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Liquid Chromatography / Mass Spectrometry / Mass Spectrometry (LC/MS/MS) is a powerful technique for identifying unknown non-volatile organic compounds dissolved in liquids. One type of LC/MS/MS that is gaining popularity is quadrupole-time-of-flight (QqTOF) mass spectrometry. This technique is now in use at the Johnson Space Center for identification of unknown nonvolatile organics in water samples from the space program. An example of the successful identification of an unknown peak in U.S. Lab Condensate is reviewed in detail in this paper. Each step of the procedure is described in the identification of triethylene glycol mono-n-butyl ether (TGBE) as the unknown analyte. The advantages of time-of-flight instrumentation are demonstrated through this example as well as the strategy employed in using time-of-flight data to identify unknowns. The use of the instrument for quantitative analysis is also demonstrated.

At present, spacecraft water quality is assessed when samples collected on the International Space Station (ISS) are returned to Earth. Several months, however, may pass between sample collection and analysis, potentially compromising sample integrity by risking degradation. For example, iodine and silver, which are the respective biocides used in the U.S. and Russian spacecraft potable water systems, must be held at levels that prevent bacterial growth, while avoiding adverse effects on crew health. A comparable need exists for the detection of many heavy metals, toxic organic compounds, and microorganisms. Lead, cadmium, and nickel have been found, for instance, in the ISS potable water system at amounts that surpass existent requirements. There have been similar occurrences with hazardous organic compounds like formaldehyde and ethylene glycol. Microorganism counts above acceptable limits have also been reported in a few instances.

The Johnson Space Center Water and Food Analytical Laboratory (WAFAL) performed detailed ground-based analyses of archival water samples for verification of the chemical quality of the International Space Station (ISS) potable water supplies for Expeditions 14 and 15. During the 12-month duration of both expeditions, the Space Shuttle docked with the ISS on four occasions to continue construction and deliver additional crew and supplies; however, no Shuttle potable water was transferred to the station during Expedition 14. Russian ground-supplied potable water and potable water from regeneration of humidity condensate were both available onboard the ISS for consumption by the Expeditions 14 and 15 crews. A total of 16 chemical archival water samples were collected with U.S. hardware during Expeditions 14 and 15 and returned on Shuttle flights STS-116 (12A.1), STS-117 (13A), STS-118 (13A.1), and STS-120 (10A) in December 2006, and June, August, and November of 2007, respectively.

We are developing a drinking water test kit based on colorimetric-solid phase extraction (C-SPE) for use onboard the International Space Station (ISS) and on future Lunar and/or Mars missions. C-SPE involves measuring the change in diffuse reflectance of indicator disks following their exposure to a water sample. We previously demonstrated the effectiveness of C-SPE in measuring iodine in microgravity. This analytical method has now been extended to encompass the measurement of total I (i.e., iodine, iodide, and triiodide). This objective was accomplished by introducing an oxidizing agent to convert iodide and triiodide to iodine, which is then measured using the indicator disks previously developed for iodine. We report here the results of a recent series of C-9 microgravity tests of this method. The results demonstrate that C-SPE technology is poised to meet the total I monitoring requirements of the international space program.

Aqueous silver(I) is added at trace levels (0.1 – 1.0 mg/L) to spacecraft potable water as a biocide. Development of a method that can be deployed on orbit and in future Lunar and Mars missions is therefore central to maintenance of safe drinking water and crew health. To address this need, our laboratory has created an analytical technique that couples a selective sorption process based on solid phase extraction (SPE) with the quantitative measurement of the extract by a hand-held diffuse reflection spectrophotometer. This technique, referred to as colorimetric-solid phase extraction (C-SPE), enables the low level detection (limit of detection ∼5 ppb) of silver(I) by metering 1.0 mL of a water sample through a reagent-impregnated (i.e., 5-(p-dimethyl-aminobenzylidene)rhodanine, DMABR) SPE membrane. The total workup time for the analysis is only 60-90 s.

The crews of Expeditions 12 and 13 aboard the International Space Station (ISS) continued to rely on potable water from two different sources, regenerated humidity condensate and Russian ground-supplied water. The Space Shuttle launched twice during the 12-months spanning both expeditions and docked with the ISS for delivery of hardware and supplies. However, no Shuttle potable water was transferred to the station during either of these missions. The chemical quality of the ISS onboard potable water supplies was verified by performing ground analyses of archival water samples at the Johnson Space Center (JSC) Water and Food Analytical Laboratory (WAFAL). Since no Shuttle flights launched during Expedition 12 and there was restricted return volume on the Russian Soyuz vehicle, only one chemical archive potable water sample was collected with U.S. hardware and returned during Expedition 12. This sample was collected in March 2006 and returned on Soyuz 11.

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). 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.

Colorimetric-solid phase extraction (C-SPE) is being developed as a method for in-flight monitoring of spacecraft water quality. C-SPE is based on measuring the change in the diffuse reflectance spectrum of indicator disks following exposure to a water sample. Previous microgravity testing has shown that air bubbles suspended in water samples can cause uncertainty in the volume of liquid passed through the disks, leading to errors in the determination of water quality parameter concentrations. We report here the results of a recent series of C-9 microgravity experiments designed to evaluate manual manipulation as a means to collect bubble-free water samples of specified volumes from water sample bags containing up to 47% air. The effectiveness of manual manipulation was verified by comparing the results from C-SPE analyses of silver(I) and iodine performed in-flight using samples collected and debubbled in microgravity to those performed on-ground using bubble-free samples.

During the twelve month period comprising Expeditions 10 and 11, the chemical quality of the potable water onboard the International Space Station (ISS) was verified through the return and ground analysis of water samples. The two-man Expedition 10 crew relied solely on Russian-provided ground water and reclaimed cabin humidity condensate as their sources of potable water. Collection of archival water samples with U.S. hardware has remained extremely restricted since the Columbia tragedy because of very limited return volume on Russian Soyuz vehicles. As a result only two such samples were collected during Expedition 10 and returned on Soyuz 9. The average return sample volume was only 250 milliliters, which limited the breadth of chemical analysis that could be performed. Despite the Space Shuttle vehicle returning to flight in July 2005, only two potable water samples were collected with U.S. hardware during Expedition 11 and returned on Shuttle flight STS-114 (LF1).

Potable water for the Shuttle orbiter is generated as a by-product of electricity production by the fuel cells. Water from the fuel cells flows through a Microbial Check Valve (MCV), which releases biocidal iodine into the water before it enters one of four storage tanks. Potable water is dispensed on-orbit at the rehydration unit of the galley. Due to crew health concerns, iodine removal hardware is installed in the chilled water inlet line to the galley to remove the iodine from the potable water before it is consumed by the crew. The Shuttle water system is sampled to ensure water quality is maintained during all operational phases from the disinfection of the ground servicing equipment through the completion of each mission. This paper describes and summarizes the Shuttle water quality requirements, the servicing of the Shuttle water system, the collection and analysis of Shuttle water samples, and the results of the analyses.

Approximately 50% of the water consumed by International Space Station crewmembers is water recovered from cabin humidity condensate. Condensing heat exchangers in the Russian Service Module (SM) and the United States On-Orbit Segment (USOS) are used to control cabin humidity levels. In the SM, humidity condensate flows directly from the heat exchanger to a water recovery system. In the USOS, a metal bellows tank located in the US Laboratory Module (LAB) collects and stores condensate, which is periodically off-loaded in about 20-liter batches to Contingency Water Containers (CWCs). The CWCs can then be transferred to the SM and connected to a Condensate Feed Unit that pumps the condensate from the CWCs into the water recovery system for processing. Samples of the condensate in the tank are collected during the off-loads and returned to Earth for analyses.

With the Shuttle fleet grounded, limited capability exists to resupply in-flight water quality monitoring hardware onboard the International Space Station (ISS). As such, verification of the chemical quality of the potable water supplies on ISS has depended entirely upon the collection, return, and ground-analysis of archival water samples. Despite the loss of Shuttle-transferred water as a water source, the two-man crews during Expedition 8 and Expedition 9 maintained station operations for nearly a year relying solely on the two remaining sources of potable water; reclaimed humidity condensate and Russian-launched ground water. Archival potable water samples were only collected every 3 to 4 months from the systems that regenerate water from condensate (SRV-K) and distribute stored potable water (SVO-ZV).

Preliminary results on the development of quick, simple analytical method for the low level of lead(II) in water samples are described. The method concentrates lead(II) on a small solid-phase extraction disk, which is then quantified directly on the disk by diffuse reflectance spectroscopy (DRS). This method, termed colorimetric solid-phase extraction (C-SPE), requires only 1–2 min for complete workup and is suitable for use in a wide range of applications, including the microgravity environment on the International Space Station. The procedure first adds an excess of potassium iodide to a 10.0 mL sample at a pH of 3.0–3.5 to produce the anionic PbI42− colored complex, which is exhaustively extracted by the disk that was previously impregnated with cetylpyridinium chloride (CPC). The amount of complex extracted is then determined at 420 nm by a hand-held DRS instrument.

Contamination of spacecraft water by heavy metals, such as cadmium and lead, is of growing concern. As a consequence, there is need for a rapid, on-board, easy-to-use method for the determination of cadmium(II) at low ppb levels in spacecraft drinking water supplies. This paper describes the preliminary development of a method for the selective, low level determination of cadmium(II) based on colorimetric-solid phase extraction (C-SPE) [1, 2]. In C-SPE, an analyte is extracted from a water sample onto a membrane that has been previously impregnated with a colorimetric reagent, and then quantified as its colorimetric complex directly on the membrane surface using diffuse reflectance spectroscopy. Results from preliminary tests that screened the performance of 1-(4-nitrophenyl)-3-(4-phenyl-azophenyl)triazene (cadion), and organic dyes, rhodamine B, brilliant green, and methyl violet as colorimetric reagents for potential use in a C-SPE analysis of cadmium(II) are described.

The need to preserve crew health during space missions, combined with the level of demand on both crew time and cargo space, dictates the development of fast, facile methods capable of monitoring trace quantities of several analytes in spacecraft water. This presentation describes our efforts to address this need by using Multiplexed Colorimetric Solid Phase Extraction (MC-SPE). MC-SPE is a sorption-spectrophotometric platform based upon the extraction of analytes onto membranes impregnated with selective colorimetric agents. Quantification is accomplished using Kubelka-Munk values calculated from the diffuse reflectance spectrum of the complex on the surface of the membrane and calibration curves. In traditional C-SPE, concentration factors of up to 1000 can be realized for a single analysis, yielding low detection limits (ppb – ppm range) with a total analysis time of 75–90 s. Herein, we describe the performance and continued refinement of the MC-SPE platform.

Colorimetric solid-phase extraction (C-SPE) is an integrated technique in which a selected analyte is concentrated onto a disk by SPE and then measured quantitatively by diffuse reflectance spectroscopy (DRS). Although several C-SPE methods have been tested successfully in microgravity simulations, incorporation of air bubbles often makes it difficult to accurately measure the volume of aqueous sample used for the analysis. This paper investigates the application of negligible depletion (ND) to C-SPE. ND is based on reaching an equilibrium in which the concentration of analyte in the original sample and in the outflow from the disk are equal after a minimum volume of sample has passed through the disk. As a result, the amount of extracted analyte is proportional to the sample concentration but independent of sample volume. With this approach, called C-SPE-ND, the precise measurement of sample volume is no longer necessary.

Space exploration by humans requires maintenance of an adequate potable water supply. Biocide levels must therefore be kept within allowable limits to prevent bacterial growth without causing adverse effects on crew health. Likewise, contaminants such as heavy metals and toxic organic compounds must be held at or below acceptable limits. Currently, spacecraft water quality analyses are performed on samples collected on the International Space Station and returned to Earth. Several months, however, can pass between sample collection and analysis, which may compromise sample integrity due to degradation. These delays also inhibit implementation of real time correction scenarios. There is, therefore, a critical need for rapid, on-board methods for monitoring trace quantities of several analytes in spacecraft drinking water supplies.

We are developing a spacecraft water quality monitoring system based on measuring the change in diffuse reflectance of indicator disks following exposure to a water sample. The most widely used approach for deriving quantitative information from a diffuse reflectance spectrum involves an initial Kubelka-Munk transformation of the reflectance data. Provided the assumptions underlying the transformation are satisfied, the magnitude of the resulting function varies linearly with analyte concentration. We measure diffuse reflectance spectra using a commercial-off-the-shelf handheld spectrophotometer designed for color matching applications. Spectra are currently downloaded and transformed to obtain the value of the Kubelka-Munk function at a detection wavelength diagnostic of the analyte. This value is then used to quantify the analyte via a standard response curve.

Ever since the first crew arrived at the International Space Station (ISS), archival potable water samples have been collected and returned to the ground for detailed chemical analysis in order to verify that the water supplies onboard are suitable for crew consumption. The Columbia tragedy, unfortunately, has had a dramatic impact on continued ISS operations. A major portion of the ISS water supply had previously consisted of Shuttle-transferred water. The other two remaining sources of potable water, i.e., reclaimed humidity condensate and Russian-launched ground water, are together insufficient to maintain 3-person crews. The Expedition 7 crew launched in April of 2003 was, therefore, reduced from three to two persons. Without the Shuttle, resupply of ISS crews and supplies is dependent entirely on Russian launch vehicles (Soyuz and Progress) with severely limited up and down mass.

Archived water samples collected on the International Space Station (ISS) and returned to Earth for analysis have, in a few instances, contained trace levels of heavy metals. Building on our previous advances using Colorimetric Solid Phase Extraction (C-SPE) as a biocide monitoring technique [1, 2], we are devising methods for the low level monitoring of nickel(II), lead(II) and other heavy metals. C-SPE is a sorption-spectrophotometric platform based on the extraction of analytes onto a membrane impregnated with a colorimetric reagent that are then quantified on the surface of the membrane using a diffuse reflectance spectrophotometer. Along these lines, we have analyzed nickel(II) via complexation with dimethylglyoxime (DMG) and begun to examine the analysis of lead(II) by its reaction with 2,5-dimercapto-1, 3, 4-thiadiazole (DMTD) and 4-(2-pyridylazo)-resorcinol (PAR).