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Preliminary results Skylab experiment TO27 optical contamination in space

Current results from the TO27 experiment which was performed on the first two Skylab missions are presented. The purpose of the experiment was to determine the change in optical properties of various transmissive windows, mirrors, and diffraction gratings caused by the deposition of contaminants found about the orbital assembly and to measure the sky brightness background caused by solar illumination of particulate contaminants. The sample array system containing 248 optical surfaces and exposed outside the orbital workshop did not collect any significant contaminants. Only trace amounts of surface deposited contaminants have been seen, in all cases the measurement was near the limiting sensitivity of the instrument. Unfortunate performance compromises and the relative cleanliness of the assembly on the anti-solar side appeared to place the amount of available surface contaminants near the limiting sensitivity of the sample array. Mass spectroscopy on the trace contaminants show the presence of high molecular weight species, up to 773 amu. The data suggests the presence of condensed aromatics.

Muscari, J. A.↗

Lidar remote measurements of Space Shuttle ground cloud emissions

The application of lidar remote sensing techniques to the measurement of spacecraft-booster-exhaust-cloud parameters is illustrated, using data obtained from the launch of STS-3. Mie-scatter measurements of plume and cloud particulates were made by a mobile unit with computer controlled elevation and azimuth coverage. Scattergraphs of typical STS-3 lidar data are presented and discussed. The potential use of DIAL techniques to measure the concentrations of HCl, N2H4, and NO2 is evaluated in terms of EPA overall-standard-deviation guidelines. It is shown that currently operational lidar systems can be modified to determine contamination or air pollution by these molecular species resulting from spacecraft launches.

Caputo, B.↗

Air Purification in Closed Environments: An Overview of Spacecraft Systems

The primary goal for a collective protection system and a spacecraft environmental control and life support system (ECLSS) are strikingly similar. Essentially both function to provide the occupants of a building or vehicle with a safe, habitable environment. The collective protection system shields military and civilian personnel from short-term exposure to external threats presented by toxic agents and industrial chemicals while an ECLSS sustains astronauts for extended periods within the hostile environment of space. Both have air quality control similarities with various aircraft and 'tight' buildings. This paper reviews basic similarities between air purification system requirements for collective protection and an ECLSS that define surprisingly common technological challenges and solutions. Systems developed for air revitalization on board spacecraft are discussed along with some history on their early development as well as a view of future needs. Emphasis is placed upon two systems implemented by the National Aeronautics and Space Administration (NASA) onboard the International Space Station (ISS): the trace contaminant control system (TCCS) and the molecular sieve-based carbon dioxide removal assembly (CDRA). Over its history, the NASA has developed and implemented many life support systems for astronauts. As the duration, complexity, and crew size of manned missions increased from minutes or hours for a single astronaut during Project Mercury to days and ultimately months for crews of 3 or more during the Apollo, Skylab, Shuttle, and ISS programs, these systems have become more sophisticated. Systems aboard spacecraft such as the ISS have been designed to provide long-term environmental control and life support. Challenges facing the NASA's efforts include minimizing mass, volume, and power for such systems, while maximizing their safety, reliability, and performance. This paper will highlight similarities and differences among air purification systems. Additional information is included in the original extended abstract.

Perry, Jay L.↗

Contamination of Critical Surfaces from NVR Glove Residues Via Dry Handling and Solvent Cleaning

Gloves are often used to prevent the contamination of critical surfaces during handling. The type of glove chosen for use should be the glove that produces the least amount of non-volatile residue (NVR). This paper covers the analysis of polyethylene, nitrile, latex, vinyl, and polyurethane gloves using the contact transfer and gravimetric determination methods covered in the NASA GSFC work instruction Gravimetric Determination and Contact Transfer of Non-volatile Residue (NVR) in Cleanroom Glove Samples, 541-WI-5330.1.21 and in the ASTM Standard E-1731M-95, Standard Test Method for Gravimetric Determination of Non-Volatile Residue from Cleanroom Gloves. The tests performed focus on contamination of critical surfaces at the molecular level. The study found that for the most part, all of the gloves performed equally well in the contact transfer testing. However, the polyethylene gloves performed the best in the gravimetric determination testing, and therefore should be used whenever solvent contact is a possibility. The nitrile gloves may be used as a substitute for latex gloves when latex sensitivity is an issue. The use of vinyl gloves should be avoided, especially if solvent contact is a possibility. A glove database will be established by Goddard Space Flight Center (GSFC) Code 541 to compile the results from future testing of new gloves and different glove lots.

Sovinski, Marjorie F.↗

Molecular Isotopic Characterization of the ALH 85013.50 Meteorite: Defining the Extraterrestrial Organic Compounds

The Antarctic Meteorite Program has returned over 16,000 meteorites from the ice sheets of the Antarctic. This more than doubles the number of preexisting meteorite collection and adds important and rare specimens to the assemblage. The CM carbonaceous chondrites are of particular interest because of their high organic component. The Antarctic carbonaceous chondrites provide a large, previously uninvestigated suite of meteorites. Of the 161 CM chondrites listed in the Catalogue of Meteorites 138 of them have been recovered from the Antarctic ice sheets,. However, these meteorites have typically been exposed to Earth s conditions for long periods of time. The extent of terrestrial organic contamination and weathering that has taken place on these carbonaceous chondrites is unknown. In the past, stable isotope analysis was used to identify bulk organics that were extraterrestrial in origin. Although useful, this method could not exclude the possibility of terrestrial contamination contributing to the isotopic measurement. Compound specific isotope analysis of organic meteorite material has provided the opportunity to discern the terrestrial contamination from extraterrestrial organic compounds on the molecular level.

Fuller, M.↗

Exploiting the Vacuum of Space

Molecular-beam epitaxy and other processes tested with minimal contamination. Vacuum experimental facility for outer space creates vacuums higher than those available in terrestrial vacuum chambers. Facility minimizes contamination of work from walls and allows rapid removal of gases and heat generated by experimental processes. Used for processes such as molecular-beam epitaxy (growing semiconductor superlattices), metal/organic chemical vapor deposition, coating mirrors and other optical components, and ultrapurification.

Naumann, R. J.↗

A review of contamination issues associated with an orbiting Space Station external environment

Techniques for measuring, modeling, and limiting the effluent contamination of external spacecraft and instrument surfaces are reviewed, with an emphasis on their application to the Space Station. The major factors addressed by contamination studies are outlined; typical contamination sources are characterized; the critical measurement parameters are defined (molecular column density, background spectral intensity from UV to IR, particle size and velocity distribution, molecular deposition on ambient and cryogenic surfaces, molecular return flux for gaseous species, particulate deposition on surfaces, and optical-surface degradation); and measurement instrumentation is described. Contamination limits for quiescent operation periods of the Space Station are proposed, including column density 10 to the 11th/sq cm for H2O + CO2, 10 to the 13th/sq cm for O2 + N2, and 10 to the 10th/sq cm for other species; particle release no greater than 15-micron particle/orbit/0.00001 sr FOV for a 1-m telescope, and surface deposition 4 pg/sq cm sec for 298-K surfaces and 10 pg/sq cm sec for 4-K surfaces.

Smith, A. C.↗

Microbial Contamination of Allende and Murchison Carbonaceous Chondrites; Developing a Protocol for Life Detection in Extraterrestrial Materials Using Biotechnology

The arguments used to refute the McKay et al., (1996) hypothesis of possible Martian life in ALH84001 failed to use contamination of the meteorite as a source. This has worrying implications for our ability to detect terrestrial microbiota in meteorites and therefore any potential extraterrestrial biosignatures in both meteorites and possible returned samples. We report on imaging and microbial culturing of both Allende and Murchison carbonaceous chondrites and on the use of molecular biology techniques on a sample of Allende. Contaminating fungi and bacteria were observed (in the case of Murchison) and cultured from both meteorites. DNA was successfully extracted and subsequent PCR showed the presence of both bacterial and fungal DNA although no Archaea were detected. These results show that it is possible to use molecular biological techniques on very small quantities (300 mg) of extraterrestrial material.

Steele, A.↗

Environmental monitoring for Space Station WP01

External contamination monitoring instrumentation for the Space Station work package one (WP01) elements, were imposed on the contractor as deliverable hardware. The monitoring instrumentation proposed by the WP01 contractor in response to the contract requirement includes both real time measurements and passive samples. Real time measurement instrumentation consists of quartz crystal microbalances for molecular deposition, ion gaseous species identification. Internal environmental contamination monitoring for particulates is included in both Lab and HAB modules. Passive samples consists of four sample mounting plates mounted external to the Space Station modules, two on the U.S. LAB, and two on the HAB module.

Zwiener, J. M.↗

X-Ray Absorption near Edge Structure Spectroscopic Study of Hayabusa Category 3 Carbonaceous Particles

Analyses with a scanning transmission x-ray microscope (STXM) using x-ray absorption near edge structure (XANES) spectroscopy were applied for the molecular characterization of two kinds of carbonaceous particles of unknown origin, termed category 3, which were collected from the Hayabusa spacecraft sample catcher. Carbon-XANES spectra of the category 3 particles displayed typical spectral patterns of heterogeneous organic macromolecules; peaks corresponding to aromatic/olefinic carbon, heterocyclic nitrogen and/or nitrile, and carboxyl carbon were all detected. Nitrogen-XANES spectra of the particles showed the presence of N-functional groups such as imine, nitrile, aromatic nitrogen, amide, pyrrole, and amine. An oxygen-XANES spectrum of one of the particles showed a ketone group. Differences in carbon- and nitrogen-XANES spectra of the category 3 particles before and after transmission electron microscopic (TEM) observations were observed, which demonstrates that the carbonaceous materials are electron beam sensitive. Calcium-XANES spectroscopy and elemental contrast mapping identified a calcium carbonate grain from one of the category 3 particles. No fluorine-containing molecular species were detected in fluorine-XANES spectra of the particles. The organic macromolecular features of the category 3 particles were distinct from commercial and/or biological ‘fresh (non-degraded)’ polymers, but the category 3 molecular features could possibly reflect degradation of contaminant polymer materials or polymer materials used on the Hayabusa spacecraft. However, an extraterrestrial origin for these materials cannot currently be ruled out.

Asteroides↗

STS-2, -3, -4 Induced Environment Contamination Monitor (ICEM)

The second, third, and fourth space transportation system missions are described including the location of the IECM in the payload bay and the shuttle coordinate systems used. Measurement results from the three flights are given for each instrument with comparisons to original goals for preflight environment and induced environment contamination. These results include very low levels of molecular mass accumulation rates, absence of molecular films on optical samples, outgassing species above 50 amu undetectable generally low levels of on-orbit particulates, and decay rates for early mission water dump particulates. Results of exposure of several optical materials and coatings to atomic oxygen are also presented. From these results, it is concluded that the space shuttle met the established induced environment contamination goals.

Miller, E. R.↗

Superhydrophilicity of $α$-alumina surfaces results from tight binding of interfacial waters to specific aluminols

Understanding the microscopic driving force of water wetting is challenging and important for design of materials. The relations between structure, dynamics and hydrogen bonds of interfacial water can be investigated using molecular dynamics simulations. Here, contact angles at the alumina (0001) and ($11\bar{2}0$) surfaces are studied using both classical molecular dynamics simulations and experiments. To test the superhydrophilicity, the free energy cost of removing waters near the interfaces are calculated using the density fluctuations method. The strength of hydrogen bonds is determined by their lifetime and geometry. Both surfaces are superhydrophilic and the (0001) surface is more hydrophilic. Interactions between surfaces and interfacial waters promote a templating effect whereby the latter are aligned in a pattern that follows the underlying lattice of the surfaces. Translational and rotational dynamics of interfacial water molecules are slower than in bulk water. Hydrogen bonds between water and both surfaces are asymmetric, water-to-aluminol ones are stronger than aluminol-to-water ones. Molecular dynamics simulations eliminate the impacts of surface contamination when measuring contact angles and the results reveal the microscopic origin of the macroscopic superhydrophilicity of alumina surfaces: strong water-to-aluminol hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical and Flowfield Modeling for Enhanced Analysis of Contamination Experiments

This paper describes the application of a new Direct Simulation Monte Carlo (DSMC) code, the Molecular Beam Simulator (MBS), which is designed to analyze laboratory scale molecular beam-surface (and crossed-beam) experiments. The MBS is primarily intended to model experiments associated with spacecraft contamination effects, but it can also be used to simulate a variety of surface chemistry and reactive flow measurements. The MBS code is fully three-dimensional, includes a wide-range of chemical processes, and can model one or multiple pulsed (non-steady) sources. As an example application of the MBS code, a fast, pulsed, oxygen atom-surface experiment which examines the chemistry behind erosion of graphite by oxygen atoms is analyzed. Unsteady DSMC simulations show that experimental observations of excited molecular states after the pulse has hit the surface are consistent with two distinct chemical mechanisms: a direct one where the excited molecules are formed on the surface, and a two-step mechanism where ground state molecules formed on the surface are collisionally excited after they leave the surface by trailing oxygen atoms in the pulse. Further DSMC calculations suggest experiments which can distinguish between these mechanisms.

Braunstein, Matthew↗

Surface contamination on LDEF exposed materials

X-ray photoelectron spectroscopy (XPS) has been used to study the surface composition and chemistry of Long Duration Exposure Facility (LDEF) exposed materials including silvered Teflon (Ag/FEP), Kapton, S13GLO paint, quartz crystal monitors (QCM's), carbon fiber/organic matrix composites, and carbon fiber/Al Alloy composites. In each set of samples, silicones were the major contributors to the molecular film accumulated on the LDEF exposed surfaces. All surfaces analyzed have been contaminated with Si, O, and C; most have low levels (less than 1 atom percent) of N, S, and F. Occasionally observed contaminants included Cl, Na, K, P, and various metals. Orange/brown discoloration observed near vent slots in some Ag/FEP blankets were higher in carbon, sulfur, and nitrogen relative to other contamination types. The source of contamination has not been identified, but amine/amide functionalities were detected. It is probable that this same source of contamination account for the low levels of sulfur and nitrogen observed on most LDEF exposed surfaces. XPS, which probes 50 to 100 A in depth, detected the major sample components underneath the contaminant film in every analysis. This probably indicates that the contaminant overlayer is patchy, with significant areas covered by less that 100 A of molecular film. Energy dispersive x-ray spectroscopy (EDS) of LDEF exposed surfaces during secondary electron microscopy (SEM) of the samples confirmed contamination of the surfaces with Si and O. In general, particulates were not observed to develop from the contaminant overlayer on the exposed LDEF material surfaces. However, many SiO2 submicron particles were seen on a masked edge of an Ag/FEP blanket. In some cases such as the carbon fiber/organic matrix composites, interpretation of the contamination data was hindered by the lack of good laboratory controls. Examination of laboratory controls for the carbon fiber/Al alloy composites showed that preflight contamination was the most significant factor for all the contaminants generally detected at less than 1 atom percent, or detected only occasionally (i.e., all but Si, O, and C). Flight control surfaces, including sample backsides not exposed to space radiation or atomic oxygen flux, have accumulated some contamination on flight (compared to laboratory controls), but experimentally, the LDEF exposed surface contamination levels are generally higher for the contaminants Si and O. For most materials analyzed, Si contamination levels were higher on the leading edge surfaces than on the trailing edge surfaces. This was true even for the composite samples where considerable atomic oxygen erosion of the leading edge surfaces was observed by SEM. It is probable that the return flux associated with atmospheric backscatter resulted in enhanced deposition of silicones and other contaminants on the leading edge flight surfaces relative to the trailing edge. Although the Si concentration data suggested greater on-flight deposition of contaminants on the leading edge surfaces, the XPS analyses did not conclusively show different relative total thicknesses of flight deposited contamination for leading and trailing edge surfaces. It is possible that atomic oxygen reactions on the leading edge resulted in greater volatilization of the carbon component of the deposited silicones, effectively 'thinning' the leading edge deposited overlayer. Unlike other materials, exposed polymers such as Kapton and FEP-type Teflon had very low contamination on the leading edge surfaces. SEM evidence showed that undercutting of the contaminant overlayer and damaged polymer layers occurred during atomic oxygen erosion, which would enhance loss of material from the exposed surface.

Hemminger, Carol S.↗

Contamination measurements on experiment M0003

The contamination monitors on the M0003 experiment consisted of passive sample collectors to measure molecular and particulate deposition. The collectors were placed in the leading and trailing edge trays of M0003. The objective was to quantify the contaminants and determine how contamination affected the other materials in the trays. Duplicate collectors were placed inside the vacuum canisters that provided protection from the launch, ascent, deployment, and recovery environments. Analyses of the samples show small quantities of molecular deposition on both the leading and trailing edge trays. Silicone deposits are negligible. The aluminized fused silica, second surface mirrors showed small changes in solar absorptances. This is consistent with the small quantities of molecular deposits deduced from the FTIR measurements. The results of particle deposition, light scatter, and a micrometeoroid (or debris) impact are presented.

Borson, Eugene N.↗