Thomas Limero

Electro-thermal vaporization direct analysis in real time-mass spectrometry for water contaminant analysis during space missions.

The development of a direct analysis in real time-mass spectrometry (DART-MS) method and first prototype vaporizer for the detection of low molecular weight (∼30-100 Da) contaminants representative of those detected in water samples from the International Space Station is reported. A temperature-programmable, electro-thermal vaporizer (ETV) was designed, constructed, and evaluated as a sampling interface for DART-MS. The ETV facilitates analysis of water samples with minimum user intervention while maximizing analytical sensitivity and sample throughput. The integrated DART-ETV-MS methodology was evaluated in both positive and negative ion modes to (1) determine experimental conditions suitable for coupling DART with ETV as a sample inlet and ionization platform for time-of-flight MS, (2) to identify analyte response ions, (3) to determine the detection limit and dynamic range for target analyte measurement, and (4) to determine the reproducibility of measurements made with the method when using manual sample introduction into the vaporizer. Nitrogen was used as the DART working gas, and the target analytes chosen for the study were ethyl acetate, acetone, acetaldehyde, ethanol, ethylene glycol, dimethylsilanediol, formaldehyde, isopropanol, methanol, methylethyl ketone, methylsulfone, propylene glycol, and trimethylsilanol.

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. Ethylenes 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.

Results of the Air Quality Monitor's Experiment to Measure Volatile Organic Compounds aboard the International Space Station

The Volatile Organic Analyzer (VOA) provided 9 years of information on the trace volatile organic compounds (VOCs) in the atmosphere of the International Space Station (ISS), but it was decommissioned in August 2009. The NASA’s Toxicology Laboratory at Johnson Space Center and others have been evaluating technologies to replace the VOA for several years. One system investigated by the NASA’s Toxicology Laboratory was Sionex’s microAnalyzer™ (later designated the Air Quality Monitor-AQM), whose small size demanded attention. Early versions of the microAnalyzer™ were thoroughly tested and the results showed great promise for it to meet or exceed the performance of the VOA. Two AQMs were prepared as a station detailed test objective (SDTO) and flown to ISS aboard the Space Shuttle in March 2009. The purpose of the SDTO was to evaluate the AQM performance, in the intended operational environment, as a replacement for the VOA. This paper will present a brief overview of the AQM technology (gas chromatography/differential mobility spectrometry) and briefly discuss the flight preparation of the AQM for the SDTO. The major portion of the paper will be devoted to on-orbit results and comparison of data from simultaneously acquired AQM runs and archival samples.

A Volatile Organic Analyzer for Space Station - Description and evaluation of a gas chromatography/ion mobility spectrometer

A Volatile Organic Analyzer (VOA) is being developed as an essential component of the Space Stations Environmental Health System (EHS) air quality monitoring strategy to provide warning to the crew and ground personnel if volatile organic compounds exceed established exposure limits. The short duration of most Shuttle flights and the relative simplicity of the contaminant removal mechanism have lessened the concern about crew exposure to air contaminants on the Shuttle. However, the longer missions associated with the Space Station, the complex air revitalization system and the proposed number of experiments have led to a desire for real-time monitoring of the contaminants in the Space Station atmosphere. Achieving the performance requirements established for the VOA within the Space Station resource (e.g., power, weight) allocations led to a novel approach that joined a gas chromatograph (GC) to an ion mobility spectrometer (IMS). The authors of this paper will discuss the rational for selecting the GC/IMS technology as opposed to the more established gas chromatography/mass spectrometry (GC/MS) for the foundation of the VOA. The data presented from preliminary evaluations will demonstrate the versatile capability of the GC/IMS to analyze the major contaminants expected in the Space Station atmosphere. The favorable GC/IMS characteristics illustrated in this paper included excellent sensitivity, dual-mode operation for selective detection, and mobility drift times to distinguish co-eluting GC peaks. Preliminary studies have shown that the GC/IMS technology can meet surpass the performance requirements of the Space Station VOA.

A Combustion Products Analyzer for Contingency Use During Thermodegradation Events on Spacecraft

The Toxicology Laboratory at JSC and Exidyne Instrumentation Technologies (EIT) have developed a prototype Combustion Products Analyzer (CPA) to monitor, in real time, combustion products from a thermodegradation event on board spacecraft. The CPA monitors the four gases that are the most hazardous compounds (based on the toxicity potential and quantity produced) likely to be released during thermodegradation of synthetic materials: hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen cyanide (HCN), and carbon monoxide (CO). The levels of these compounds serve as markers to assist toxicologists in determining when the cabin atmosphere is safe for the crew to breathe following the contingency event. The CPA is a hand-held, battery-operated instrument containing four electrochemical sensors, one for each target gas, and a pump for drawing air across the sensors. The sensors are unique in their small size and zero-g compatibility. The immobilized electrolytes in each sensor permit the instrument to function in space and eliminate the possibility of electrolye leaks. The sample inlet system is equipped with a particulate filter that prevents clogging from airborne particulate matter. The CPA has a large digital display for gas concentrations and warming signals for low flow and low battery conditions. The CPA has flown on 13 missions beginning with STS 41 in Oct. 1990. Current efforts include the development of a microprocessor, an improved carbon monoxide sensor, and a ground-based test program to evaluate the CPA during actual thermodegradation of selected materials.

Electrothermal Vaporization Sample Introduction for Spaceflight Water Quality Monitoring via Gas Chromatography-Differential Mobility Spectrometry.

In the history of manned spaceflight, environmental monitoring has relied heavily on archival sampling. However, with the construction of the International Space Station (ISS) and the subsequent extension in mission duration up to one year, an enhanced, real-time method for environmental monitoring is necessary. The station air is currently monitored for trace volatile organic compounds (VOCs) using gas chromatography-differential mobility spectrometry (GC-DMS) via the Air Quality Monitor (AQM), while water is analyzed to measure total organic carbon and biocide concentrations using the Total Organic Carbon Analyzer (TOCA) and the Colorimetric Water Quality Monitoring Kit (CWQMK), respectively. As mission scenarios extend beyond low Earth orbit, a convergence in analytical instrumentation to analyze both air and water samples is highly desirable. Since the AQM currently provides quantitative, compound-specific information for air samples and many of the targets in air are also common to water, this platform is a logical starting point for developing a multimatrix monitor. Here, we report on the interfacing of an electrothermal vaporization (ETV) sample introduction unit with a ground-based AQM for monitoring target analytes in water. The results show that each of the compounds tested from water have similar GC-DMS parameters as the compounds tested in air. Moreover, the ETV enabled AQM detection of dimethlsilanediol (DMSD), a compound whose analysis had proven challenging using other sample introduction methods. Analysis of authentic ISS water samples using the ETV-AQM showed that DMSD could be successfully quantified, while the concentrations obtained for the other compounds also agreed well with laboratory results.

The Role of Environmental Health System Air Quality Monitors in SpaceStation Contingency Operations

This paper describes the Space Station Freedom (SSF) Environmental Health Systems air-quality monitoring strategy and instrumentation. A two-tier system has been developed, consisting of first-alert instruments that warn the crew of airborne contamination and a volatile organic analyzer that can identify volatile organic contaminants in near-real time. The strategy for air quality monitoring on SSF is designed to provide early detection so that the contamination can be confined to one module and so that crew health and safety can be protected throughout the contingency event. The use of air-quality monitors in fixed and portable modes will be presented as a means of following the progress of decontamination efforts and ensuring acceptable air quality in a module after an incident. The technology of each instrument will be reviewed briefly; the main focus of this paper, however, will be the use of air-quality monitors before, during, and after contingency incidents.

Microplasma Ionization of Volatile Organics for Improving Air/Water Monitoring Systems On-Board the International Space Station

AbstractLow molecular weight polar organics are commonly observed in spacecraft environments. Increasing concentrations of one or more of these contaminants can negatively impact Environmental Control and Life Support (ECLS) systems and/or the health of crew members, posing potential risks to the success of manned space missions. Ambient plasma ionization mass spectrometry (MS) is finding effective use as part of the analytical methodologies being tested for next-generation space module environmental analysis. However, ambient ionization methods employing atmospheric plasmas typically require relatively high operation voltages and power, thus limiting their applicability in combination with fieldable mass spectrometers. In this work, we investigate the use of a low power microplasma device in the microhollow cathode discharge (MHCD) configuration for the analysis of polar organics encountered in space missions. A metal-insulator-metal (MIM) structure with molybdenum foil disc electrodes and a mica insulator was used to form a 300 μm diameter plasma discharge cavity. We demonstrate the application of these MIM microplasmas as part of a versatile miniature ion source for the analysis of typical volatile contaminants found in the International Space Station (ISS) environment, highlighting their advantages as low cost and simple analytical devices. Graphical Abstractᅟ

Studies of the ionization chemistry in the re-circulation loop of the differential mobility spectrometer analyzer used to monitor air quality in the international space station

In-flight monitoring of volatile organic compounds on the International Space Station (ISS) has been routine since 2009 using gas chromatography, with a preconcentration inlet, and a differential mobility spectrometer detector; first as a station detailed technical objective (SDTO) instrument and then as the air quality monitor (AQM), a fully integrated instrument including imbedded computer for control and data acquisition. A combination of AQM with an atmospheric pressure ionization mass spectrometer was developed to allow exploration of instrument behavior associated with the composition of the internal re-circulated gas atmosphere. The first aspects of AQM to be explored using the AQM-mass spectrometer included explanations for mobility drift of the negative reactant ion peak, methanol, and acetaldyehyde peaks (carbon dioxide in the gas recirculation loop) with operation on ISS. The AQM-mass spectrometer system helped ascertain the identity of artifact peaks in the negative polarity associated with materials in the flow system of AQM. Further experiments investigated the influence of water from humidity in ambient air, which is absorbed on the preconcentration trap during sampling and desorbed into the gas chromatograph-differential mobility spectrometer (GC-DMS) measurement and the incorporation of a trap purge to reduce effects of water co-eluting with target contaminants.

A Second Generation Volatile Organic Analyzer for the International Space Station

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-90s. 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.