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At least 37 records · Page 2

Ketene Formation in Interstellar Ices: A Laboratory Study

The formation of ketene (H2CCO, ethenone) in polar and apolar ices was studied with in situ 0.8 MeV proton irradiation, far-UVphotolysis, and infrared spectroscopic analyses at 10-20 K. Using isotopically enriched reagents, unequivocal evidencewas obtained for ketene synthesis in H2O-rich and CO2-rich ices, and several reaction products were identified. Results from scavenging experiments suggested that ketene was formed by free-radical pathways, as opposed to acid-base processes or redox reactions. Finally, we use our results to draw conclusions about the formation and stability of ketene in the interstellar medium.

molecules↗

Evolution of the Earth and Origin of Life: The Role of Gas/Fluid Interactions with Rocks

The work under the Cooperative Agreement will be centered on questions of the evolution of Life on the early Earth and possibly on Mars. It is still hotly debated whether the essential organic molecules were delivered to the early Earth from space (by comets, meteorites or interplanetary dust particles) or were generated in situ on Earth. Prior work that has shown that the matrix of igneous minerals is a medium in which progenitors of organic molecules assemble from H2O, C02 and N2 incorporated as minority "impurities" in minerals of igneous rocks during crystallization from H2O/CO2/N2-laden magmas. The underlying processes involve a redox. conversion whereby C, H, and N become chemically reduced, while 0 becomes oxidized to the peroxy state. During Year 02 the work will be divided into three tasks. Task 1: After carboxylic (fatty) acids and N-bearing compounds have been identified, other extractable organic molecules including lipids, oily substances and amino acids will be studied. Dedicated lipid analysis will be combined with gas chromatographic-mass spectroscopic (GCMS) analysis of organic compounds extracted from minerals and rocks. Task 2: Using infrared (IR) spectroscopy, C-H entities that are indicators for the organic progenitors in mineral matrices will be studied. A preliminary heating experiment with MgO single crystals has shown that the C-H entities can be pyrolyzed, causing the IR bands to disappear, but at room temperature the IR bands reappear in a matter of days to weeks. This work will be expanded, both by studying synthetic MgO crystals and olivine crystals from the Earth's upper mantle. The C-H bands will be compared to the published "organic" IR feature of dust in the interstellar medium (ISM) and interplanetary dust particles (IDP). Task 3: A paradox marks the evolution of early Life: Oxygen is highly toxic to primitive life, yet early organisms "learned" to detoxify reactive oxygen species, to utilize oxygen, and even produce it. Why would organisms on the early anaerobic Earth be under evolutionary pressure to evolve defenses against reactive oxygen species? Minerals in igneous rocks are now known to contain peroxy. When such minerals weather, the peroxy hydrolyzes to H2O2. The hypothesis will be tested whether organisms living in intimate contact with rock surfaces are subjected to a constant trickle of H202 and thus under stress to develop strategies to either detoxify the reactive oxygen species or repair the molecular damage that they cause. Understanding these processes is central to the Astrobiology mission. It opens new avenues toward understanding the evolution of early life on Earth, and the potential for aerobic life elsewhere. This Cooperative Agreement also has a strong educational and public outreach component involving high school, undergraduate students, and high school teachers.

Freund, Friedemann↗

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

The CheMin XRD instrument aboard Mars Science Laboratory (MSL) has documented clay minerals in various drill samples during its traverse of Gale Crater's floor and ascent of Mt. Sharp. The most recent samples, named Marimba, Quela and Sebina were acquired from the Murray Formation in the Murray Buttes region of lower Mt. Sharp. Marimba and Quela come from a approx. 30 m package of finely laminated lacustrine mudstones. Sebina comes from an overlying package of heterolithic mudstone-sandstones. Clay minerals make up approx.15-25 wt.% of the bulk rock with similar contributions to XRD patterns in all three samples. Broad basal reflections at approx. 10deg 2(theta) CoK(alpha) indicate the presence of 2:1 group clay minerals. The 02(lambda) clay mineral band lies at approx. 22.9deg 2(theta), a region typically occupied by Fe-bearing dioctahedral 2:1 clay minerals like nontronite or Fe-illite. The low humidity within the CheMin instrument, which is open to the martian atmosphere, promotes loss of interlayer H2O and collapse of smectite interlayers making them difficult to distinguish from illites. However, based on the low K content of the bulk samples, it appears that smectitic clay minerals are dominant. Peak dehydroxylation of the Marimba sample measured by the SAM instrument on MSL occurred at 610C and 780C. Fe-bearing smectites are not consistent with these dehydroxylation temperatures. Thus, we suggest that a mixture of dioctahedral and trioctahedral smectite phases are present giving the appearance of intermediate octahedral occupancy in XRD. Dioctahedral smectites have not previously been reported in Gale Crater by MSL. Earlier in the mission, relatively clay mineral rich samples (approx. 20 wt.%) from lacustrine mudstones in Yellowknife Bay (YKB) were found to contain ferrian saponites. It is proposed that YKB saponites formed via isochemical aqueous alteration of detrital olivine close to the time of sediment deposition, under anoxic to poorly oxidizing conditions. In terrestrial settings where alteration sequences of basaltic rocks or sediments are observed, first-stage alteration clay minerals are typically trioctahedral smectite species, as reported from YKB. In later alteration stages trioctahedral clay minerals are replaced by dioctahedral clays as a result of removal and/or oxidation of Fe2+ and Mg. Observed changes in clay mineralogy between YKB and Murray Buttes samples correspond with differences in bulk mineralogy, including: 1) a transition from magnetite to hematite as the main Fe-oxide, 2) increasing abundances of Ca-sulfates and 3) a reduction in the quantity of reactive mafic minerals. This mineralogical change indicates an increasing degree of aqueous alteration and oxidation of mafic detritus in the upper part of the Murray Formation. These results broaden the spectrum of mineralogical facies documented by MSL. Together sedimentology and mineralogy indicate a long-lasting, dynamic fluvial-lacustrine system encompassing a range aqueous geochemical processes under varying redox conditions. Future work is needed to unravel the influence of global and local controls on the range of ancient conditions observed at Gale Crater.

MSL↗

Oxychlorine Detections on Mars: Implications for Cl Cycling

The Sample Analysis at Mars (SAM) instrument has detected evolved O2 and HCl indicating the presence of perchlorate and/or chlorate (oxychlorine) in all 11 sediments analyzed to date. The hyperarid martian climate is believed to have allowed accumulation of oxychlorine and assumed chloride contents similar to those in hyperarid terrestrial settings. The linear correlation of oxychlorine and chloride of Gale Crater sediments is low (r (sup 2) equals 0.64). Correlations present in hyperarid Antarctica and the Atacama Desert are attributed to unaltered atmospheric source coupled with minimal redox cycling by biological activity. Terrestrial semi-arid to arid settings have low correlations similar to Gale Crater and are attributed to additional inputs of Cl minus from sea salt, dust, and/or proximal playa settings, and possible reduction of oxychlorine phases during wetter periods. While microbiological processes could contribute to low oxychlorine/chloride correlations on Mars, several abiotic mechanisms are more likely, such as changing oxychlorine production rates with time and/or post-depositional geochemical redox processes that altered the Gale Crater oxychlorine and chloride contents.

Sutter, B.↗

Stress-Activated Positive Holes (O− in a Matrix of O2–) Cause DNA Damage in Surface-Dwelling Organisms: Unveiling Mutation-Induced Secrets of Nature

Peroxy defects consist of pairs of tightly bonded oxygen anions in the –1 valence state such as in O3X/OO\YO3 with X, Y = Si4+, Al3+ etc. They commonly occur in igneous, metamorphic and many sedimentary rocks. When such rocks are stressed by tectonic forces, peroxy defects break up, releasing highly mobile electronic charge carriers: defect electrons in the O2– sublattice, i.e. unbound O–, known as “positive holes”, h•. The h• can flow out of stressed rock volumes, spreading far and wide, causing electric currents and electrochemical reactions. This study explores how the h• impact the electron flow in the electron transport chain (ETC) of organisms on the surface of rocks such as gabbro and granite. We found that, by forming hydroxyl radicals and superoxide anions, the h• disrupt the in vivo coordination of reduction-oxidation reactions that are essential for the timing of the redox cycle. Our observations show that stress activation of h• delays the sprouting of certain plant seeds and impedes the growth of yeast cultures, Saccharomyces cerevisiae. The h• induce mutations and affect plant development as evidenced by reduced stem length and leaf size. At the same time, the h• serve as a source of abiotic oxidation, capable of forming various organic compounds in situ. Through the generation of radical species that create new carbon-carbon bonds the h• facilitate the abiotic synthesis of hydrocarbons and other organic molecules essential to life, including porphyrins. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, revealing their significant role in influencing the growth and development of organisms in tectonically stressed crustal environments. Understanding these effects enhances our broader comprehension of redox biology and the influence of environmental factors on cellular development in natural settings.

astrobiology↗

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

Mittlefehldt, D. W.↗

Impact of Stress-Activated Positive Holes on the Redox Timing in Organisms Living at the Surface of Rocks: Unlocking Nature's Secrets

Squeezing and deforming igneous and/or high-grade metamorphic rocks activates electronic charge carriers known as positive holes, h•, that are defect electrons in the O2– sublattice. Similar to h• in semiconductors the h• in rocks affect electrical and thermal properties. They produce electrochemical reactions, localized electrical signals, and currents. In this study, we explore the effects of positive holes on the electron flow in the electron transport chain (ETC) of organisms living at the surface of rocks such as gabbro or granite. We found that positive holes, h•, disrupt the temporal coordination in vivo governed by oscillating reduction-oxidation reactions, known as the redox cycle. Positive holes affect the timing of the redox cycle by interacting with molecules in vivo, leading to the formation of superoxide anions and hydroxyl radicals. Thus, we observed that positive holes significantly impede the growth of yeast Saccharomyces cerevisiae (i.e., colony size) and delay the sprouting of broccoli and chia seeds. Additionally, positive holes were found to exert discernible impacts on plant development such as stem length and leaf size. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, shedding light on the potentially significant role of positive holes in influencing the growth and development of organisms in tectonically stressed rock environments. Understanding these effects has implications for a broader understanding of redox biology and of how environmental factors can influence cellular development in natural settings.

Redox Timing in Organisms↗

Impact of Stress-Activated Positive Holes on the Redox Timing in Organisms Living at the Surface of Rocks: Unlocking Nature's Secrets

Stressing and deforming igneous and/or high-grade metamorphic rocks activates electronic charge carriers known as positive holes, h•, that are defect electrons in the O2–sublattice, e.g. O-states. Like h•in semiconductors, the h•in rocks affect electrical and thermal properties. They produce electrochemical reactions, localized electrical signals, and currents. In this study, we explore the effects of positive holes on the electron flow in the electron transport chain (ETC) of organisms living at the surface of rocks such as gabbro or granite. We found that positive holes, h•, disrupt the in vivotemporal coordination governed by oscillating reduction-oxidation reactions, known as the redox cycle. Positive holes affect the timing of the redox cycle by interacting with essentialmolecules in vivo, leading to the formation of hydroxyl radicals and superoxide anions. We observed that positive holes significantly impede the growth of yeast Saccharomyces cerevisiae(i.e., colony size) and delay the sprouting of broccoli seeds. Additionally, positive holes were found to exert discernible impacts on plant development such as stem length and leaf size. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, shedding light on the potentially significant role of positive holes in influencing the growth and development of organisms in tectonically stressed crustal environments. Understanding these effects has implications for a broader understanding of redox biology and of how environmental factors can influence cellular development in natural settings.

hypermutation↗

Application of Fe Isotopes to the Search for Life and Habitable Planets

The relatively new field of Fe isotope geochemistry can make important contributions to tracing the geochemical cycling of Fe, which bears on issues such as metabolic processing of Fe, surface redox conditions, and development of planetary atmospheres and biospheres. It appears that Fe isotope fractionation in nature and the lab spans about 4 per mil (%) in Fe-56/Fe-54, and although this range is small, our new analytical methods produce a precision of +/- 0.05% on sample sizes as small as 100 ng (10(exp -7) g); this now provides us with a sufficient "signal-to-noise" ratio to make this isotope system useful. We review our work in three areas: 1) the terrestrial and lunar rock record, 2) experiments on inorganic fractionation, and 3) experiments involving biological processing of Fe. Additional information is contained in the original extended abstract.

Johnson, Clark M.↗

Natural sunlight-driven oxidation of Mn 2+ (aq) and heterogeneous formation of Mn oxides on hematite

The oxidation of dissolved Mn 2+ (aq) plays a critical role in driving manganese cycles and regulating the fate of essential elements and contaminants in environmental systems. Based on sluggish oxidation rate, abiotic processes have been considered less effective oxidation pathway for manganese oxidation in environmental systems. Interestingly, a recent study (Jung et al., 2021) has shown that the rapid photochemical oxidation of Mn 2+ (aq) could be a feasible scenario to uncover the potential significance of abiotic Mn 2+ (aq) oxidation. Nevertheless, the significance of photochemical oxidation of Mn 2+ (aq) under natural sunlight exposure remains unclear. Here, we demonstrate the rapid photocatalytic oxidation of Mn 2+ (aq) and the heterogeneous growth of tunnel-structured Mn oxides under simulated freshwater and seawater conditions in the presence of natural sunlight and hematite. The natural sunlight-driven photocatalytic oxidation of Mn 2+ (aq) by hematite showed kinetic constants of 1.02 h -−1 and 0.342 h −1 under freshwater and seawater conditions, respectively. The natural sunlight-driven photocatalytic oxidation rates are quite comparable to the results obtained from the previous laboratory test using artificial sunlight, which has ∼4.5 times stronger light intensity. It is likely because of ∼5.5 times larger light exposure area in the natural sunlight-driven photocatalytic oxidation than that of the laboratory test using artificial sunlight. We also elucidate the roles of cation species in controlling the oxidation rate of Mn 2+ (aq) and the crystalline structure of Mn oxide products. Specifically, in the presence of large amounts of cations, the oxidation rate of Mn 2+ (aq) was slower likely because of competitive adsorption. Furthermore, our findings highlight that Mn 2+ contributes significantly to the formation of large-tunneled Mn oxides. These results illuminate the importance of abiotic photocatalytic processes in controlling the redox chemistry of Mn in real environmental aqueous systems on the oxidation of Mn 2+ (aq), and provide an environmentally sustainable approach to effectively remediate water contaminated with Mn 2+ (aq) using natural sunlight.

Junyeong Choi↗

Competitive Oxidation and Hydration During Aqueous Alteration of Asteroids

Introduction: Studies of chondrites show that incorporation of H2O ice during formation of asteroids followed by radioactive heating caused partial oxidation and hydration of primary reduced and anhydrous rocks. Oxidation of kamacite, phosphides, troilite and organic polymers occurred through consumption of water s oxygen and release of H2. Hydration caused formation of serpentine, saponite, chlorite, talc and hydrated salts. Since H2O was the major reactant in oxidation and hydration, these processes could have been competitive. Redox reactions in asteroids should have been closely connected to hydration (dehydration) during aqueous alteration and thermal metamorphism. For example, dehydration and reduction release H2O that can be consumed in oxidation and hydration, respectively. We model asteroidal processes in order to quantify the fate of H2O and water s oxygen in major redox and hydration/dehydration reactions. Model: Equilibrium compositions in the gas-solid-liquid

Zolotov, M. Y.↗

Reaction of N2O5 with H2O on carbonaceous surfaces

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Brouwer, L.↗

An electromotive force series in a borosilicate glass-forming melt

An electromotive force series for redox couples was defined as a function of oxygen fugacity in a borosilicate melt at 1150 C. The resulting order of relative reduction potentials can be used to estimate the amounts of redox species in glass during processing. The electromotive force series in this melt is comparable to those in other silicate glass-forming melts and in aqueous systems but differs in detail because of interaction of the solvents with individual redox couples.

Schreiber, H. D.↗

A geostatistical analysis of small-scale spatial variability in bacterial abundance and community structure in salt marsh creek bank sediments

Small-scale variations in bacterial abundance and community structure were examined in salt marsh sediments from Virginia's eastern shore. Samples were collected at 5 cm intervals (horizontally) along a 50 cm elevation gradient, over a 215 cm horizontal transect. For each sample, bacterial abundance was determined using acridine orange direct counts and community structure was analyzed using randomly amplified polymorphic DNA fingerprinting of whole-community DNA extracts. A geostatistical analysis was used to determine the degree of spatial autocorrelation among the samples, for each variable and each direction (horizontal and vertical). The proportion of variance in bacterial abundance that could be accounted for by the spatial model was quite high (vertical: 60%, horizontal: 73%); significant autocorrelation was found among samples separated by 25 cm in the vertical direction and up to 115 cm horizontally. In contrast, most of the variability in community structure was not accounted for by simply considering the spatial separation of samples (vertical: 11%, horizontal: 22%), and must reflect variability from other parameters (e.g., variation at other spatial scales, experimental error, or environmental heterogeneity). Microbial community patch size based upon overall similarity in community structure varied between 17 cm (vertical) and 35 cm (horizontal). Overall, variability due to horizontal position (distance from the creek bank) was much smaller than that due to vertical position (elevation) for both community properties assayed. This suggests that processes more correlated with elevation (e.g., drainage and redox potential) vary at a smaller scale (therefore producing smaller patch sizes) than processes controlled by distance from the creek bank. c2002 Federation of European Microbiological Societies. Published by Elsevier Science B.V. All rights reserved.

Non-NASA Center↗

Transcriptomic Response of Drosophila Melanogaster Pupae Developed in Hypergravity

The metamorphosis of Drosophila is evolutionarily adapted to Earth's gravity, and is a tightly regulated process. Deviation from 1g to microgravity or hypergravity can influence metamorphosis, and alter associated gene expression. Understanding the relationship between an altered gravity environment and developmental processes is important for NASA's space travel goals. In the present study, 20 female and 20 male synchronized (Canton S, 2 to 3day old) flies were allowed to lay eggs while being maintained in a hypergravity environment (3g). Centrifugation was briefly stopped to discard the parent flies after 24hrs of egg laying, and then immediately continued until the eggs developed into P6-staged pupae (25 - 43 hours after pupation initiation). Post hypergravity exposure, P6-staged pupae were collected, total RNA was extracted using Qiagen RNeasy mini kits. We used RNA-Seq and qRT-PCR techniques to profile global transcriptomic changes in early pupae exposed to chronic hypergravity. During the pupal stage, Drosophila relies upon gravitational cues for proper development. Assessing gene expression changes in the pupa under altered gravity conditions helps highlight gravity dependent genetic pathways. A robust transcriptional response was observed in hypergravity-exposed pupae compared to controls, with 1,513 genes showing a significant (q < 0.05) difference in gene expression. Five major biological processes were affected: ion transport, redox homeostasis, immune response, proteolysis, and cuticle development. This outlines the underlying molecular changes occurring in Drosophila pupae in response to hypergravity.

RNASeq↗

Redox Interactions between Iron and Carbon in Planetary Mantles: Implications for Degassing and Melting Processes

Carbon stability in planetary mantles has been studied by numerous authors because it is thought to be the source of C-bearing atmospheres and of C-rich lavas observed at the planetary surface. In the Earth, carbonaceous peridotites and eclogites compositions have been experimentally studied at mantle conditions [1] [2] [3]. [4] showed that the fO2 variations observed in martian meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Based on thermodynamic calculations [4] and [5] inferred that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond), and equilibrium with melts would be a source of CO2 for the martian atmosphere. Considering the high content of iron in the Martian mantle (approx.18.0 wt% FeO; [6]), compared to Earth s mantle (8.0 wt% FeO; [7]) Fe/C redox interactions should be studied in more detail.

Martin, A.↗

Evidence for Multiple Diagenetic Episodes in Ancient Fluvial‐Lacustrine Sedimentary Rocks in Gale Crater, Mars

The Curiosity rover's exploration of rocks and soils in Gale crater has provided diverse geochemical and mineralogical data sets, underscoring the complex geological history of the region. We report the crystalline, clay mineral, and amorphous phase distributions of four Gale crater rocks from an 80‐m stratigraphic interval. The mineralogy of the four samples is strongly influenced by aqueous alteration processes, including variations in water chemistries, redox, pH, and temperature. Localized hydrothermal events are evidenced by gray hematite and maturation of amorphous SiO 2 to opal‐CT. Low‐temperature diagenetic events are associated with fluctuating lake levels, evaporative events, and ground water infiltration. Among all mudstones analyzed in Gale crater, the diversity in diagenetic processes is primarily captured by the mineralogy and X‐ray amorphous chemistry of the drilled rocks. Variations indicate a transition from magnetite to hematite and an increase in matrix‐associated sulfates suggesting intensifying influence from oxic, diagenetic fluids up section. Furthermore, diagenetic fluid pathways are shown to be strongly affected by unconformities and sedimentary transitions, as evidenced by the intensity of alteration inferred from the mineralogy of sediments sampled adjacent to stratigraphic contacts.

C N Achilles↗

Development of electrodes for the NASA iron/chromium

This program was directed primarily to the development of the negative (Cr3+/Cr2+) electrode for the NASA chromous/ferric Redox battery. The investigation of the effects of substrate processing and gold/lead catalyzation parameters on electrochemical performance were continued. In addition, the effects of reactant cross-mixing, acidity level, and temperature were examined for both Redox couples. Finally, the performance of optimized electrodes was tested in system hardware (1/3 square foot single cell). The major findings are discussed: (1) The recommended processing temperature for the carbon felt, as a substrate for the negative electrode, is 1650 to 1750 C, (2) The recommended gold catalyzation procedure is essentially the published NASA procedure (NASA TM-82724, Nov. 1981) based on deposition from aqueous methanol solution, with the imposition of a few controls such as temperature (25 C) and precatalyzation pH of the felt (7), (3) Experimental observations of the gold catalyzation process and subsequent electron microscopy indicate that the gold is deposited from the colloidal state, induced by contact of the solution with the carbon felt, (4) Electrodeposited lead appears to be present as a thin uniform layer over the entire surface of the carbon fibers, rather than an discrete particles, and (5) Cross-mixing of reactants (Fe-2+ in negative electrode solution or Cr-3+ in the positive electrode solution) did not appear to produce significant interference at either electrode.

Swette, L.↗