Environmental Implications of Ionic Liquid and Deep Eutectic Solvent in Geothermal Application: Comparing Traditional and New Approach Methods
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Method of determining toxicities of chemicals involves recording and analysis of spider-web patterns. Based on observation spiders exposed to various chemicals spin webs that differ, in various ways, from normal webs. Potential alternative to toxicity testing on higher animals.
An apparatus and a method for rapidly determining chemical toxicity have been evaluated as an alternative to the rabbit eye initancy test (Draize). The toxicity monitor includes an automated scoring of how motile biological cells (Tetrahymena pyriformis) slow down or otherwise change their swimming patterns in a hostile chemical environment. The method, called the motility assay (MA), is tested for 30 s to determine the chemical toxicity in 20 aqueous samples containing trace organics and salts. With equal or better detection limits, results compare favorably to in vivo animal tests of eye irritancy.
Protocol to determine toxicities of chemicals implemented relatively cheaply by use of equipment and materials packaged in convenient kit form. Tests involve observation of macroscopic patterns formed at high concentrations of free-swimming protozoan species Tetrahymena pyriformis in liquid media. Provides more-sensitive indication of toxicity and costs less. Given that there are no data on toxicities of 70 to 80 percent of commercial chemicals, high cost of, and current opposition to, testing on higher animals, new protocol helps meet pressing need.
White Sands Test Facility Core Capabilities: a) Remote Hazardous Testing of Reactive, Explosive, and Toxic Materials and Fluids; b) Hypergolic Fluids Materials and Systems Testing; c) Oxygen Materials and System Testing; d) Hypervelocity Impact Testing; e)Flight Hardware Processing; and e) Propulsion Testing. There is no impact to any drinking water well. Includes public wells and the NASA supply well. There is no public exposure. Groundwater is several hundred feet below ground. No air or surface water exposure. Plume is moving very slowly to the west. Plume Front Treatment system will stop this westward movement. NASA performs on-going monitoring. More than 200 wells and zones are routinely sampled. Approx. 850 samples are obtained monthly and analyzed for over 300 different hazardous chemicals.
In this study, three different mineral acids were substituted for sulfuric acid (H2SO4) in the urine stabilizer solution to eliminate the excess of sulfate ions in pretreated urine and assess the impact on maximum water recovery to avoid precipitation of minerals during distillation. The study evaluated replacing 98% sulfuric acid with 85% phosphoric acid (H3PO4), 37% hydrochloric acid (HCl), or 70% nitric acid (HNO3). The effect of lowering the oxidizer concentration in the pretreatment formulation also was studied. This paper summarizes the test results, defines candidate formulations for further study, and specifies the injection masses required to stabilize urine and minimize the risk of mineral precipitation during distillation. In the first test with a brine ersatz acidified with different acids, the solubility of calcium in gypsum saturated solutions was measured. The solubility of gypsum was doubled in the brines acidified with the alternative acids compared to sulfuric acid. In a second series of tests, the alternative acid pretreatment concentrations were effective at preventing precipitation of gypsum and other minerals up to 85% water recovery from 95th-percentile pretreated, augmented urine. Based on test results, phosphoric acid is recommended as the safest alternative to sulfuric acid. It also is recommended that the injected mass concentration of chromium trioxide solution be reduced by 75% to minimize liquid resupply mass by about 50%, reduce toxicity of brines, and reduce the concentration of organic acids in distillate. The new stabilizer solution formulations and required doses to stabilize urine and prevent precipitation of minerals up to 85% water recovery are given. The formulations in this study were tested on a limited number of artificially augmented urine batches collected from employees at the Johnson Space Center (JSC). This study successfully demonstrated that the desired physical and chemical stability of pretreated urine and brines can be achieved using alternate pretreatment formulations under laboratory conditions. Additional testing and hazard assessments will be required to determine the feasibility of utilizing the proposed urine pretreatment formulations on ISS.
In the ever-changing paradigm of efficient and capable spacecraft design, scientific missions continue pushing the envelope enabling spacecraft subsystems to deliver effective solutions to meet challenging new mission/spacecraft needs. From an in-space storable liquid chemical propulsion perspective, monopropellant hydrazine has been, and continues to be, a dependable propellant with considerable flight heritage, a variety of engine thrust classes available from multiple vendors, with repeatable and reliable performance. Additionally, the space propulsion industry has learned to successfully handle hydrazine, its regulations, the safety protocols, the personnel protective equipment, and the unique training standards–all requisite for loading spacecraft propulsion systems with toxic hypergolic hydrazine. The question now arises as to “what is next for in-space chemical propulsion?” Further, with the evolution and concrete advancements in innovative in-space green propellant technologies, capable of providing realizable benefits to scientific missions, concern over the reliability and availability of this higher performing and safer to handle class of propellants is waning. As science missions move forward with the potential flight in fusion of High Performance Green Propulsion (HPGP), NASA and its industry partners are working to address any gaps in system reliability, performance, or unique operational considerations. Propellant technology that offers both higher performance and significant reduction in personnel hazards compared to hydrazine presents an attractive propulsion subsystem design opportunity. Increased propulsion subsystem performance can result in lower spacecraft launch mass, larger scientific payloads, or extended on-orbit lifetimes. Mission trades using green propulsion technologies have been documented on multiple NASA Goddard Space Flight Center (GSFC) mission classes, examining various parameters and requirements to support mission architectures in Low Earth Orbit (LEO), High Earth Orbit (HEO), geostationary, lunar, planetary, and Quasi-halo orbit around Sun-Earth Lagrange point (L2). The results of these trade studies show promising, attainable benefits. The perceived programmatic risk of flying a newer propulsion technology has, unfortunately, not outweighed the benefits to date. To take advantage of the improved performance and mitigate programmatic risk, HPGP engines must demonstrate life testing at higher propellant throughputs than have currently been demonstrated. In an effort to proactively address the challenges with technology infusion into a risk-averse community, NASA and the Swedish National Space Agency (SNSA) outlined a collaborative Implementing Arrangement (IA) for the respective agencies to pursue increased HPGP technology maturation. This initial IA effort began in 2013, fresh off the heels of the successful PRISMA HPGP technology demonstration mission. The IA targeted objective is to reduce risk to potential future HPGP missions and fully characterize the LMP-103S propellant and associated engine performance. Over the past eight years, HPGP has flown in propulsion systems on twenty-five(25) spacecraft from seven(7) different Launch Ranges around the globe and on seven (7) different Launch Vehicles. Six(6) of these launches involved multiple loading operations for multiple spacecraft. For U.S. Range operations, nine (9) HPGP systems have been processed at Vandenberg Space Force Base(VSFB):six(6) in 2017, and three (3) in 2018. Six (6) more have been processed at Cape Canaveral Air Force Station (CCAFS)in May 2020, with three (3) systems launched in June 2020 and the remaining three (3) system were left loaded and ready until their launch in August of 2020. Three (3) more systems have been processed at Wallops Flight Facility(WFF)and launched in June 2021. In addition, these propulsion subsystems employed heritage propulsion subsystem component such as valves, filters, and pressure transducers, and have further demonstrated nominal functionality in both diaphragm and Propellant Management Device (PDM) propellant tanks. Based on these successes, HPGP technology continues to be considered for NASA Science Mission Directorate missions at GSFC. The work presented herein represents many years of development and collaborative efforts to successfully align higher performance, low toxicity hydrazine alternatives into scientific missions. NASA GSFC Propulsion Engineering, in collaboration with Bradford ECAPS, has developed mission specific thruster design and testing requirements to establish GSFC’s desired test conditions and firing sequences.In2017, the first flight-like 22N HPGP thruster Engineering Qualification Model (EQM-1)was designed and built by Bradford ECAPS to prove out the thruster design, materials, build process, and test campaign with respect to NASA GSFC critical component and mission requirements. This test program was developed to comprehensively test the thruster, the technology, and ultimately increase the 22N HPGP Technology Readiness Level(TRL). EQM-1was tested to environmental qualification levels prior to hot fire performance testing to represent the relevant end-to-end environment (launch to on-orbit operation)with required margin. This thruster demonstrated steady-state and pulse mode operational capability with propellant thruster throughput up to~53kg.At this throughput level, the EQM-1 engine began to present off-nominal performance and the test campaign was halted to allow for non-destructive testing and identify the root cause for the an omalous performance. Capitalizing on the successful elements of the EQM-1 campaign, an upgraded 22N HPGP EQM-2 has been manufactured by Bradford ECAPS to meet the complete GSFC requirements. The EQM-2 thruster’s test campaign has further demonstrated the robustness of the HPGP propulsion technology and increased the Technology Readiness Level (TRL) by undergoing a full acceptance test program, then proceeding into qualification, including environmental testing (vibration and shock to qualification levels),as well as hot-fire life testing, operating at steady-state and pulse modes with increased propellant thruster throughput to~150kg. The HPGP thruster performance testing enables effective HPGP thruster readiness evaluation to meet NASA candidate mission requirements in the future.
The current NASA Space Shuttle auxiliary propulsion system utilizes nitrogen tetroxide (NTO) and monomethylhydrazine (MMH), hypergolic propellants. This use of these propellants has resulted in high levels of maintenance and precautions that contribute to costly launch operations. By employing alternate propellant combinations, those less toxic to humans, the hazards and time required between missions can be significantly reduced. Use of alternate propellants can thereby increase the efficiency and lower the cost in launch operations. In support of NASA's Space Launch Initiative (SLI), TRW proposed a three-phase project structured to significantly increase the technology readiness of a high-performance reaction control subsystem (RCS) thruster using non-toxic propellant for an operationally efficient and reusable auxiliary propulsion system (APS). The project enables the development of an integrated primary/vernier thruster capable of providing dual-thrust levels of both 1000-lbf class thrust and 25-lbf thrust. The intent of the project is to reduce the risk associated with the development of an improved RCS flight design that meets the primary NASA objectives of improved safety and reliability while reducing systems operations and maintenance costs. TRW proposed two non-toxic auxiliary propulsion engine designs, one using liquid oxygen and liquid hydrogen and the other using liquid oxygen and liquid ethanol, as candidates to meet the goals of reliability and affordability at the RCS level. Both of these propellant combinations offer the advantage of a safe environment for maintenance, while at the same time providing adequate to excellent performance for a conventional liquid propulsion systems. The key enabling technology incorporated in both TRW thrusters is the coaxial liquid on liquid pintle injector. This paper will concentrate on only the design and testing of one of the thrusters, the liquid oxygen (LOX) and liquid hydrogen (LH2) thruster. The LOX/LH2 thruster design includes a LOX-centered pintle injector, consisting of two rows of slots that create a radial spoke spray pattern in the combustion chamber. The main fuel injector creates a continuous sheet of LH2 originating upstream of the LOX pintle injector. The two propellants impinge at the pintle slots, where the resulting momentum ratio and spray pattern determines the combustion efficiency and thermal effects on the hardware. Another enabling technology used in the design of this thruster is fuel film cooling through a duct, lining the inner wall of the combustion chamber barrel section. The duct is also acts as a secondary fuel injection point. The variation in the amount of LH2 used for the duct allows for adjustments in the cooling capacity for the thruster. The Non-Toxic LOX-LH2 RCS Workhorse Thruster was tested at the NASA Marshall Space Flight Center's Test Stand 500. Hot-fire tests were conducted between March 08, 2002 and April 05, 2002. All testing during the program base period were performed at sea-level conditions. During the test program, 7 configurations were tested, including 2 combustion chambers, 3 LOX injector pintle tips, and 4 LH2 injector stroke settings. The operating conditions that were surveyed varied thrust levels, mixture ratio and LH2 duct cooling flow. The copper heat sink chamber was used for 16 burns, each burn lasting from 0.4 to 10 seconds, totaling 51.4 seconds, followed by Haynes chamber testing ranging from 0.9 to 120 seconds, totaling 300.9 seconds. The total accumulated burn time for the test program is 352.3 seconds. C* efficiency was calculated and found to be within expectable limits for most operating conditions. The temperature on the Haynes combustion chamber remained below established material limits, with the exception of one localized hot spot. The test results demonstrate that both the coaxial liquid-on-liquid pintle injector design and fuel duct concepts are viable for the intended application. The thruster head-e design maintained cryogenic injection temperatures while firing, which validates the concept for minimal heat soak back. By injecting fuel into the duct, the throat temperatures were manageable, yet the split of fuel through the cooling duct does not compromise the overall combustion efficiency, which indicates that, provided proper design refinement, such a concept can be applied to a high-performance version of the thruster. These hot fire tests demonstrate the robustness of the duct design concept and good capability to withstand off-nominal operating conditions without adversely impacting the thermal response of the engine, a key design feature for a cryogenic thruster.
Although Freon 21 has been assumed to be the coolant fluid for both the Space Shuttle Orbiter's primary heat rejection system and Spacelab's pallet heat transport loop, the fluid's supplier has considered stopping its production. This fact, together with the recent determination that maximum allowable toxicity levels must be reduced by a factor of 100, has prompted NASA's present investigation of a Freon 21 replacement which would provide comparable heat transport/rejection capability without requiring the redesign of existing hardware. Systems performance was analytically evaluated for many fluids, together with tests establishing material compatibility with alternate fluids and the character of any synergistic effects. Test results have indicated that Freon 114 is a viable alternative for some of the systems in question.
The use of non-toxic propellants in future exploration vehicles would enable safer, more cost effective mission scenarios. One promising "green" alternative to existing hypergols is liquid methane/liquid oxygen. To demonstrate performance and prove feasibility of this propellant combination, a 100lbf LO2/LCH4 engine was developed and tested under the NASA Propulsion and Cryogenic Advanced Development (PCAD) project. Since high ignition energy is a perceived drawback of this propellant combination, a test program was performed to explore ignition performance and reliability versus delivered spark energy. The sensitivity of ignition to spark timing and repetition rate was also examined. Three different exciter units were used with the engine s augmented (torch) igniter. Propellant temperature was also varied within the liquid range. Captured waveforms indicated spark behavior in hot fire conditions was inconsistent compared to the well-behaved dry sparks (in quiescent, room air). The escalating pressure and flow environment increases spark impedance and may at some point compromise an exciter s ability to deliver a spark. Reduced spark energies of these sparks result in more erratic ignitions and adversely affect ignition probability. The timing of the sparks relative to the pressure/flow conditions also impacted the probability of ignition. Sparks occurring early in the flow could trigger ignition with energies as low as 1-6mJ, though multiple, similarly timed sparks of 55-75mJ were required for reliable ignition. An optimum time interval for spark application and ignition coincided with propellant introduction to the igniter and engine. Shifts of ignition timing were manifested by changes in the characteristics of the resulting ignition.
The use of non-toxic propellants in future exploration vehicles would enable safer, more cost effective mission scenarios. One promising "green" alternative to existing hypergols is liquid methane/liquid oxygen. To demonstrate performance and prove feasibility of this propellant combination, a 100lbf LO2/LCH4 engine was developed and tested under the NASA Propulsion and Cryogenic Advanced Development (PCAD) project. Since high ignition energy is a perceived drawback of this propellant combination, a test program was performed to explore ignition performance and reliability versus delivered spark energy. The sensitivity of ignition to spark timing and repetition rate was also examined. Three different exciter units were used with the engine's augmented (torch) igniter. Propellant temperature was also varied within the liquid range. Captured waveforms indicated spark behavior in hot fire conditions was inconsistent compared to the well-behaved dry sparks (in quiescent, room air). The escalating pressure and flow environment increases spark impedance and may at some point compromise an exciter.s ability to deliver a spark. Reduced spark energies of these sparks result in more erratic ignitions and adversely affect ignition probability. The timing of the sparks relative to the pressure/flow conditions also impacted the probability of ignition. Sparks occurring early in the flow could trigger ignition with energies as low as 1-6mJ, though multiple, similarly timed sparks of 55-75mJ were required for reliable ignition. An optimum time interval for spark application and ignition coincided with propellant introduction to the igniter and engine. Shifts of ignition timing were manifested by changes in the characteristics of the resulting ignition.
Two recently invented families of conversion- coating processes have been found to be effective in reducing or preventing corrosion of aluminum alloys. These processes offer less-toxic alternatives to prior conversion-coating processes that are highly effective but have fallen out of favor because they generate chromate wastes, which are toxic and carcinogenic. Specimens subjected to these processes were found to perform well in standard salt-fog corrosion tests.
This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.
This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.
Improved method of assessing toxicities of various substances based on observation of effects of those substances on motilities of manageably small number of cells of protozoan species Tetrahema pyriformis. Provides repeatable, standardized tests with minimal handling by technicians and with minimal exposure of technicians to chemicals. Rapid and economical alternative to Draize test.
Alternative sandwich panel decorative films were investigated as replacements for the polyvinyl fluoride currently used in aircraft interiors. Candidate films were studied for flammability, smoke emission, toxic gas emission, flame spread, and suitability as a printing surface for the decorative acrylic ink system. Several of the candidate films tested were flame modified polyvinyl fluoride, polyvinylidene fluoride, polyimide, polyamide, polysulfone, polyphenylsulfone, polyethersulfone, polybenzimidazole, polycarbonate, polyparabanic acid, polyphosphazene, polyetheretherketon, and polyester. The films were evaluated as pure films only, films silk-screened with an acrylic ink, and films adhered to a phenolic fiberglass substrate. Films which exhibited the highest fire resistant properties included PEEK polyetheretherketon, Aramid polyamide, and ISO-BPE polyester.
Alternative sandwich panel decorative films were investigated as replacements for the polyvinyl fluoride currently used in aircraft interiors. Candidate films were studied for flammability, smoke emission, toxic gas emission, flame spread, and suitability as a printing surface for the decorative acrylic ink system. Several of the candidate films tested were flame modified polyvinyl fluoride, polyvinylidene fluoride, polyimide, polyamide, polysulfone, polyphenylsulfone, polyethersulfone, polybenzimidazole, polycarbonate, polyparabanic acid, polyphosphazene, polyetheretherketon, and polyester. The films were evaluated as pure films only, films silk-screened with an acrylic ink, and films adhered to a phenolic fiberglass substrate. Films which exhibited the highest fire resistant properties included PEEK polyetheretherketon, Aramid polyamide, and ISO-BPE polyester. Previously announced in STAR as N83-22320
This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and de-icing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP (the Dept. of Defense's (DoD's) Environmental Security Technology Certification Program) demonstration effort.The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kilograms. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow-on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft de-icing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization. Abstract for Appendix A. Toxicology Report: Corrosion controls a significant problem for military equipment. Many surface treatment materials currently in use on items of military or aerospace materiel contain chromium (VI) as a component, a source of significant human health and environmental hazard. The formulation under evaluation contains no chromium. Most of the proposed components are low to moderate toxicity and are not a significant concern. Two of the formulation components are associated with some cancer hazard - 2-mercaptobenzothiazole and formaldehyde, but both find widespread use in industry and additional investigation is not required for this project.