Design, Certification, and Deployment of the Colorimetric Water Quality Monitoring Kit (CWQMK) Daniel B. Gazda', Daniel J. Nolan', Jeff A. Rutz', and John R. Schultz4 Wile Integrated Science and Engineering Group, Houston, TX 77058 Lorraine M. Siperko' and Marc D. Porter University of Utah, Salt Lake City, UT 84112 Robert J. Lipert' Iowa State University, Ames, IA 50011 and Stephanie M. Flmt8 and J. Torin McCoy National Aeronautics and Space Administration, Johnson Space Center, Houston, TX 77058 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 flown and deployed as a Station Development Test Objective (SDTO) experiment on the ISS. The goal of the SDTO experiment is to evaluate the acceptability of CSPE technology for routine water quality monitoring on the 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 the ISS. The initial results obtained from the SDTO experiment are also reported and discussed in detail. Nomenclature AEMC = Advanced Environmental Monitoring and Controls Brij-30 = polyoxyethylene (4) lauryl ether COTS = commercial orbital transportation services CSPE = colorimetric solid phase extraction CWQMK = colorimetric water quality monitoring kit EMI = electromagnetic interference DMABR = 5-(p-dimethylaminobenzylidene)rhodanine DRS = diffuse reflectance spectrophotometer IP = International Partners ISS = International Space Station JPL = Jet Propulsion Laboratory ' Senior Environmental Scientist, Water and Food Analytical Laboratory. ' Senior Engineer, Flight Hardware Department- 3 Senior Scientist, Water and Food Analytical Laboratory. 4 Supervisor, Water and Food Analytical Laboratory. 5 Research Scientist, Nano Institute, University of Utah. 6 Professor; Nano Institute, University of Utah- 7 Associate Scientist, Institute for Physical Research and Technology- 8 CWQMK Project Manager, Environmental Factors Branch. 9 Technical Monitor, Water and Food Analytical Laboratory, Environmental Factors Branch- 1 American Institute of Aeronautics and Astronautics .ISC = Johnson Space Center MORD = medical operations requirements document PVP = polyvinylpyrrolidone PWD = potable water dispenser RAM = random access memory SDTO = Station Development Test Objective SVO-ZV = Russian system for dispensing ground-supplied water US = United States I. Introduction Representative water quality data must be collected in order to ensure that a safe supply of potable water is available to the crew on the International Space Station (ISS). Currently, most of the water quality data for the environmental control and life support systems on the ISS are obtained by collecting archive water samples in-flight and returning them for ground analysis. This archival approach to water quality monitoring has several limitations, most notably the time lapse between sample collection and ground analysis. Samples collected on-orbit must be stored until they can be manifested for return aboard the Shuttle or a Soyuz vehicle. Typical on-orbit storage times for water samples can range from 1-4 months, but in certain situations it can be much longer due to launch delays and limited return payload capacity. This time lapse between sampling and analysis precludes implementation of real time adjustments or corrective actions when water does not meet specifications. Sample integrity is another concern associated with relying on archival samples for water quality monitoring. The storage and transport conditions that archive water samples are subjected to are not ideal, and, as a result, the concentrations of certain compounds in the samples may be affected. This can complicate data interpretation and raise questions about whether or not the results from ground analyses are representative of the water quality on-orbit. The upcoming retirement of the Shuttle Orbiter fleet creates additional challenges for sample return and makes continued reliance on archival samples for water quality monitoring on the ISS impractical. Following the final Shuttle mission, there will be a sharp decrease in available return payload mass. This will limit both the volume and total number of samples that can be returned and may significantly increase the time lapse between sample collection and analysis. Additionally, since the US will be forced to rely on Commercial Orbital Transportation Services (COTS) and International Partner (IP) vehicles, the process for transporting archive samples to the laboratory once they are returned to the ground may become more difficult. Following Shuttle retirement, it will no longer be feasible to rely solely on archive water samples to collect such data. Since the vast majority of analytical instruments used to analyze water samples in ground laboratories are not suitable for deployment in-flight, new hardware systems capable of monitoring water quality in-flight on the ISS need to be developed. The unique operational environment on the ISS 1. impregnate membranes 2. cut membrane into 13-mm with colorimetric reagent disks and load in filter holder and the rigorous safety regulations applied to hardware deployed on the —► ^^ ---► ^, ISS dictate that any water quality =IOWA vacuum monitoring system developed for use in-flight possess several key -i characteristics. The "ideal' water quality monitoring system for the ISS must be small, light weight, provide direct real time readout of results, minimize waste, contain no hazardous materials, meet strict storage and power guidelines, and cont:iuier y^^ function effectively in zero gravity. 3. withdraw sample 4. pass sample 5. acquirreefl e7ctance Further, the system must also be from sample through disk spectruisk with bag via syringe portablespectrometer rapid and easy to use so that the crew time required for training and Figure 1. Overview of CSPE Process operation is minimal. American Institute of Aeronautics and Astronautics One candidate technology that embodies many of the characteristic of the ideal water quality monitoring platform for the ISS is Colorimetric Solid Phase Extraction (CSPE). CSPE is a sorption-spectrophotometric tecluiique that combines colorimetric reagents, solid-phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water samples. In CSPE, a syringe is used to meter a known volume of sample through an analysis cartridge that contains a membrane disk impregnated with an analyte-specific colorimetric reagent and any additives required to optimize the complexation of the reagent and analyte. As the sample is passed throu gh the analysis cartridge, analytes are selectively extracted and complexed on the membrane. Forination of the analyte- reagent complex causes a detectable change in the color of the membrane disk that is proportional to the analyte concentration. The analyte is then quantified by measuring the color of the membrane disk surface using a hand- held diffuse reflectance spectrophotometer (DRS). This entire process is illustrated in Fig. 1. To date, CSPE methods have been developed for a variety of analytes. Current methods include ionic silver, 1,2 4,5 total silver,' iodine and total iodine," nickel(II),M chromium(VI),' copper (II),' iron (III),' and formaldehyde.' These methods have all been tested extensively in a terrestrial environment to assess analytical performance and identify potential interferences. Additionally, several of the methods (silver, iodine, and total iodine) were successfully tested on a series of parabolic flights to assess their performance in microgravity. 2.9,10,11''2,13 Those microgravity experiments clearly demonstrated the potential for a CSPE based system to address some of the water quality monitoring requirements on the ISS. As a result, a Station Development Test Objective (SDTO) experiment was designed to evaluate the suitability of CSPE technology for routine use on the ISS. The experiment, SDTO #15012-U "Near Real-time Water Quality Monitoring Demonstration for ISS Biocides Using Colorimetric Solid Phase Extraction (CSPE)" was launched on STS-128/17A in August of 2009 and is currently deployed on the ISS. The following sections of this paper provide an overview of the SDTO experiment and describe the experiment hardware, the Colorimetric Water Quality Monitoring Kit (CWQMK), in detail. Also discussed are the certification process for the experiment hardware and initial results from deployment of the CWQMK on the ISS. IL Overview of SDTO Experiment A. Purpose The primary purpose of the SDTO experiment is to demonstrate the capability to collect in-flight water quality data on the ISS using CSPE technology. This will be accomplished by using the CWQMK hardware to measure ionic silver and molecular iodine concentrations in ISS water samples on-orbit. Secondary objectives of the experiment include evaluating the accuracy and reproducibility of the CSPE methods, assessing the long-term stability of the DRS and consumable items included in the kit (standard solutions and analysis cartridges), examining approaches to manually manipulate sample bags to isolate and collect bubble-free aliquots of samples, and utilizing downlinked data to verify the results of on-orbit analyses and facilitate real-time troubleshooting, if needed. B. Analytes Silver and iodine were selected as test analytes for the SDTO experiment because they are the biocides used in the potable water storage and distribution systems on the ISS. Biocides are added to the potable water systems on spacecraft to inhibit microbial growth. On the United States (US) segment of the ISS molecular iodine serves as the biocide, while the Russian space agency utilizes silver as a biocide in their systems. In both cases, the biocides must be maintained at a level sufficient to control bacterial growth, but low enough to avoid any negative effects on crew health. The presence of high levels of iodine in water can cause taste and odor issues that result in diminished water consumption. There are also concerns about potential impacts on thyroid function following exposure to high levels of iodine. Long term consumption of water containing high levels of silver may result in an irreversible blue-gray discoloration of the skin, a condition known as argyria. Ensuring biocides are maintained at safe, effective levels is one application that clearly illustrates the need to develop in-flight water quality monitoring systems to ensure the health and safety of spaceflight crews. In addition to illustrating the need to develop in-flight water quality monitoring systems, there is also an umnet requirement to perform in-flight iodine monitoring on the US segment of the ISS. The requirements for in-flight water quality assessment on the ISS are listed in the ISS Medical Operations Requirements Document (MORD). Section B of requirement 7.2.2.2 in the MORD contains the list of parameters that should be monitored in water 14 samples collected from the US segment. Based on reconunendations from the NASA Aerospace Medicine Board, iodine, iodide, and iodine compounds are included in that list. At present time, no flight-certified hardware exists American Institute of Aeronautics and Astronautics that is capable of measuring iodine, iodide, or iodine compounds in water samples on-orbit. Therefore, successful execution of the SDTO experiment will not only demonstrate the ability to collect in-flight water quality data with CSPE technology, it may also serve as the first step towards developing a system that will address an unmet MORD requirement C. Approach The capability to collect water quality data in-flight on the ISS will be demonstrated through a combination of in-flight analyses performed with the CWQMK hardware and experiments conducted on the ground. The SDTO experiment will consist of six in-flight analysis sessions. During each session, ground supplied standard solutions and water samples collected from different points on the ISS will be analyzed with the CWQMK hardware. Water samples will be analyzed in triplicate to assess the reproducibility of the CSPE methods. Samples will be collected from both the US and Russian segments of the ISS. In the US segment, samples will be collected from two different points; the US Potable Water Dispenser (PWD) dispensing needle and the PWD auxiliary port. Multiple sampling points are being utilized in the US segment because the MORD requires the total iodine concentration in potable water to be <0.2 mg/L at the point of consumption. Initially, samples for the SDTO experiment were only going to be collected from points of crew consumption. However, since the most of the iodine is removed from the US potable water before it reaches the PWD dispensing needle there were concerns that analysis of samples collected at the dispensing needle would not fully demonstrate the ability to measure iodine concentrations on the ISS with CSPE. To ensure that the objectives of the SDTO experiment were being met, the PWD auxiliary port was added as an additional sampling point. The PWD auxiliary port is upstream of the iodine removal hardware in the PWD, so theses water samples should contain the nonunal biocidal concentration of molecular iodine (1-4 mg/L). In the Russian segment, samples will be collected from the system for dispensing ground-supplied water (SVO-ZV). Samples from the US segment will be analyzed for molecular iodine and samples from the Russian segment will be analyzed for ionic silver. The unused portions of the water samples analyzed in each session will be temporarily stowed in the CWQMK until they can be returned to around for laboratory analysis. At the conclusion of the analysis session; data will be downloaded from the DRS onto the ISS network using an Excel spreadsheet. The data will then be downlinked from the ISS network and transferred to the project team on the ground. Ground experiments will be conducted in parallel with the in-flight analysis sessions to serve as a control for the in-flight analyses. The ground studies will be performed with the same standard solutions used in the kit and analysis cartridges that were prepared at the same time as those launched in the CWQMK. The standard solutions will be analyzed with standard laboratory methods to assess their stability. The analysis cartridges will be exposed to test solutions containing known concentrations of either molecular iodine or ionic silver. The iodine and silver concentrations obtained from the analysis cartridges will be compared to results from standard laboratory methods and percent recoveries will be calculated for each analyte. The ground experiments will be used to assess the stability of the standard solutions and analysis cartridges as well check for any degradation in performance that may occur as a result of exposure to launch environments and storage conditions on the ISS. The ultimate determination of the suitability of CSPE technology for routine use in a water quality monitoring system for the ISS will be based upon reproducibility of the measurements and agreement between the results from the in-flight analyses and the results from ground analyses performed on the unused portions of the samples. As described above, the unused portions of the water samples collected in support of the SDTO experiment will be stowed in the CWQMK until they can be returned to ground. Once returned, the unused samples will be analyzed with standard laboratory methods and the results will be used to evaluate the performance of the CWQMK. III. Hardivare Description The components of the CWQMK were launched in a 16" x 6" x 9" pouch made of natural Nomex fabric. The kit contains all the consumables and equipment required to analyze water samples for molecular iodine and ionic silver. Items provided in the CWQMK include two DRSs with attached sample locators (one primary, one spare), two data transfer cables, calibration standards for both DRS units, a staging/work pallet with iodine standard syringe and drying syringe, six monthly analysis packs, a water pack, and a spares pack. The only consumables from the ISS inventory needed to support the SDTO experiment are batteries (qty. = 8, AA alkaline) from the ISS battery pantry that are used to power the DRS units and the water that is collected for analysis (600 niL total). Additional details about the major components of the CWQMK and how they are used in the SDTO experiment are provided in the following sections. A picture of CWQMK S/N 1001 configured for flight is shown in Fig. 2. American Institute of Aeronautics and Astronautics A. Diffuse Reflectance Spectrophotometers The instruments used to measure molecular iodine and ionic silver concentrations during the CWQMK in-flight analysis sessions and the ground experiments are BYK-Gardner spectro-guide sphere (d/8° spin) diffuse reflectance spectrophotometers (Model 6839). These hand-held instruments are small, lightweight, battery operated, and collect spectral data over the visible range (400 nm - 700 mm) t with 10-nm resolution. They are simple to operate and collect data 1 rapidly; acquisition of a single reflectance spectrum requires only 2 1 sec. The instruments are also very rugged. They use LED light sources and require no optical alignment. The aperture of the ^^• ! instrument is 11-mm, which readily acconunodates the 13-nun diameter membrane disks loaded in the analysis cartridges. hmmmh^ The only differences between the DRSs used in the SDTO experiment and the connnercially available units sold by BYK- Figure 2. CWQMK S/N 1001 configured Gardner are the addition of a sample locator and modification of the for flight. instrument firmware. The sample locator was fabricated in-house and allows membrane disks to be positioned reproducibly at the instrument aperture. The instrument firmware was modified by the manufacturer to calculate analyte concentrations and provide direct readout of the concentrations on the instrument screen. Analyte concentrations are calculated using response functions that were determined experimentally. The response functions are based on the value of the Kubelka-Munk function at the wavelength of detection for each analyte. The Kubelka-Munk function is shown in Eq. 1, _ (1—R )2 F(R) (1) 2 where R is the relative reflectance of the membrane disk surface at a given wavelength. F(R) is directly related to the concentration of the complexed analyte, C, by Eq. 2,15 F(R) _ 2.303FC (2) where c is the absorptivity of the analyte-reagent complex and s is the scattering coefficient of the membrane surface. The experimentally derived response functions for molecular iodine and ionic silver are shown in Eqs. 3 and 4, respectively. rI ] _ F(R)44onm+0.0149 (3) L 2 0.2393 r +l _ —0.1394+ 0.13942—(4x0.0367 x(0.0011—F(R)5sonm)) A g J L 2x0.0367 ( ) The subscripts to F(R) in equations 3 and 4 denote the detection wavelengths for the analytes. B. Calibration Standards Calibration standards were included in the CWQMK to perform initial calibration of the DRSs detector response and run periodic calibration checks. The standards consist of a black standard, two white standards, and two green standards. The black standard is a felt lined cup that functions as a light trap. It is used to set 0% reflectance on the instruments. The white standards are painted metal coupons that approximate ideal diffuse reflectors. They are used to set 100% reflectance on the instruments. The green standards are painted metal coupons that are used to check the calibration of the DRSs. Green standards are used because the reflectance spectrum of the standards spans the entire spectral range of the instruments (400 nm - 700 nm). A single black standard was included in the CWQMK. American Institute of Aeronautics and Astronautics The black standard is universal and can be used with either DRS in the kit. The white and green standards are unique to each spectrophotometer, so separate sets of standards were required for each instrument. The white and green standards are unique to a given instrument because they are used by the manufacturer to establish the reference reflectance values that are used during the calibration check. The DRSs and the white and green standards flown in the CWQMK are serialized to ensure that the correct standards are used when calibrating or checking the calibration of the instruments in-flight. The black, white, and green standards are shown in Fig. 3. The initial calibration of the DRSs is part of the activation and check-out of the CWQMK hardware. After installing the batteries, the instruments will be powered on and calibrated with the black and white standards. As part of the calibration procedure, a calibration check is run immediately after calibrating the instrument. Figure 4 shows the green standard positioned at the aperture of the DRS for the calibrations check. During the calibration check, the relative reflectance values at each wavelength in the spectrum of the green standard are compared to the reference values loaded in the instrument's memory by the manufacturer. If the relative reflectance values are within the acceptable tolerances of the reference Figure 3. Calibration values the instrument is calibrated. standards included in the CWQMK. Black standard (A), white standard (B), and green standard (C). Once calibrated, the DRSs f should not need to be recalibrated for the duration of SarnPle Locator the SDTO experiment. The Green fi calibration of the DRS used to Slar,dard perform analyses will be Figure 4. Green standard positioned at the aperture of the DRS. checked at the beginning of each in-flight analysis session by analyzing the green standard. If the DRS is out of calibration, the calibration procedure will be repeated with the black and white standards before continuing the session. C. Staging/`Vork Pallet The staging/work pallet is a 7" x 81/z" rectangle of reinforced natural Nomex fabric that is used to organize the samples, standards, and consumables while conducting in-flight analyses with the CWQMK. The front side of the pallet contains pockets to hold the analysis cartridges and silver syringes and elastic straps to hold the sample bags, standard bags, waste bag, iodine syringes, and drying syringe. Velcro squares are stitched onto the backside of the pallet so that it can be affixed to the interior surfaces of the ISS in a position that is convenient for the crew member. Two items are permanently stowed on the staging/work pallet, the iodine standard syringe and the drying syringe. The iodine standard syringe is a 10 mL, glass-barrel syringe (SGE Analytical Science, P/N 008962) that is covered with transparent heat shrink tubing. The heat shrink tubing is used to prevent shards of glass from escaping into the ISS atmosphere in the event of the barrel breaking. The drying syringe is a 60 mL plastic syringe (Becton Dickinson, P/N 301035) that is used to remove residual water from the analysis cartridges and dry the membrane disks prior to analysis. These two items are stored on the staging/work pallet because they are reused Figure >. Staging/work pallet during each analysis session. All other items are either consumed during the populated for analysis. analysis session or removed at the conclusion of the session and either discarded or stowed elsewhere in the CWQMK. A photo of the staging/work pallet populated to conduct analyses is shown in Fig. 5. American Institute of Aeronautics and Astronautics D. Monthly Analysis Packs Six monthly analysis packs are provided in the CWQMK. The monthly analysis packs are 12" x 6" Ziploc bags that contain the consumables used to perform in-flight silver and iodine measurements. Each pack includes silver syringes, an iodine sample syringe, a waste bag, and silver and iodine cartridge pack assemblies. Two silver syringes are included in each monthly analysis pack: one standard syringe and one sample syringe. These syringes are 1 mL plastic syringes (Henke-Sass, Wolfe P/N 4010-200VD) that are discarded after analyses are complete. The iodine sample syringe is identical to the iodine standard syringe described above. The iodine sample syringe is also discarded at the end of each analysis session. The waste bag is a 2-port, 1 L Teflon bag (American Fluoroseal, P/N 2PF-0270) that is fitted with a reflux valve (B-Braun, P/N 415068) and tethered cap (Qosina, P/N 65455) on one of the ports. The second port is fitted with a plug that is supplied by the manufacturer and held in place with heat- shrink tubing. The waste bag is used to collect the effluent from the analysis cartridges during analyses. The silver and iodine cartridge pack assemblies contain the analysis cartridges used to perform silver and iodine analyses. Each cartridge pack assembly consists of 4 analysis cartridges (either silver or iodine) that are vacuum sealed in a pouch made of CadPack-P (Cadillac Products) laminate film. The analysis cartridges are loaded with membrane 16 disks that were prepared according to established procedures. Membrane disks in the silver analysis cartridges are treated with 5-(p-dimethylaminobenzylidene)rhodanine (DMABR) and polyoxyethylene (4) lauryl ether (Brij-30). Iodine sensitive membrane disks are treated with polyvinylpyrrolidone (PVP). At the conclusion of each analysis session, the Ziploc bag that contained the consumables is used as a trash container. All discarded items are placed in the Ziploc bag and it is discarded in the ISS trash. E. Water Pack The water pack is a 51/" x 9" x 2" soft goods pouch made of natural Nomex fabric. The pack is used to store empty sample bags, samples waiting to be analyzed, archive samples waiting to be returned to the ground, and the ground supplied standard solutions. A photo of the water pack is shown in Fig. 6. Empty silver and iodine sample bags are stored in the "Empty Sample Bags" pocket in the pack. Silver sample bags are 30 mL Teflon bags (American Fluoroseal, P/N 1PF-0030) that are fitted with the same reflux valves and tethered caps used on the waste bags. The iodine sample bags are 70 mL Teflon bags (American Fluoroseal, P/N 1PF-0071-CTRV) that come from the vendor with a reflux valve and tethered cap installed. Once the sample bags are filled, they are temporarily stowed under elastic straps in the water pack until they can be analyzed. Once analysis is complete, the sample bags with the unused portion of the Figure 6. Water pack opened shoe ing silver samples are stored in the "Archived Sample Bags" pocket of the and iodine standard solutions. water pack until they are returned to the ground. The ground supplied silver and iodine standard solutions are also stored in the water pack. These standard solutions serve as a control for the in-flight analysis sessions: they will be used to assess potential degradation of the analysis cartridges during storage on the ISS. A solution of silver fluoride containing 400 f 40 µg,1 of ionic silver is used as the silver standard. The iodine standard is a dilute solution of molecular iodine that contains 2.0 f 0.2 mg/L iodine as molecular iodine. Both standard solutions are stored in 2-port Teflon bags that are configured similar to the waste bag. One port is fitted with a reflux valve and tethered cap and the other port is fitted with a plug supplied by the manufacturer and held in place with heat-shrink tubing. The silver standard bag is a 55 mL, bag (American Fluoroseal, P/N 2PF-0055) that was filled with 50 f 5 mL of standard prior to launch. The iodine standard bag is a 150 mL, bag (American Fluoroseal, P/N 2PF-0150-K) that was filled with 150 f 15 mL, of iodine standard. F. Spares Pack A spares pack was included in the CWQMK for contingency situations. The pack is a 31/z" x 11/" x 6%/ soft goods pouch made of natural Nomex fabric that contains an extra set of consumables, extra sample bags, sampling adapters, a silver syringe, an iodine syringe, and a drying syringe. In the event that any of the items in the monthly analysis packs are damaged or either of the syringes stored on the staging/work pallet are inadvertently discarded, a replacement can be taken from the spares pack and the analysis session can be completed. American Institute of Aeronautics and Astronautics Sampling adapters for the US PWD and the SVO-ZV were included in the spares pack to simplify scheduling the CWQMK in-flight analysis sessions. Under normal circumstances, the water samples analyzed as part of the SDTO experiment will be collected during the routine monthly water sampling sessions using the adapters provided in the water sampling kit. While this minimizes the crew time associated with the SDTO experiment and reduces the overall mass of the CWQMK, it also adds constraints to scheduling the in-flight analysis sessions. Since samples must be collected prior to the analysis, the in-flight analysis sessions with the CWQMK must be scheduled after the monthly water sampling activity. If the monthly water sampling sessions are cancelled due to conflicts on crew timelines or issues with the ISS systems then no in-flight analysis session can be conducted. Providing sampling adapters in the spares pack allows the samples for the SDTO experiment to be collected independent of the nominal archive water samples and adds the capability to perform in-flight analysis sessions when monthly waster sampling sessions are cancelled. IV. Certification of the CWQMK The CWQMK is experimental hardware that was launched as a SDTO experiment for ISS. Typically, the only requirements levied against experimental hardware are those related to safety. After being reviewed by the Johnson Space Center (JSC) Safety Review Panel, it was determined that no new or unique hazards were associated with deployment of the CWQMK hardware on the ISS. As such, certification of the CWQMK for use on the ISS consisted of addressing the generic hazards listed in the ISS Fli ght Hardware Standardized Hazard Control Report. form # JSC 1366. y In addition to verifying that all safety requirements were met, the CWQMK hardware also underwent functional testing prior to delivery. There were two elements to the functional testin g: radiation susceptibility and performance validation. The radiation susceptibility test evaluated the impact of ionizing radiation on several of the CWQMK components. Performance validation testing was conducted to ensure that the DRSs and analysis cartridges launched in the CWQMK met the performance requirements established for the hardware. Additional details pertaining to the safety certification and functional testing of the CWQMK are provided in the following sections. A. Safety Certification As stated above, the safety certification of the CWQMK consisted of addressing the generic hazards listed in the ISS Flight Hardware Standardized Hazard Control Report, form # JSC 1366. There are 17 individual hazards listed in the report. 9 of which were deemed to be applicable to the CWQMK hardware. The applicable hazards were structural failure, sharp edges, shatterable material release, flammable materials, material off-gassing, non-ionizing radiation, battery failure, touch temperature, and pinch points. For 6 of the applicable hazards, verification of control was accomplished through analysis of the materials used to fabricate the hardware and inspection of the as- built hardware. Only the hazards associated with material off-gassing, non-ionizing radiation, and touch temperature required testing for verification of the hazard control. Off-gas testing of the CWQMK hardware was conducted at the White Sands Test Facility. The test focused on the unique components of the CWQMK that are not commonly used in the ISS environment. As such, no soft goods assemblies or packing foam were included in the test. Two separate off-gas tests were performed with the components of the kit. The first test was conducted with the DRS (including batteries), the calibration standards, and the data transfer cable. The second test was performed with the silver and iodine cartrid ge pack assemblies and the silver and iodine standard solutions. Both tests were conducted using standard test procedures. All components were tested for 72 hours at a temperature of 120° F (49° Q. In both tests, the Toxic Hazard Indices (T-values) for all detected compounds were well below acceptable levels for the ISS environment. 17'18 Non-ionizing radiation testing was performed in the Electromagnetic Interference (EMI) laboratory at the Johnson Space Center. This testing was focused on the electromagnetic emissions from the DRS when it is connected to a laptop computer, similar to the confi guration that will be used during data transfer on the ISS. During the test, the configuration exceeded the acceptable envssion limits at frequencies below 30 MHz, at 264.15 MHz, and at 312.2 MHz. The test results were reviewed by the ISS Electromagnetic Effects Panel and a Tailoring/Interpretation Agreement was prepared to address the exceedances. 19 The panel determined that none of the exceedances posed a concern for the ISS and no operational constraints were imposed on the CWQMK hardware. Exceedances below 30 MHz do not affect any ISS hardware because no ISS or visiting vehicle intentional receivers operate at frequencies that low. The higher frequency exceedances were also deemed to pose American Institute of Aeronautics and Astronautics minimal risk to ISS hardware. While 264.15 MHz is close to a downlink frequency used by the Shuttle vehicles, the emission from the DRS will be attenuated by the shielding of the ISS and the exceedance is not expected to interfere with Shuttle communications. Touch temperature testing was conducted in the flight hardware laboratories of the Wyle Integrated Science and Engineering Group. Testing verified that the DRS does not exceed the 113 °F (45 °C) touch temperature limit for continuous contact specified in the ISS Safety Requirements Document .20 As a result, no operational controls or hardware modification was required for operating the DRS on the ISS. B. Functional Testing The functional tests performed on the CWQMK hardware focused on assessing the susceptibility of the CWQMK components to ionizing radiation and evaluating the performance of the DRSs and analysis cartridges launched in the kit. Radiation susceptibility testing examined the impacts of ionizing radiation on the DRSs, analysis cartridges, and standard solutions. The performance evaluation was conducted to verify that the DRSs and analysis cartridges met performance requirements established for the CWQMK.21 Radiation susceptibility testing was performed at the Indiana University Cyclotron Facility in Bloomington, Indiana. A DRS, silver and iodine analysis cartridges; and silver and iodine standard solutions were irradiated with a proton beam to simulate the worst-case ionizing radiation environment on the ISS. The test articles were exposed to a proton beam with a minimum proton density of 1 x 1010 protons/cm2, which equates to a radiation dose of 600 rad. This is the standard radiation exposure used when testing hardware for use on the ISS. The susceptibility of the DRS to the radiation beam was examined by remotely connnanding the DRS to collect data while the instrument was being irradiated. Additionally, data stored in the instrument memory was periodically downloaded to a computer to check for corrupt data files. To assess the impact of the radiation dose on the analysis cartridges; irradiated analysis cartridges were exposed to solutions with known silver or iodine concentrations. The results obtained from the irradiated cartridges were then compared to results obtained with non-irradiated cartridges that had been exposed to the same solutions. The effect of the radiation dose on the standard solutions was evaluated by comparing silver and iodine concentrations measured by CSPE in the standard solutions before and after irradiation. Two main issues were observed with the DRS during the radiation susceptibility test. The first issue was corruption of data files that resulted from exposure to ionizing radiation. Potential corruption of the data files on the DRS was a known risk prior to the test. Data files are stored in static random access memory (RAM) on the instrument, which is known to be susceptible to ionizing radiation. In order to nutigate the risk, the instrument manufacturer modified the firmware on the DRS to store data in multiple memory locations, each data file is written in three distinct locations on the static RAM. An error checking and data recovery protocol was also added to the firmware that allows the instrument to detect corrupt data files and repair them by comparing the data values stored in the different memory locations. This mitigation strategy proved to be very effective; all corrupt data files that occurred as a result of irradiation were successfully detected and repaired by the instrument. The second issue was a lock up of the DRS that led to early termination of the test. The test plan called for the radiation beam to be focused on six different areas of the instrument. Irradiation of the first two areas on the instrument, on the back side of the display screen, resulted in corrupt data files (described above). When the focal point of the radiation beam was moved closer to the integrating sphere, the instrument froze and could not be recovered. At this point the test was terminated. The result from this test was very surprising because the operational code for the instrument is stored in a flash memory module. Previous testing performed on other flight hardware has shown that flash memory is very robust and is not affected by ionizing radiation. After discussing the test results with the instrument manufacturer, it was discovered that while the operating code for the DRS is stored in the flash memory, several variables used by the code are written to the static RAM. The manufacturer confirmed that corruption of these variables would cause an error that could cause the instrument to lock up. Fortunately, two reset functions were incorporated in the instrument firmware that allows these variables to be reset and makes it possible to recover from this type of error. The `soft' reset function resets the operating variables stored in the static RAM but leaves all other data intact. The `hard' reset function deletes all data stored in the static RAM then resets the operating variables to their default values. If either reset function is used, the instrument must be recalibrated before performing any analyses. Once the DRS was returned from the test facility, operation was successfully restored using the `soft' reset function. While the possibility for a radiation incident to lock up the DRS is not ideal, it should be noted that the test conditions represented a worst-case scenario for radiation exposure. The nonvnal American Institute of Aeronautics and Astronautics radiation levels on ISS are significantly lower than the test dose. Also, the risk of a radiation induced instrument lock up preventing data collection is sufficiently mitigated by the capability to restore operation using the reset functions and the fact that two DRSs are provided in the kit. Exposure of the analysis cartridges and standard solutions to the radiation beam had no observable effect on the performance of the analysis cartridges or the analyte concentrations in the standard solutions. Mean analyte concentrations (N=3) obtained from the irradiated analysis cartridges were within 15% of the pre-test value. The silver concentration in the standard solution following radiation exposure was within 15% of the pre-test value measured by CSPE. Iodine concentrations measured in the standard solution with CSPE before and after irradiation differed by less than 5%. The performance evaluation was conducted to verify that the DRSs and analysis cartridges in the CWQMK met the performance requirements listed in JSC-64149, Science Requirements Document for the Colorimetric Solid Phase Extraction (CSPE) Technology Demonstration. This document lists the top level science and performance requirements that must be met by the CWQMK hardware. It states that the CWQMK must provide the capability to measure ionic silver and molecular iodine in water samples collected on ISS. Analytical ranges for the two analytes are also specified in this document. The CWQMK hardware must be capable of measuring ionic silver in the range from 0.1 — 1.0 mg/L and molecular iodine in the range from 0.2 — 4.0 mg/L. In order to verify that these performance requirements are met by the CWQMK, tests were conducted with the DRSs that were launched in the flight kit and analysis cartridges prepared at the same time as those launched in the kit. During the test, analysis cartridges were exposed to solutions with known concentrations of either ionic silver or molecular iodine that spanned the required analytical range for each analyte. The cartridges were then analyzed with the flight DRSs to measure silver and iodine concentrations that were compared to reference concentrations by calculating a percent recovery for the analysis cartridges. The percent recovery was calculated by dividing the analyte concentration obtained with CSPE by the reference concentration measured with standard laboratory methods and multiplying by 100. Silver reference concentrations were measured using inductively coupled plasma mass spectrometry. Iodine reference concentrations were measured using the leuco-crystal violet spectrophotometric method. Results from this test are summarized in Table 1. The overall agreement between the silver and iodine concentrations measured by CSPE and the standard laboratory methods was excellent. The percent recoveries for silver ranged from 77 to 113.5 and the iodine recoveries ranged from 108.5 to 115.0. These data clearly demonstrate that the CWQMK hardware provides the capability to measure ionic silver and molecular iodine in the required analytical ranges. Table 1. Data from the performance evaluation of the DRS units and analysis cartridges. DRS S/N 1001 DRS S/N 1002 Mean Mean Reference concentration concentration Analyte concentration measured by % Recovery measured by % Recovery (rig/L) CSPE (mg/L), CSPE (mg/L), N=3 N=3 Silver 0.140 0.108 77.1 0.118 84.3 0.540 0.533 98.7 0.613 113.5 1.040 1.001 96.3 1.057 101.6 Iodine 0.20 0.22 110.0 0.22 110.0 1.93 2. 2 2 11.5.0 2.11 109.3 5.03 5.46 108.5 5.67 112.7 V. Initial Results To date, four of the six planned in-flight analysis sessions with the CWQMK have been completed. During the first three sessions, samples from the PWD dispensing needle and the SVO-ZV system were analyzed. The plan for the SDTO experiment was to alternate the sampling point in the US segment between the PWD dispensing needle and the PWD auxiliary port. However, due to delays preparing the procedure for sampling the PWD auxiliary port no samples could be collected from that point until the fourth analysis session. The first sample from the PWD auxiliary port was analyzed during the fourth session, along with another sample from the SVO-ZV system. Issues 10 American Institute of Aeronautics and Astronautics