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At least 379 records · Page 21

Liquefying Lignins: Determining Phase-Transition Temperatures in the Presence of Aqueous Organic Solvents

Under appropriate conditions of temperature and solvent composition, single-phase aqueous organic solvents are capable of liquefying lignin to form a lignin-rich liquid phase separate from the solvent phase, creating liquid–liquid equilibrium. The extent to which this phenomenon occurs when Kraft lignin is combined with the solvents methanol, ethanol, isopropanol, and acetone was determined, with solid–liquid (SL) to liquid–liquid (LL) phase-transition temperatures being measured over the range of applicable organic–water compositions. Lignins tested from a variety of biomass sources were all discovered to form this liquid–liquid equilibrium with aqueous ethanol solutions. Furthermore, the formation of such phase behavior between lignin and economical, green solvents creates new opportunities for the large-scale purification and fractionation of raw bulk (i.e., technical) lignins.

09 BIOMASS FUELS↗

Solutocapillary Convection Effects on Polymeric Membrane Morphology

Macro voids are undesirable large pores in membranes used for purification. They form when membranes are cast as thin films on a smooth surface by evaporating solvent (acetone) from a polymer solution. There are two un-tested hypotheses explaining the growth of macro voids. One states that diffusion of the non-solvent (water) is solely responsible, while the other states that solutocapillary convection is the primary cause of macro void growth. Solutocapillary convection is flow-caused by a concentration induced surface-tension gradient. Macrovoid growth in the former hypothesis is gravity independent, while in the latter it is opposed by gravity. To distinguish between these two hypotheses, experiments were designed to cast membranes in zero-gravity. A semi-automated apparatus was designed and built for casting membranes during the 20 secs of zero-g time available in parabolic aircraft flight such as NASA's KC-135. The phase changes were monitored optically, and membrane morphology was evaluated by scanning electron microscopy (SEM). These studies appear to be the first quantitative studies of membrane casting in micro-gravity which incorporate real-time data acquisition. Morphological studies of membranes cast at 0, 1, and 1.8 g revealed the presence of numerous, sparse and no macrovoids respectively. These results are consistent with the predictions of the solutocapillary hypothesis of macrovoid growth.

Krantz, William B.↗

Pool Purification

Caribbean Clear, Inc. used NASA's silver ion technology as a basis for its automatic pool purifier. System offers alternative approach to conventional purification chemicals. Caribbean Clear's principal markets are swimming pool owners who want to eliminate chlorine and bromine. Purifiers in Caribbean Clear System are same silver ions used in Apollo System to kill bacteria, plus copper ions to kill algae. They produce spa or pool water that exceeds EPA Standards for drinking water.

Source record↗

Treatment of Spacecraft Wastewater Using a Hollow Fiber Membrane Biofilm Redox Control Reactor

The purpose of this project was to develop and evaluate design concepts for biological treatment reactors for the purification of spacecraft wastewater prior to reverse osmosis treatment. The motivating factor is that wastewater recovery represents the greatest single potential reduction in the resupply requirements for crewed space missions. Spacecraft wastewater composition was estimated from the characteristics of the three major component streams: urine/flush water, hygiene water, and atmospheric condensate. The key characteristics of composite spacecraft wastewater are a theoretical oxygen demand of 4519 mg/L, of which 65% is nitrogenous oxygen demand, in a volume of 11.5 liter/crew-day. The organic carbon to nitrogen ratio of composite wastewater is 0.86. Urine represents 93% of nitrogen and 49% of the organic carbon in the composite wastestream. Various bioreaction scenarios were evaluated to project stoichiometric oxygen demands and the ability of wastewater carbon to support denitrification. Ammonia nitrification to the nitrite oxidation state reduced the oxygen requirement and enabled wastewater carbon to provide nearly complete denitrification. A conceptual bioreactor design was established using hollow fiber membranes for bubbleless oxygen transfer in a gravity-free environment, in close spatial juxtaposition to a second interspaced hollow fiber array for supplying molecular hydrogen. Highly versatile redox control and an enhanced ability to engineer syntrophic associations are stated advantages. A prototype reactor was constructed using a microporous hollow fiber membrane module for aeration. Maintaining inlet gas pressure within 0.25 psi of the external water pressure resulted in bubble free operation with no water ingress into hollow fiber lumens. Recommendations include the design and operational testing of hollow fiber bioreactors using: 1) Partial nitrification/nitrite predenitrification; 2) Limited aeration for simultaneous nitrification/denitrification or for nitrite reduction/ammonia oxidation; 3) Hydrogenotrophic denitrification.

Smith, Daniel P.↗

Biochemical and spectroscopic characterizations of the oligomeric antenna of the coral symbiotic Symbiodiniaceae Fugacium kawagutii

Light-harvesting antennas in photosynthesis capture light energy and transfer it to the reaction centers (RCs) where photochemistry takes place. The sustainable growth of the reef-building corals relies on a constant supply of the photosynthates produced by the endosymbiotic dinoflagellate, belonging to the family of Symbiodiniaceae. The antenna system in this group consists of the water-soluble peridinin-chlorophyll $\textit{a}$-protein (PCP) and the intrinsic membrane chlorophyll $\textit{a}$-chlorophyll $c_2$-peridinin protein complex (acpPC). In this report, a nonameric acpPC is reported in a dinoflagellate, Fugasium kawagutii (formerly Symbiodinium kawagutii sp. CS-156). We found that extensive biochemical purification altered the oligomerization states of the initially isolated nonameric acpPC. The excitation energy transfer pathways in the acpPC nonamer and its variants were studied using time-resolved fluorescence and time-resolved absorption spectroscopic techniques at 77 K. Compared to the well-characterized trimeric acpPC, the nonameric acpPC contains an 11 nm red-shifted terminal energy emitter and substantially altered excited state lifetimes of Chl $\textit{a}$. The observed energetic overlap of the fluorescence terminal energy emitters with the absorption of RCs is hypothesized to enable efficient downhill excitation energy transfer. Additionally, the shortened Chl $\textit{a}$ fluorescence decay lifetime in the oligomeric acpPC indicate a protective self-relaxation strategy. We propose that the highly-oligomerized acpPC nonamer represents an intact functional unit in the Symbiodiniaceae thylakoid membrane. They perform efficient excitation energy transfer (to RCs), and are under manageable regulations in favor of photoprotection.

59 BASIC BIOLOGICAL SCIENCES↗

Contaminant Migration Modeling to Support the In Situ Decommissioning of Hardened Nuclear Facilities - 20215

The decommissioning of hardened nuclear facilities provides a unique challenge in balancing current worker dose with exposure to future receptors and media. In situ decommissioning (ISD) is a cost-effective and safe option for the closure of such facilities but requires a detailed understanding of the threat that radioactive and hazardous constituents remaining in the facilities pose to groundwater and surrounding surface water. The Savannah River Site (SRS) extensively employs contaminant migration models within the decommissioning process to develop site-specific removal, grouting, and monitoring strategies in support of safe and effective final end states of nuclear facilities. This work discusses the use of contaminant migration modeling in the ISD process at SRS, including specific examples from the closure of P-Reactor and R-Reactor, Building 235-F, F-Canyon and F/H Laboratory Complex. Migration models developed during the closure of P-Reactor and R-Reactor were divided into four source areas: the reactor vessel, the process area, the disassembly basin, and the purification wing. Each source area was assigned a specific inventory and migration pathway and was then subject to varying hypothetical removal, capping, and grouting schemes. Modeling indicated that groundwater Maximum Concentration Limits (MCLs) might be exceeded if no action was taken for eleven and ten constituents of concern (COCs) at P-Reactor and R-Reactor, respectively. These exceedances could occur in as few as 200 to 500 years. Alternatively, the migration modeling demonstrated that the selected ISD actions reduced contaminant mobility which allowed for significant radioactive decay and resulted in fewer predicted exceedances of groundwater MCLs (five COCs for P-Reactor; eight COCs for R-Reactor). In response to the modeling results for P-Reactor and R-Reactor, effectiveness monitoring programs were developed to target contaminants, specific to each reactor, that may migrate to groundwater. Contaminant migration modeling also revealed that roof collapse was a large factor in the release of COCs to the environment, giving rise to roof improvements, and an inspection and vegetation control program to ensure roof stability over time. Contaminant migration modeling is also aiding in the closure planning for hardened facilities in F Area. Building 235-F housed the Actinide Billet Line, which produced Np-237 billets for irradiation in SRS reactors, and the Plutonium Fuel Form (PuFF) facility that produced Pu-238 heat sources for the space program. As a result of these missions, areas within Building 235-F contain considerable residual amounts of both Pu-238 and Np-237. Contaminant migration modeling of Building 235-F was originally performed in 2012 to identify the feasibility of ISD and the amount of radioactive material removal required to prevent the exceedance of groundwater MCLs. The original model indicated that a 60% reduction in the PuFF facility Pu-238 inventory could keep groundwater concentrations below standards, while Np-237 did not pose a threat to groundwater. However, updates to the model with an emphasis on source impact pathways revealed that, due to the orientation of the source areas relative to groundwater flow, no amount of reasonable removal of Pu-238 would keep groundwater concentrations below MCLs and that Np-237 could be a large contributor to localized MCL exceedances. With this insight, the refined 2019 model is being used to assist in the development of grouting plans specific to each facility source area, where bentonite may be utilized to slow the migration of Pu-238 and its daughter products from the PuFF facility and a reducing grout may decrease Np-237 transport by ensuring the nuclide remains in the less mobile +IV oxidation state. The beginning phases of contaminant migration modeling are underway for F-Canyon and associated facilities using lessons learned from the Reactors and Building 235-F. A contaminant migration pathway, similar to the pathway used for the reactor vessels, is being developed for the hot and warm canyons. The F-Canyon inventories are being spatially refined to identify specific and localized source zones, comparable to Building 235-F, that may impact groundwater. Contaminant migration modeling provides vital input within the ISD process, from facility investigation to post closure effectiveness monitoring, making it a valuable tool in the development of safe and effective end states for hardened nuclear facilities at SRS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Developing an Efficient Cyanobacterial Sugar Production System

Researchers at the LBNL Advanced Biofuels Process Development Unit, in collaboration with Sandia National Laboratory and HelioBioSys, Inc., demonstrated pilot scale recovery and purification of polysaccharides produced by a unique marine cyanobacterial consortium. LBNL researchers tested new methods to quantify biomass and exopolysaccharide content during cultivation, and demonstrated separation of biomass and salt from polysaccharides at the 1,000L scale. Production of marine cyanobacterial polysaccharides from the consortium requires no fresh water, added carbon dioxide, or added nutrients, enabling use of marginal land and water resources for production of these unique biopolymers.

09 BIOMASS FUELS↗

Regenerable Incinerator Exhaust Purification and Trace Contaminant Control System

In this novel approach to air purification, contaminants removed from a process air stream by a high-capacity adsorbent are displaced periodically by a warm, high-humidity, reverse-flow air stream. Displaced contaminants flow into a closed regeneration loop, in which organic compounds are oxidized catalytically and acid gases are removed by a gas- water contactor (which also serves as the source of the water vapor). These features are expected to result in a design that has few expendables and lower energy consumption than alternative regenerable techniques. The joint project between NASA Ames Research Center and Vanderbilt University has completed its third year. Breadboard development continues at NASA Ames, while Vanderbilt has completed most of its adsorption equilibria development. Vanderbilt has completed its fixed-bed apparatus for investigation of dynamic adsorption and desorption processes for trace organic compounds and water vapor, and is continuing its development of the mathematical model describing the column dynamics.

Finn, John E.↗

Water-Based Coating Simplifies Circuit Board Manufacturing

The Structures and Materials Division at Glenn Research Center is devoted to developing advanced, high-temperature materials and processes for future aerospace propulsion and power generation systems. The Polymers Branch falls under this division, and it is involved in the development of high-performance materials, including polymers for high-temperature polymer matrix composites; nanocomposites for both high- and low-temperature applications; durable aerogels; purification and functionalization of carbon nanotubes and their use in composites; computational modeling of materials and biological systems and processes; and developing polymer-derived molecular sensors. Essentially, this branch creates high-performance materials to reduce the weight and boost performance of components for space missions and aircraft engine components. Under the leadership of chemical engineer, Dr. Michael Meador, the Polymers Branch boasts world-class laboratories, composite manufacturing facilities, testing stations, and some of the best scientists in the field.

Source record↗

Electrochemical Investigation of Moisture Byproducts in Molten Calcium Chloride

Residual water in molten CaCl 2 reacts to form different byproducts, such as HCl, which can impact the corrosivity of the salt and efficiency of electrochemical operations, such as electrolytic oxide reduction and electrorefining. The ability to detect and quantify these byproducts electrochemically can provide feedback on the efficacy of vacuum drying and other purification methods, as well as the impact of these byproducts on process operations. An electrochemical signal’s association with the production of H 2 is verified and characterized using cyclic voltammetry (CV) and residual gas analysis. CV estimated a 2-electron exchange process associated with H 2 production. CV detected trace quantities of an oxidized species containing hydrogen in the salt on the order of 10 ppm. Different salt handling methods were compared for their impact on the hydrogen electrochemical signal. It was found that 30 min of exposure of CaCl 2 in a beaker to low-humidity air (<20%) had minimal impact on the H 2 production signal.

Electrochemistry↗

Method Development for In Situ Microbiome Profiling of the Water Recovery System’s Wastewater Tank Onboard the International Space Station

A distinctive microbial community has inhabited the wastewater tank within the International Space Station Water Recovery System (WRS) for over 14 years and experienced the stressors associated with the microgravity environment. The WRS generates potable water for the crew from urine distillate, humidity condensate, Sabatier product water, and the occasional off-loading of ground-supplied water. The reservoir for these products, the wastewater tank, does not have a means of microbial control. While samples are occasionally collected for analysis, the time between sample collection and the return to Earth, as well as the lack of preservation, results in a skewed depiction of the microbiome. Routinely observed from these returned samples are high counts (105 – 106 colony forming units per mL) and two prevailing genera, Burkholderia and Ralstonia. The wastewater tank likely contains a more diverse microbiome, as a higher diversity of bacteria and fungus has been noted upstream and downstream of the tank. To characterize the microbial profile of the tank, analysis needs to occur at the time of sample collection. Toward this goal, a method for in situ analysis based on nanopore sequencing was developed. The filter-to-sequencer method evolved from previous work that has been validated onboard the ISS (BEST payload and the BioMole Crew Health Care Systems Facility). The method, including filtration, DNA extraction, purification, amplification, library preparation, and nanopore sequencing will be described. Additionally, data collected with this method from both ISS and terrestrial samples will be detailed. The consumables needed to support in situ analysis of the tank are set to the launch to the ISS in the spring of 2023. This investigation will allow for the first accurate characterization of the microbiome of the tank providing insight for crew health, planetary protection, and has the potential to enable engineering controls for future space station water systems.

Sarah Stahl-Rommel↗

Electrochemical Cycling of Liquid Organic Hydrogen Carriers as a Sustainable Approach for Hydrogen Storage and Transportation

Hydrogen (H 2 ), as a high-energy-density molecule, offers a clean solution to carry energy. However, the high diffusivity and low volumetric density of H 2 pose a challenge for long-term storage and transportation. Liquid organic hydrogen carriers (LOHCs) have been suggested as a strategic way to store and transport hydrogen in stable molecules. More so, electrochemical LOHC cycling renders an opportunity to utilize renewable energy for hydrogen storage and transportation toward the goal of eliminating carbon emissions. In this Perspective, examples of electrochemical reactions of organic molecules and their suitability for LOHC couples are examined. A comparative carbon footprint assessment of electrochemical LOHC cycling processes against thermochemical and hybrid LOHC cycling processes was performed. The electrochemical LOHC cycling process had the lowest relative carbon footprint only when highly concentrated LOHCs were used as the feed or when purification of the LOHC product was not required. The carbon footprint in electrochemical cycling of diluted LOHC was primarily contributed to by the LOHC distillation separation process. A sensitivity analysis showed the carbon footprint LOHC concentration dependence during the electrochemical cycling process. Moreover, the electrolyte composition significantly affects the carbon footprint during electrochemical LOHC cycling. Energy utilization, water usage, and toxicity for electrochemical LOHC cycling are discussed to provide an overview for better economic and environmental practices. There are significant opportunities in the electrochemical cycling of LOHCs if appropriate conditions such as high concentrations of reactant, reversible redox cycling ability, high Faradaic efficiencies, and catalyst stabilities are achieved.

25 ENERGY STORAGE↗

CO2 Acquisition Membrane (CAM)

The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport mechanisms. The Membrane Test Facility (MTF) has been developed to measure membrane permeance over a wide range of temperature and pressure. The facility uses two volume compartments separated by the membrane that are instrumented to measure temperature, delta pressure across the membrane, and gas composition. A thermal shroud supports and encloses the membrane, and provides temperature control. Methods were developed to determine membrane permeance using the first order decay of the pressure difference between the sealed compartments, using the total pressure for pure gases, and partial pressure of each species in gas mixtures. The technique provides an end-to-end measurement of gas permeance that includes concentration polarization effects. Experiments have shown that in addition to membrane permeance properties, the geometry and design of associated structures play an important role in how membrane systems will function on Mars.

Mason, Larry W.↗

Polymer-Derived Amorphous Aluminosilicate Nanomembranes for H 2 Purification

Aluminosilicate zeolite membranes with robust microporous crystalline structures are attractive for the molecular separation of H 2 from light gases, but their large-scale fabrication is complicated and costly, hindering their practical applications. Herein, we present polymer-derived amorphous aluminosilicate nanomembranes that combine the exceptional processability of polymers with the superior gas separation properties of aluminosilicates. Specifically, thin-film composite membranes comprising 150 nm polydimethylsiloxane were first treated with oxygen plasma to generate 10 nm polyorganosilica (POSi) on the surface, which were then subjected to few-cycle atomic layer deposition (ALD) using trimethylaluminum as a metal precursor and water vapor as a coreactant. This scalable two-step process yields few-nanometer amorphous aluminosilicates with strong size-sieving ability. For example, three-cycle ALD treatment of POSi increases H 2 /CO 2 selectivity from 39 to 200 and H 2 /CH 4 selectivity from 190 to 500, while decreasing H 2 permeance from 990 to 210 GPU at 150 °C, superior to the state-of-the-art membranes. In conclusion, rapid and scalable manufacturing of amorphous aluminosilicate nanolayers can also be of interest for catalysis and adsorption applications.

36 MATERIALS SCIENCE↗

Cost-efficient and Scalable Nitration of Cyanoacetic Acid with Potassium Nitrate in Methanesulfonic Acid Gives Pure 3,4-Dicyanofuroxan Following Modified Steam Distillation Methodologies

Two issues exist in the preparation of 3,4-dicyanofuroxan (1, DCFO) by a nitration of cyanoacetic acid (CAA) with 100% of HNO 3 in trifluoroacetic acid (TFA) or in H 2 SO 4 /CH 2 Cl 2 : (1) the cost of 100% of HNO 3 and (2) the isolation and purification of the product. In this paper, we report a cost-efficient nitration methodology by replacing 100% of HNO 3 with KNO 3 in methanesulfonic acid (MSA). The methodology includes adding KNO 3 and CAA portionwise to the solution of MSA at 45-50 ºC and keeping total nitrating time < 90 mins; purifying the product using our newly developed Water-Co-Distilling process or Modified Steam Distillation at atmosphere pressure. Here, the methodology, in general, provided DCFO in 50-60% of yield with >99% of purity as identified by NMR and GC-MS.

3,4-dicyanofuroxan↗

The effects of surface pretreatment and nitrogen tetroxide purification on the corrosion rate of Type 304L stainless steel

Corrosion rates of 304L stainless steel coupons in MON-1 oxidizer have been measured as a function of cleaning procedures employed, surface layer positions, propellant impurity levels, and short-term exposure durations (14 to 90 days). Of special interest was propellant contamination by buildup of soluble iron, which may cause flow decay. Surface treatments employed were combinations of cleaning, pickling, and passivation procedures. Propellants used were MIL-SPEC MON-1 and several types of purified NTO (i.e., low water, low chloride) which may, at a later time, be specified as spacecraft grade. Pretest coupon surface analysis by X-ray photoelectron spectroscopy (XPS-ESCA) has revealed important differences, for the different cleaning procedures, in the make-up of the surface layer, both in composition and state of chemical combination of the elements involved. Comparisons will be made of XPS/ESCA data, for different cleaning procedures, for specimens before and after propellant exposure.

Blue, G. D.↗

Methane Post-Processing and Hydrogen Separation for Spacecraft Oxygen Loop Closure

State-of-the-art life support oxygen recovery technology on the International Space Station is based on the Sabatier reaction where only about half of the oxygen required for the crew is recovered from metabolic carbon dioxide (CO2). The Sabatier reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by both the limited availability of reactant hydrogen from water electrolysis and Sabatier methane (CH4) being vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover this hydrogen has the potential to substantially increase oxygen recovery and thus dramatically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. A purification system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of acetylene removal systems and PPA system architectures are presented and discussed.

Greenwood, Zachary W.↗

A study of volatile contaminants in recovered water

The recovery and reuse of water during long term space flight is discussed. Particular attention was given to obtaining basic information on the volatile impurities in urine samples and in water recovered from urine by distillation. Data also cover laboratory distillation tests to determine the nature and extent of volatile constituents in the distillate and an evaluation of possible problems in distillation due to iodine used for control of microbial contamination. Efforts made to develop design criteria for distillation equipment to minimize the problems of volatile contaminants various methods which might be used for purification subsequent to recovery are included.

Mckee, H. C.↗