accomplished. The literature that describes health effects of exposure to toxic terrestrial dusts provides substantial basis for concern that prolonged exposure to respirable celestial dust could be detrimental to human health. Celestial bodies where a substantial portion of the dust is in the respirable range or where the dusts have large reactive surface areas or contain transition metals or volatile organics, represent greater risks of adverse effects from exposure to the dust. It is possible that in addition to adverse effects to the respiratory system, inhalation and ingestion of celestial dusts could pose risks to other systems

Scully, Robert R.↗

NASA NTRS1973

Toxicology

Oxygen toxicity is examined, including the effects of oxygen partial pressure variations on toxicity and oxygen effects on ozone and nitrogen dioxide toxicity. Toxicity of fuels and oxidizers, such as hydrazines, are reported. Carbon monoxide, spacecraft threshold limit values, emergency exposure limits, spacecraft contaminants, and water quality standards for space missions are briefly summarized.

Macewen, J. W.↗

NASA NTRS1990

A biosensor for cadmium based on bioconvective patterns

An 'in vitro' method for monitoring cadmium, one of the most lethal bivalent heavy metals, can detect biologically active levels. The effects of cadmium tend to concentrate in protozoa far above natural levels and therein begin transferring through freshwater food chains to animals and humans. In a small sample volume (approximately 5 ml) the method uses the toxic response to the protozoa, Tetrahymena pyriformis, to cadmium. The assay relies on macroscopic bioconvective patterns to measure the toxic response, giving a sensitivity better than 1 micro-g/1 and a toxicity threshold to 7 micro-g/1 for Cd(2+). Cadmium hinders pattern formation in a dose-dependent manner. Arrested organism growth arises from slowed division and mutation to non-dividing classes. Unlike previous efforts, this method can be performed in a shallow flow device and does not require electronic or chemical analyses to monitor toxicity.

Noever, David A.↗

NASA NTRS1994

Modeling aerosol emissions from the combustion of composite materials

The use of advanced composite materials (ACM) in the B-2 bomber, composite armored vehicle, and F-22 advanced tactical fighter has rekindled interest concerning the health risk of burned or burning ACM. The objective of this work was to determine smoke production from burning ACM and its toxicity. A commercial version of the UPITT II combustion toxicity method developed at the University of Pittsburgh, and subsequently refined through a US Army-funded basic research project, was used to established controlled combustion conditions which were selected to evaluate real-world exposure scenarios. Production and yield of toxic species varied with the combustion conditions. Previous work with this method showed that the combustion conditions directly influenced the toxicity of the decomposition products from a variety of materials.

Roop, J. A.↗

NASA NTRS1996

Microbial Diffraction Gratings as Optical Detectors for Heavy Metal Pollutants

As a significant industrial pollutant, cadmium is implicated as the cause of itai-itai disease. For biological detection of cadmium toxicity, an assay device has been developed using the motile response of the protozoa species, Tetrahymena pyriformis. This mobile protozoa measures 50 microns in diameter, swims at 10 body lengths per second, and aggregates into macroscopically visible patterns at high organism concentrations. The assay demonstrates a Cd(+2) sensitivity better than 1 micro-M and a toxicity threshold to 5 micro-M, thus encouraging the study of these microbial cultures as viable pollution detectors. Using two-dimensional diffraction patterns within a Tetrahymena culture, the scattered light intensity varies with different organism densities (population counts). The resulting density profile correlates strongly with the toxic effects at very low dosages for cadmium (less than 5 ppm) and then for poison protection directly (with nickel and copper antagonists competing with cadmium absorption). In particular, copper dosages as low as 0.1-0.5 mM Cu have shown protective antagonism against cadmium, have enhanced density variability for cultures containing 1 mM Cd(+2) and therefore have demonstrated the sensitivity of the optical detection system. In this way, such microbial diffraction patterns give a responsive optical measure of biological culture changes and toxicity determination in aqueous samples of heavy metals and industrial pollutants.

Noever, David↗

NASA NTRS1996

Ampoule Failure System

An ampoule failure system for use in material processing furnaces comprising a containment cartridge and an ampoule failure sensor. The containment cartridge contains an ampoule of toxic material therein and is positioned within a furnace for processing. An ampoule failure probe is positioned in the containment cartridge adjacent the ampoule for detecting a potential harmful release of toxic material therefrom during processing. The failure probe is spaced a predetermined distance from the ampoule and is chemically chosen so as to undergo a timely chemical reaction with the toxic material upon the harmful release thereof. The ampoule failure system further comprises a data acquisition system which is positioned externally of the furnace and is electrically connected to the ampoule failure probe so as to form a communicating electrical circuit. The data acquisition system includes an automatic shutdown device for shutting down the furnace upon the harmful release of toxic material. It also includes a resistance measuring device for measuring the resistance of the failure probe during processing. The chemical reaction causes a step increase in resistance of the failure probe whereupon the automatic shutdown device will responsively shut down the furnace.

Watring, Dale A.↗

NASA NTRS1999

JANNAF 28th Propellant Development and Characterization Subcommittee and 17th Safety and Environmental Protection Subcommittee Joint Meeting

This volume contains 37 unclassified/unlimited-distribution technical papers that were presented at the JANNAF 28th Propellant Development & Characterization Subcommittee (PDCS) and 17th Safety & Environmental Protection Subcommittee (S&EPS) Joint Meeting, held 26-30 April 1999 at the Town & Country Hotel and the Naval Submarine Base, San Diego, California. Volume II contains 29 unclassified/limited-distribution papers that were presented at the 28th PDCS and 17th S&EPS Joint Meeting. Volume III contains a classified paper that was presented at the 28th PDCS Meeting on 27 April 1999. Topics covered in PDCS sessions include: solid propellant rheology; solid propellant surveillance and aging; propellant process engineering; new solid propellant ingredients and formulation development; reduced toxicity liquid propellants; characterization of hypergolic propellants; and solid propellant chemical analysis methods. Topics covered in S&EPS sessions include: space launch range safety; liquid propellant hazards; vapor detection methods for toxic propellant vapors and other hazardous gases; toxicity of propellants, ingredients, and propellant combustion products; personal protective equipment for toxic liquid propellants; and demilitarization/treatment of energetic material wastes.

Cocchiaro, James E.↗

NASA NTRS1999

Gas Sensor Evaluations in Polymer Combustion Product Atmospheres

Toxic gases produced by the combustion or thermo-oxidative degradation of materials such as wire insulation, foam, plastics, or electronic circuit boards in space shuttle or space station crew cabins may pose a significant hazard to the flight crew. Toxic gas sensors are routinely evaluated in pure gas standard mixtures, but the possible interferences from polymer combustion products are not routinely evaluated. The NASA White Sands Test Facility (WSTF) has developed a test system that provides atmospheres containing predetermined quantities of target gases combined with the coincidental combustion products of common spacecraft materials. The target gases are quantitated in real time by infrared (IR) spectroscopy and verified by grab samples. The sensor responses are recorded in real time and are compared to the IR and validation analyses. Target gases such as carbon monoxide, hydrogen cyanide, hydrogen chloride, and hydrogen fluoride can be generated by the combustion of poly(vinyl chloride), polyimide-fluoropolymer wire insulation, polyurethane foam, or electronic circuit board materials. The kinetics and product identifications for the combustion of the various materials were determined by thermogravimetric-IR spectroscopic studies. These data were then scaled to provide the required levels of target gases in the sensor evaluation system. Multisensor toxic gas monitors from two manufacturers were evaluated using this system. In general, the sensor responses satisfactorily tracked the real-time concentrations of toxic gases in a dynamic mixture. Interferences from a number of organic combustion products including acetaldehyde and bisphenol-A were minimal. Hydrogen bromide in the products of circuit board combustion registered as hydrogen chloride. The use of actual polymer combustion atmospheres for the evaluation of sensors can provide additional confidence in the reliability of the sensor response.

Delgado, Rafael H.↗

NASA NTRS2000

Toxicological Risks During Human Space Exploration

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.

James, John T.↗

NASA NTRS2002

Safety on Earth From MARSS

ENSCO, Inc., developed the Meteorological and Atmospheric Real-time Safety Support (MARSS) system for real-time assessment of meteorological data displays and toxic material spills. MARSS also provides mock scenarios to guide preparations for emergencies involving meteorological hazards and toxic substances. Developed under a Small Business Innovation Research (SBIR) contract with Kennedy Space Center, MARSS was designed to measure how safe NASA and Air Force range safety personnel are while performing weather sensitive operations around launch pads. The system augments a ground operations safety plan that limits certain work operations to very specific weather conditions. It also provides toxic hazard prediction models to assist safety managers in planning for and reacting to releases of hazardous materials. MARSS can be used in agricultural, industrial, and scientific applications that require weather forecasts and predictions of toxic smoke movement. MARSS is also designed to protect urban areas, seaports, rail facilities, and airports from airborne releases of hazardous chemical substances. The system can integrate with local facility protection units and provide instant threat detection and assessment data that is reportable for local and national distribution.

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