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Papermills in U.S. annually produce 3 million tons of sulfite waste liquor solids; other fractions of waste liquor are monomeric sugars and lignosulfonates in solution. Recovery of lignosulfonates involves precipitation and cross-linking of sulfonates to form useful solid ion-exchange resin. Contamination of sugars recovered from liquor is avoided by first converting them to ethanol, then removing ethanol by distillation.
Six of the seven chain isomers of six-carbon acyclic primary alpha-amino alkanoic acids (leucine isomers) have been either identified or confirmed in hot-water extracts of the Murchison meteorite using combined gas chromatography-mass spectrometry (GC-MS) and ion exchange chromatography. 2-Amino-2-ethylbutyric acid, 2-amino-2,3-dimethylbutyric acid, pseudoleucine, and 2-methylnorvaline were positively identified by GC-MS. These amino acids have not been previously reported to occur in natural materials and may be uniquely meteoritic in origin. The presence of leucine and isoleucine (including the diastereoisomer, alloisoleucine) was confirmed. Peaks corresponding to norleucine were seen by ion-exchange and gas chromatography but characteristic mass spectra were not obtained. The alpha-branched chain isomers in this series are quantitatively the most significant. These results are compared with literature data on amino acid synthesis by electrical discharge and Fischer-Tropsch-type catalysis. Neither model system produces an amino acid suite that is completely comparable to that found in the Murchison meteorite.
The Microbial Check Valve (MCV) is a flight qualified assembly that provides bacteriologically safe drinking water for the Space Shuttle. The 1-lb unit is basically a canister packed with an iodinated ion-exchange resin. The device is used to destroy organisms in a water stream as the water passes through it. It is equally effective for fluid flow in either direction and its primary method of disinfection is killing rather than filtering. The MCV was developed to disinfect the fuel cell water and to prevent back contamination of stored potable water on the Space Shuttle. This paper reports its potential for space applications beyond the basic Shuttle mission. Data are presented that indicate the MCV is suitable for use in advanced systems that NASA has under development for the reclamation of humidity condensate, wash water and human urine.
Thus far, organic analysis of carbonaceous chondrites has proven the only fruitful means of examining complex organic matter of extraterrestrial origin. The present paper presents the results of organic analysis of two Antarctic meteorites, Allan Hills (77306) and Yamato (74662), which may be considered free from terrestrial contamination. Ion-exchange chromatography, gas chromatography and mass spectrometery of meteorite samples reveal the presence in Yamato of 15 and in Allan Hills of 20 protein and nonprotein amino acids, the most abundant of which are glycine and alanine. Abundances of the D and L enantiomers of each amino acid are also found to be nearly equal. Data thus indicate an abiotic extraterrestrial origin for the matter, and confirm a lack of terrestrial contamination.
A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.
The Redox Storage System Technology Project was jointly supported by the U.S. Department of Energy and NASA. The objectives of the project were to develop the Redox flow battery concept and to probe its technical and economic viability. The iron and chromium redox couples were selected as the reactants. Membranes and electrodes were developed for the original mode of operating at 25 C with the reactants separated by an ion-exchange membrane. Analytical capabilities and system-level operating concepts were developed and verified in a 1-kW, 13-kWh preprototype system. A subsequent change was made in operating mode, going to 65 C and using mixed reactants. New membranes and a new electrode catalyst were developed, resulting in single cell operation as high as 80 mA/sq cm with energy efficiencies greater than 80 percent. Studies indicate a likely system cost of about $75/kWh. Standard Oil of Ohio (Sohio) has undertaken further development of the Redox system. An exclusive patent license was obtained from NASA by Sohio. Transfer of Redox technology to Sohio is supported by the NASA Technology Utilization Office.
The Cr(III) complexes present in the acidified chromium solutions used in the iron-chromium redox energy storage system have been isolated and identified as Cr(H2O)6(3+) and Cr(H2O)5Cl(2+) by ion-exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles have been followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations of the Cr(III) species calculated using Beer's law. During the charge mode, Cr(H2O)5Cl(2+) is reduced to Cr(H2O)5Cl(+), and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(2+). Electrode potential measurements also support this interpretation. Hysteresis effects in the charge-discharge curves can be explained by the slow attainment of equilibrium between Cr(H2O)6(3+) and Cr(H2O)5Cl(2+).
The overall energy conversion efficiency of a hydrogen-bromine energy storage system is highly dependent upon the characteristics and performance of the ion-exchange membrane utilized as a half-cell separator. The electrochemical performance and transport properties of a duPont Nafion membrane in an aqueous HBr-Br2 environment were investigated. Membrane conductivity data are presented as a function of HBr concentration and temperature for the determination of ohmic voltage losses across the membrane in an operational cell. Diffusion-controlled bromine permeation rates and permeabilities are presented as functions of solution composition and temperature. Relationships between the degree of membrane hydration and the membrane transport characteristics are discussed. The solution chemistry of an operational hydrogen-bromine cell undergoing charge from 45% HBr to 5% HBr is discussed, and, based upon the experimentally observed bromine permeation behavior, predicted cell coulombic losses due to bromine diffusion through the membrane are presented as a function of the cell state-of-charge.
A report on REE concentrations within the estuary of the Great Whale River in northwest Quebec and in Hudson Bay is given, showing concentrations which are less than those predicted by conservative mixing of seawater and river water, indicating removal of REE from solution. REE removal is rapid, occurring primarily at salinities less than 2 percent and ranges from about 70 percent for light REE to no more than 40 percent for heavy REE. At low salinity, Fe removal is essentially complete. The shape of Fe and REE vs. salinity profiles is not consistent with a simple model of destabilization and coagulation of Fe and REE-bearing colloidal material. A linear relationship between the activity of free ion REE(3+) and pH is consistent with a simple ion-exchange model for REE removal. Surface and subsurface samples of Hudson Bay seawater show high REE and La/Yb concentrations relative to average seawater, with the subsurface sample having a Nd concentration of 100 pmol/kg and an epsilon(Nd) of -29.3; characteristics consistent with river inputs of Hudson Bay. This indicates that rivers draining the Canadian Shield are a major source of nonradiogenic Nd and REE to the Atlantic Ocean.
An investigation of the returned Mars samples for biologically important organic compounds, with emphasis on amino acid, the puring and pyrimidine bases, and nucleosides is proposed. These studies would be conducted on subsurface samples obtained by drilling past the surface oxidizing layer with emphasis on samples containing the larges quantities of organic carbon as determined by the rover gas chromatographic mass spectrometer (GCMS). Extraction of these molecules from the returned samples will be performed using the hydrothermal extraction technique described by Cheng and Ponnamperuma. More rigorous extraction methods will be developed and evaluated. For analysis of the extract for free amino acids or amino acids present in a bound or peptidic form, aliquots will be analyzed by capillary GCMS both before and after hydrolysis with 6N hydrochloric acid. Establishment of the presence of amino acids would then lead to the next logical step which would be the use of chiral stationary gas chromatography phases to determine the enatiomeic composition of the amino acids present, and thus potentially establish their biotic or abiotic origin. Confirmational analyses for amino acids would include ion-exchange and reversed-phase liquid chromatographic analysis. For analyses of the returned Mars samples for nucleobases and nucleosides, affinity and reversed-phase liquid chromatography would be utilized. This technology coupled with scanning UV detection for identification, presents a powerful tool for nucleobase and nucleoside analysis. Mass spectrometric analysis of these compounds would confirm their presence in samples returned form Mars.
The development of a fuel cell energy storage system for the Space Station Extravehicular Mobility Unit (EMU) is discussed. The ion-exchange membrane fuel cell uses hydrogen stored as a metal hydride. Several features of the hydrogen-oxygen fuel cell are examined, including its construction, hydrogen storage, hydride recharge, water heat, water removal, and operational parameters.
The ability of iodine to control microbial contamination and biofilm formation in spacecraft water distribution systems is studied using two stainless steel water subsystems. One subsystem has an iodine level of 2.5 mg/L maintained by an iodinated ion-exchange resin. The other subsystem has no iodine added. Stainless steel coupons are removed from each system to monitor biofilm formation. Results from the first six months of operation indicate that 2.5 mg/L of iodine has limited the number of viable bacteria that can be recovered from the iodinated subsystem. Epifluorescence microscopy of the coupons taken from this subsystem, however, indicates some evidence of microbial colonization after 15 weeks of operation. Numerous bacteria have been continually removed from both the water samples and the coupons taken from the noniodinated subsystem after only 3 weeks of operation.
The initial tasks addressed by the Prairie View A&M University team were the conceptual design of a breathable-air manufacturing system, a means of drilling for underground water, and a method for storing water for future use. Subsequently, the design objective of the team for the 1987-1988 academic year was the conceptual design of an integrated system for the supply of quality water for biological consumption, farming, residential and industrial use. The source of water for these applications is assumed to be artesian or subsurface. The first step of the project was to establish design criteria and major assumptions. The second step of the effort was to generate a block diagram of the expected treatment system and assign tasks to individual students. The list of processes for water purification and wastewater treatment given above suggests that there will be a need for on-site chemicals manufacturing for ion-exchange regeneration and disinfection. The third step of the project was to establish a basis for the design capacity of the system. A total need of 10,000 gal/day was assumed to be required. It was also assumed that 30,000 gallon raw-water intake volume is needed to produce the desired effluent volume.
An NADH dehydrogenase obtained from an extremely halophilic bacterium was purified 570-fold by a combination of gel filtration, chromatography on hydroxyapatite, and ion-exchange chromatography on QAE-Sephadex. The purified enzyme appeared to be FAD-linked and bad an apparent molecular weight of 64000. Even though enzyme activity was stimulated by NaCl, considerable activity (430 % of the maximum activity observed in the presence of 2.5 M NaCl) was observed in the absence of added NaCl. The enzyme was unstable when incubated in solutions of low ionic strength. The presence of NADH enhanced the stability of the enzyme.
A methanol/air-oxygen fuel cell including an electrode formed by open-ended ion-exchange hollow fibers having a layer of catalyst deposited on the inner surface thereof and a first current collector in contact with the catalyst layer. A second current collector external of said fibers is provided which is immersed along with the hollow fiber electrode in an aqueous electrolyte body. Upon passage of air or oxygen through the hollow fiber electrode and introduction of methanol into the aqueous electrolyte, a steady current output is obtained. Two embodiments of the fuel cell are disclosed. In the first embodiment the second metal electrode is displaced away from the hollow fiber in the electrolyte body while in the second embodiment a spiral-wrap electrode is provided about the outer surface of the hollow fiber electrode.
Anion-exchange membranes (AEMs) with high anion/cation selectivity and exceptional proton-blocking ability are critical for applications such as bipolar membrane electrodialysis and electrochemical acid recovery. However, existing AEMs are constrained by a trade-off between ionic conductivity and selectivity, largely due to the intrinsic coupling between charge density and water content, and they suffer from excessive proton leakage facilitated by the Grotthuss hopping mechanism. In this work, poly(vinylimidazolium) membranes functionalized with long alkyl side chains that self-assemble into well-defined microphase-separated morphologies stabilized by hydrophobic and electrostatic interactions are reported. These unique structures localize the charge density along the polymer backbone to promote fast and selective ion transport. As a result, these membranes exhibit ionic conductivities and counter-ion diffusivities surpassing those of conventional homogeneous membranes, along with unprecedented counter-ion/co-ion selectivity and proton-blocking ability. These results establish a new design paradigm for high-performance, phase separated charged polymer membranes that overcome the limitations of homogeneous membranes, with broad implications for advanced electrochemical technologies.
Electrical resistivity tests can be used to evaluate the transport properties of concrete and provide a durability assessment. However, the electrical resistivity is largely dependent on the pore solution composition and recent work suggests that some aggregates have the capacity for cation uptake. This study first aims to provide further evidence for adsorption of cations on aggregate surfaces, without formation of reaction products (e.g. alkali-silica reaction). Secondly, hardened mortar samples were prepared using a fine aggregate with a high alkali affinity and a non-reactive fine aggregate as a control. The electrical resistivity of mortars was measured, and the pore solution of these mortars was obtained through high-pressure extraction. The effect of aggregate moisture dilution on the pore solution was decoupled by using a pore partitioning model. The results indicate that aggregate minerology can influence the pore solution composition through cation uptake. Specific minerals of minor quantity, like biotite, may be responsible for cation exchange. While adsorbed cations strongly affected pore solution and formation factor measurement, the bulk resistivity measurements on hardened mortar were only marginally influenced. Research on other implications of similar aggregate interactions with pore solutions are an intriguing area for future research.
Selective electrodialysis is attractive for recovering and recycling valuable ions. However, most studies in this field focus on membranes that are selective for monovalent ions. Multivalent cations preferentially partition into cation-exchange membranes, but low mobilities and concentration polarization limit electrodialysis selectivities for these cations. This work employs electrodialysis through an “in-series” combination of a Nafion membrane and a multilayer polyelectrolyte film (MPF)-coated Nafion membrane to concentrate and isolate La 3+ or Mg 2+ from monovalent ions. The bare Nafion membrane gives a La 3+ /Na + selectivity up to 4 (depending on conditions), which enables concentration of La 3+ with a high current efficiency. The MPF-coated membrane allows selective passage of Na + while rejecting La 3+ to increase the purity of the concentrated multivalent cation. For example, the concentration of La 3+ in the accumulation solution can reach 9 times its original concentration in the feed solution with a purity of 93 mol% (99 wt%) when starting with equimolar mixtures of NaNO 3 and La(NO 3 ) 3 . This study examines how the separation varies with the type of polyelectrolyte, the applied voltage, and the composition of feed, accumulation, and cathode solutions. Here, a high nitric acid concentration (0.5 M) in the cathode compartment allows monovalent anions to pass through the MPF-coated Nafion membrane to maintain the electroneutrality of the accumulation solution. With a low acid concentration (0.04 M) in the cathode chamber, water splitting occurs at the MPF-coated membrane and La(OH) 3 precipitates.