Daniel B. Gazda

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.

Extravehicular Mobility Unit (EMU) / International Space Station (ISS) Coolant Loop Failure and Recovery

ABSTRACT Following the Colombia accident, the Extravehicular Mobility Units (EMU) onboard ISS were unused for several months. Upon startup, the units experienced a failure in the coolant system. This failure resulted in the loss of Extravehicular Activity (EVA) capability from the US segment of ISS. With limited on-orbit evidence, a team of chemists, engineers, metallurgists, and microbiologists were able to identify the cause of the failure and develop recovery hardware and procedures. As a result of this work, the ISS crew regained the capability to perform EVAs from the US segment of the ISS Figure 1. INTRODUCTION The EMUs coolant system circulates water used to reject heat from the crewmember and the equipment. See Figure 2 for the Airlock/EMU Coolant Loop Schematic. During EVA, the EMU depends on vacuum for sublimation cooling. During EVA preparations, the Airlock coolant loop provides cooling for the EMU when it is at ambient pressures during EVA preparation. The Airlock coolant loop contains a heat exchanger and umbilicals to connect to the EMU. The EMU contains the pump and systems to circulate and degas the coolant loop along with the liquid cooling garment to provide cooling to the suited crew member FIGURE 1 – EMU work on orbit

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.

Design, Certification, and Deployment of the Colorimetric Water Quality Monitoring Kit (CWQMK)

In August 2009, an experimental water quality monitoring kit based on Colorimetric Solid Phase Extraction (CSPE) technology was delivered to the International Space Station (ISS) aboard STS-128/17A. The kit, called the Colorimetric Water Quality Monitoring Kit (CWQMK), was developed by a team of scientists and engineers from NASA s Habitability and Environmental Factors Division in the Space Life Sciences Directorate at Johnson Space Center, the Wyle Integrated Science and Engineering Group in Houston, Texas, the University of Utah, and Iowa State University. The CWQMK was flown and deployed as a Station Development Test Objective (SDTO) experiment on ISS. The goal of the SDTO experiment was to evaluate the acceptability of CSPE technology for routine water quality monitoring on ISS. This paper provides an overview of the SDTO experiment, as well as a detailed description of the CWQMK hardware and a summary of the testing and analysis conducted to certify the CWQMK for use on ISS. The results obtained from the SDTO experiment are also reported and discussed in detail.

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

Performance of the Extravehicular Mobility Unit (EMU) Airlock Coolant Loop Remediation (A/L CLR) Hardware

An EMU water processing kit (Airlock Coolant Loop Recovery A/L CLR) was developed as a corrective action to Extravehicular Mobility Unit (EMU) coolant flow disruptions experienced on the International Space Station (ISS) in May of 2004 and thereafter. Conservative schedules for A/L CLR use and component life were initially developed and implemented based on prior analysis results and analytical modeling. The examination of postflight samples and EMU hardware in November of 2006 indicated that the A/L CLR kits were functioning well and had excess capacity that would allow a relaxation of the initially conservative schedules of use and component life. A relaxed use schedule and list of component lives was implemented thereafter. Since the adoption of the relaxed A/L CLR schedules of use and component lives, several A/L CLR kit components, transport loop water samples and sensitive EMU transport loop components have been examined to gage the impact of the relaxed requirements. The intent of this paper is to summarize the findings of that evaluation, and to outline updated schedules for A/L CLR use and component life.

In-Flight Water Quality Monitoring on the International Space Station (ISS): Measuring Biocide Concentrations with Colorimetric Solid Phase Extraction (CSPE)

The colorimetric water quality monitoring kit (CWQMK) was delivered to the International Space Station (ISS) on STS-128/17A and was initially deployed in September 2009. The kit was flown as a station development test objective (SDTO) experiment to evaluate the acceptability of colorimetric solid phase extraction (CSPE) technology for routine water quality monitoring on the ISS. During the SDTO experiment, water samples from the U.S. water processor assembly (WPA), the U.S. potable water dispenser (PWD), and the Russian system for dispensing ground-supplied water (SVO-ZV) were collected and analyzed with the CWQMK. Samples from the U.S. segment of the ISS were analyzed for molecular iodine, which is the biocide added to water in the WPA. Samples from the SVOZV system were analyzed for ionic silver, the biocide used on the Russian segment of the ISS. In all, thirteen in-flight analysis sessions were completed as part of the SDTO experiment. This paper provides an overview of the experiment and reports the results obtained with the CWQMK. The forward plan for certifying the CWQMK as operational hardware and expanding the capabilities of the kit are also discussed.

Crew Exploration Vehicle (CEV) Potable Water System Verification Description

The Crew Exploration Vehicle (CEV), also known as Orion, will ferry a crew of up to six astronauts to the International Space Station (ISS), or a crew of up to four astronauts to the moon. The first launch of CEV is scheduled for approximately 2014. A stored water system on the CEV will supply the crew with potable water for various purposes: drinking and food rehydration, hygiene, medical needs, sublimation, and various contingency situations. The current baseline biocide for the stored water system is ionic silver, similar in composition to the biocide used to maintain quality of the water transferred from the Orbiter to the ISS and stored in Contingency Water Containers (CWCs). In the CEV water system, the ionic silver biocide is expected to be depleted from solution due to ionic silver plating onto the surfaces of the materials within the CEV water system, thus negating its effectiveness as a biocide. Since the biocide depletion is expected to occur within a short amount of time after loading the water into the CEV water tanks at the Kennedy Space Center (KSC), an additional microbial control is a 0.1 micron point of use filter that will be used at the outlet of the Potable Water Dispenser (PWD). Because this may be the first time NASA is considering a stored water system for longterm missions that does not maintain a residual biocide, a team of experts in materials compatibility, biofilms and point of use filters, surface treatment and coatings, and biocides has been created to pinpoint concerns and perform testing to help alleviate those concerns related to the CEV water system. Results from the test plans laid out in the paper presented to SAE last year (Crew Exploration Vehicle (CEV) Potable Water System Verification Coordination, 2008012083) will be detailed in this paper. Additionally, recommendations for the CEV verification will be described for risk mitigation in meeting the physicochemical and microbiological requirements on the CEV PWS.

Colorimetric Solid Phase Extraction for the Measurement of Total I (Iodine, Iodide, and Triiodide) in Spacecraft Drinking Water

An experimental drinking water monitoring kit for the measurement of iodine and silver(I) was recently delivered to the International Space Station (ISS). The kit is based on Colorimetric Solid Phase Extraction (CSPE) technology, which measures the change in diffuse reflectance of indicator disks following exposure to a water sample. To satisfy additional spacecraft water monitoring requirements, CSPE has now been extended to encompass the measurement of total I (iodine, iodide, and triiodide) through the introduction of an oxidizing agent, which converts iodide and triiodide to iodine, for measurement using the same indicator disks currently being tested on ISS. These disks detect iodine, but are insensitive to iodide and triiodide. We report here the operational considerations, design, and ground-based performance of the CSPE method for total I. The results demonstrate that CSPE technology is poised to meet NASAs total I monitoring requirements.

Liquid Metering Centrifuge Sticks (LMCS): A Centrifugal Approach to Metering Known Sample Volumes for Colorimetric Solid Phase Extraction (C-SPE)

Phase separation is one of the most significant obstacles encountered during the development of analytical methods for water quality monitoring in spacecraft environments. Removing air bubbles from water samples prior to analysis is a routine task on earth; however, in the absence of gravity, this routine task becomes extremely difficult. This paper details the development and initial ground testing of liquid metering centrifuge sticks (LMCS), devices designed to collect and meter a known volume of bubble-free water in microgravity. The LMCS uses centrifugal force to eliminate entrapped air and reproducibly meter liquid sample volumes for analysis with Colorimetric Solid Phase Extraction (C-SPE). C-SPE is a sorption-spectrophotometric platform that is being developed as a potential spacecraft water quality monitoring system. C-SPE utilizes solid phase extraction membranes impregnated with analyte-specific colorimetric reagents to concentrate and complex target analytes in spacecraft water samples. The mass of analyte extracted from the water sample is determined using diffuse reflectance (DR) data collected from the membrane surface and an analyte-specific calibration curve. The analyte concentration can then be calculated from the mass of extracted analyte and the volume of the sample analyzed. Previous flight experiments conducted in microgravity conditions aboard the NASA KC-135 aircraft demonstrated that the inability to collect and meter a known volume of water using a syringe was a limiting factor in the accuracy of C-SPE measurements. Herein, results obtained from ground based C-SPE experiments using ionic silver as a test analyte and either the LMCS or syringes for sample metering are compared to evaluate the performance of the LMCS. These results indicate very good agreement between the two sample metering methods and clearly illustrate the potential of utilizing centrifugal forces to achieve phase separation and metering of water samples in microgravity.