Characterization of ion processes in a GC/DMS air quality monitor by integration of the instrument to a mass spectrometer.

The air quality monitor (AQM), which included a portable gas chromatograph (GC) and a detector was interfaced to a mass spectrometer (MS) by introducing flow from the GC detector to the atmospheric pressure ion source of the MS. This small GC system, with a gas recirculation loop for carrier and detector make-up gases, comprised an inlet to preconcentrate volatile organic compounds (VOCs) in air, a thermal desorber before the GC column, a differential mobility spectrometer (DMS), and another DMS as an atmospheric pressure ionization source for the MS. Return flow to the internally recirculated air system of the AQM's DMS was replenished using purified air. Although ions and unreacted neutral vapors flowed from the detector through Viton® tubing into the source of the MS, ions were not detected in the MS without the auxillary ion source, (63)Ni as in the mobility detector. The GC-DMS-MS instrument provided a 3-D measurement platform (GC, DMS, and MS analysis) to explore the gas composition inside the GC-DMS recirculation loop and provide DMS-MS measurement of the components of a complex VOC mixture with performance significantly enhanced by mass-analysis, either with mass spectral scans or with an extracted ion chromatogram. This combination of a mobility spectrometer and a mass spectrometer was possible as vapors and ions are carried together through the DMS analyzer, thereby preserving the chromatographic separation efficiency. The critical benefit of this instrument concept is that all flows in and through the thoroughly integrated GC-DMS analyzer are kept intact allowing a full measure of the ion and vapor composition in the complete system. Performance has been evaluated using a synthetic air sample and a sample of airborne vapors in a laboratory. Capabilities and performance values are described using results from AQM-MS analysis of purified air, ambient air from a research laboratory in a chemistry building, and a sample of synthetic air of known composition. Quantitative measures of a stand-alone AQM are disclosed for VOCs in the ppb to ppm levels with an average precision of 5.8% RSD and accuracy from 4% to 28% error against a standard method.

Mass spectrometry in the U.S. space program: past, present, and future.

Recent years have witnessed significant progress on the miniaturization of mass spectrometers for a variety of field applications. This article describes the development and application of mass spectrometry (MS) instrumentation to support of goals of the U.S. space program. Its main focus is on the two most common space-related applications of MS: studying the composition of planetary atmospheres and monitoring air quality on manned space missions. Both sets of applications present special requirements in terms of analytical performance (sensitivity, selectivity, speed, etc.), logistical considerations (space, weight, and power requirements), and deployment in perhaps the harshest of all possible environments (space). The MS instruments deployed on the Pioneer Venus and Mars Viking Lander missions are reviewed for the purposes of illustrating the unique features of the sample introduction systems, mass analyzers, and vacuum systems, and for presenting their specifications which are impressive even by today's standards. The various approaches for monitoring volatile organic compounds (VOCs) in cabin atmospheres are also reviewed. In the past, ground-based GC/MS instruments have been used to identify and quantify VOCs in archival samples collected during the Mercury, Apollo, Skylab, Space Shuttle, and Mir missions. Some of the data from the more recent missions are provided to illustrate the composition data obtained and to underscore the need for instrumentation to perform such monitoring in situ. Lastly, the development of two emerging technologies, Direct Sampling Ion Trap Mass Spectrometry (DSITMS) and GC/Ion Mobility Spectrometry (GC/IMS), will be discussed to illustrate their potential utility for future missions.

Determination of ammonia in ethylene using ion mobility spectrometry.

A simple procedure to analyze ammonia in ethylene by ion mobility spectrometry is described. The spectrometer is operated with a silane polymer membrane., 63Ni ion source, H+ (H2O)n reactant ion, and nitrogen drift and source gas. Ethylene containing parts per billion (ppb) (v/v) concentrations of ammonia is pulled across the membrane and diffuses into the spectrometer. Preconcentration or preseparation is unnecessary, because the ethylene in the spectrometer has no noticeable effect on the analytical results. Ethylene does not polymerize in the radioactive source. Ethylene's flammability is negated by the nitrogen inside the spectrometer. Response to ammonia concentrations between 200 ppb and 1.5 ppm is near linear, and a detection limit of 25 ppb is calculated.

Volatile organic contaminants found in the habitable environment of the Space Shuttle: STS-26 to STS-55.

The health and performance of spacecraft crews can be adversely affected by contaminants present in the respirable air. Contaminants originate from hardware offgassing, crew and microbial metabolism, use of utility chemicals, leakage from fluid systems and payload experiments, and from electrical overheating. The quality of Shuttle air is measured by collecting contaminants in evacuated cylinders or on sorbent resin for later ground-based analysis by gas chromatography (GC) and GC mass spectrometry (MS). The results of those analyses are presented for 28 missions, including 5 Spacelabs which were flown in the payload bay of the Shuttle. The major contaminants were relatively nontoxic alcohols (ethanol, isopropanol), ketones (acetone, diacetone alcohol), alkanes, halocarbons (Halon 1301, Freon 113), and siloxanes. Occasionally, more toxic contaminants, such as methanol, acetaldehyde, and tetrachloroethene, were present at low concentrations (below 1 mg/m3). The contaminant concentrations measured in spacecraft air were compared to spacecraft maximum allowable concentrations (SMAC's) which are set to protect the crew from adverse health effects or performance decrements. Aggregate toxicity assessments (T values) of the contaminants present during each mission, calculated by summing the ratios of measured concentrations to each contaminant's SMAC, showed that air quality consistent met the criterion that the T value be less than 1.

Air quality assessments for two recent Space Shuttle flights.

Degradation of air quality in the Space Shuttle environment through chemical contamination and high solid-particulate levels may affect crew performance and health. A comprehensive study of the Shuttle atmosphere was undertaken during the STS-40 (Spacelab Space Life Sciences 1) and STS-42 (Spacelab International Microgravity Laboratory 1) missions to determine the effectiveness of contaminant control procedures by measuring concentrations of volatile organic compounds and analyzing particulate matter trapped on air filters. Analysis of volatile contaminants showed that the air was toxicologically safe to breathe during both missions with the exception of one period during STS-40 when the Orbiter Refrigerator/Freezer was releasing noxious gases into the middeck. Chemical analyses of selected particles collected on air filters facilitated their positive identification. Trace amounts of rat hair and food particles were found in the STS-40 Spacelab filters; a trace amount of soilless plant-growth media was detected in the STS-42 Spacelab filter. The low levels of particles released from these Spacelab experiments indicate that containment measures were effective.

Pyrolysis-gas chromatography/mass spectrometry analyses of biological particulates collected during recent space shuttle missions.

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.

Multisorbent tubes for collecting volatile organic compounds in spacecraft air.

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.

Ion mobility spectrometry of hydrazine, monomethylhydrazine, and ammonia in air with 5-nonanone reagent gas.

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.