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At least 1,243 records · Page 69

Isolation and Physiological Characterization of Psychrophilic Denitrifying Bacteria from Permanently Cold Arctic Fjord Sediments (Svalbard, Norway)

A large proportion of reactive nitrogen loss from polar sediments is mediated by denitrification, but microorganisms mediating denitrification in polar environments remain poorly characterized. A combined approach of most-probable-number (MPN) enumeration, cultivation and physiological characterization was used to describe psychrophilic denitrifying bacterial communities in sediments of three Arctic fjords in Svalbard (Norway). A MPN assay showed the presence of 10(sup 3)−10(sup 6) cells of psychrophilic nitrate-respiring bacteria g(sup −1) of sediment. Fifteen strains within the Proteobacteria were isolated using a systematic enrichment approach with organic acids as electron donors and nitrate as an electron acceptor. Isolates belonged to five genera, including Shewanella, Pseudomonas, Psychromonas (Gammaproteobacteria), Arcobacter (Epsilonproteobacteria) and Herminiimonas (Betaproteobacteria). All isolates were denitrifiers, except Shewanella, which exhibited the capacity for dissimilatory nitrate reduction to ammonium (DNRA). Growth from 0 to 40 degC demonstrated that all genera except Shewanella were psychrophiles with optimal growth below 15 degC, and adaptation to low temperature was demonstrated as a shift from primarily C16:0 saturated fatty acids to C16:1 monounsaturated fatty acids at lower temperatures. This study provides the first targeted enrichment and characterization of psychrophilic denitrifying bacteria from polar sediments, and two genera, Arcobacter and Herminiimonas, are isolated for the first time from permanently cold marine sediments.

Psychrophile↗

Changes in the Ozone Chemical Regime Over the Contiguous United States Inferred By the Inversion of NOx and VOC Emissions Using Satellite Observation

To investigate changes in the ozone (O3) chemical production regime over the contiguous United States (CONUS) with accurate knowledge of concentrations of its precursors, we applied an inverse modeling technique with Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide (NO2) and total formaldehyde (HCHO) retrieval products in the summers of 2011, 2014, and 2017, years in which United States National Emission Inventory were based. The inclusion of dynamic chemical lateral boundary conditions and lightning-induced nitric oxide emissions significantly account for the contribution of background sources in the free troposphere. Satellite-constrained nitrogen oxide (NOx) and non-methane volatile organic compounds (NMVOCs) emissions mitigate the discrepancy between satellite and modeled columns: the inversion suggested 2.33-2.84 (1.07-1.34) times higher NOx over the CONUS (over urban regions) and 0.28-0.81 times fewer NMVOCs emissions over the southeastern United States. The model-derived HCHO/NO2 column ratio shows gradual spatial changes in the O3 production regime near urban cores relative to previously defined threshold values representing NOx and VOC sensitive conditions. We also found apparent shifts from the NOx-saturated regime to the transition regime (or the transition regime to the NOx-limited regime) over the major cities in the western United States. In contrast, rural areas, especially in the east-southeastern United States, exhibit a decreased HCHO/NO2 column ratio by -1.30 ± 1.71 with a reduction in HCHO column primarily driven by meteorology, becoming sensitive to VOC emissions. Results show that incorporating satellite observations into numerical modeling could help policymakers implement appropriate emission control policies for O3 pollution.

HCHO/NO2 factorInverse modelingOzone chemical regi↗

The Impact of Delayed Communication on NASA’s Human-Systems Operations: Preliminary Results of a Systematic Review

Throughout the history of human spaceflight, NASA has relied on a team of ground-based experts on Earth to manage its missions, vehicles, and crews to ensure crew safety and mission success. However, as missions progress beyond low-Earth orbit (LEO), this paradigm of dependence on ground must evolve. Beyond LEO, in missions to the moon and Mars, crews will confront new challenges: limited evacuation options, reduced resupply capabilities, and significant communication delays that impede real-time support from experts on the ground. This reduction in ground support amplifies the likelihood that crews will be unable to adequately respond to unanticipated, safety-critical events. Understanding the scope of these risks and identifying effective countermeasures hinges on understanding the impact of communication delays on complex operations, especially in urgent, unforeseen events. Real-time communication currently provides the crew with continuous access to a large, extensively resourced ground team skilled in anomaly resolution. However, as communication delays grow, the need to transfer some responsibilities from ground experts to onboard crew becomes evident. NASA has been exploring this shift in operational responsibilities and its effectiveness in managing complex operations for decades. Nevertheless, a comprehensive understanding of the specific challenges posed by communication delays and the necessary countermeasures to mitigate them remains a gap. In this paper, we present an update on our systematic review of the literature on communication delays, the first in-depth review since 2013 (Rader et al.). We introduce a coding taxonomy to capture key constructs from papers of interest and discuss preliminary findings. These preliminary results suggest two significant research gaps: limited studies have been conducted 1) with lunar-like latencies and 2) on problem-solving strategies for the maximum latencies expected in Mars missions. We outline plans and propose recommendations to address these gaps through ongoing and future research.

human-systems integration↗

The Impact of Delayed Communications on NASA's Human-Systems Operations: Preliminary Results of a Systematic Review

Throughout the history of human spaceflight, NASA has relied on a team of ground-based experts on Earth to manage its missions, vehicles, and crews to ensure crew safety and mission success. However, as missions progress beyond low-Earth orbit (LEO), this paradigm of dependence on ground must evolve. Beyond LEO, in missions to the moon and Mars, crews will confront new challenges: limited evacuation options, reduced resupply capabilities, and significant communication delays that impede real-time support from experts on the ground. This reduction in ground support amplifies the likelihood that crews will be unable to adequately respond to unanticipated, safety-critical events. Understanding the scope of these risks and identifying effective countermeasures hinges on understanding the impact of communication delays on complex operations, especially in urgent, unforeseen events. Real-time communication currently provides the crew with continuous access to a large, extensively resourced ground team skilled in anomaly resolution. However, as communication delays grow, the need to transfer some responsibilities from ground experts to onboard crew becomes evident. NASA has been exploring this shift in operational responsibilities and its effectiveness in managing complex operations for decades. Nevertheless, a comprehensive understanding of the specific challenges posed by communication delays and the necessary countermeasures to mitigate them remains a gap. In this paper, we present an update on our systematic review of the literature on communication delays, the first in-depth review since 2013 (Rader et al.). We introduce a coding taxonomy to capture key constructs from papers of interest and discuss preliminary findings. These preliminary results suggest two significant research gaps: limited studies have been conducted 1) with lunar-like latencies and 2) on problem-solving strategies for the maximum latencies expected in Mars missions. We outline plans and propose recommendations to address these gaps through ongoing and future research.

earth-independence↗

Vestibular adaptation to space in monkeys

Otolith-induced eye movements of rhesus monkeys were studied before and after the 1989 COSMOS 2044 and the 1992 to 1993 COSMOS 2229 flights. Two animals flew in each mission for approximately 2 weeks. After flight, spatial orientation of the angular vestibulo-ocular reflex was altered. In one animal the time constant of postrotatory nystagmus, which had been shortened by head tilts with regard to gravity before flight, was unaffected by the same head tilts after flight. In another animal, eye velocity, which tended to align with a gravitational axis before flight, moved toward a body axis after flight. This shift of orientation disappeared by 7 days after landing. After flight, the magnitude of compensatory ocular counter-rolling was reduced by about 70% in both dynamic and static tilts. Modulation in vergence in response to naso-occipital linear acceleration during off-vertical axis rotation was reduced by more than 50%. These changes persisted for 11 days after recovery. An up and down asymmetry of vertical nystagmus was diminished for 7 days. Gains of the semicircular canal-induced horizontal and vertical angular vestibulo-ocular reflexes were unaffected in both flights, but the gain of the roll angular vestibulo-ocular reflex was decreased. These data indicate that there are short- and long-term changes in otolith-induced eye movements after adaptation to microgravity. These experiments also demonstrate the unique value of the monkey as a model for studying effects of vestibular adaptation in space. Eye movements can be measured in three dimensions in response to controlled vestibular and visual stimulation, and the results are directly applicable to human beings. Studies in monkeys to determine how otolith afferent input and central processing is altered by adaptation to microgravity should be an essential component of future space-related research.

Cosmos 2229 Project↗

Contribution of Spaceflight Environmental Factors to Vision Risks

The risk of visual impairment and elevated intracranial pressure as a result of low-earth orbit microgravity exposure has directed our attention and research efforts to the eye. While the alterations observed in astronauts returning from long duration missions include vision and neuroanatomical changes observed by non-invasive methods, other effects and subsequent tissue responses at the molecular and cellular level can only be studied by accessing the tissue itself. As a result of this need, several studies are currently taking place within the Human and Health Countermeasures Element (HHC) that use animal models for eye research. The rodent eye has many similarities to the human eye, and both rats and mice have historically been used as models of human eye disease, aiding in the identification of the disease genes, elucidation of mechanisms of disease, as well as in the assessment of therapeutic treatments. These studies attempt to answer two central questions in the etiology of possible vision alterations in the environment of space exploration missions. The first is: what effects and response mechanisms take place in the different eye structures at the cellular and molecular level? The second question is directed to elucidate the contribution of the various environmental stressors (radiation, nutrition, fluid shift) to these effects. Collaborative approaches with internal and external investigators have allowed performing these studies in a most cost-effective fashion, providing preliminary data and laying the bases for testing further hypotheses in future and specifically designed animal experiments. From a study centered on the radioadaptive response in mice, we have learned that the retina responds to low and high dose gamma radiation by elevating antioxidant-related genes at early time points (4hrs) and that this response returns to control levels after 1 day post-irradiation. We are expanding this research with another collaborative study that investigates the combined effects of radiation exposure and iron overload on sensitivity to radiation injury in rat eyes. All main eye structures will be analyzed in this study: retina, lens and cornea. A study in collaboration with the Space Human Factors and Habitability Element (SHFH) investigates the effects of lunar dust exposure on the rat cornea. It is anticipated that common underlying oxidative stress mechanisms of damage may be observed as a result of these three stressors: radiation, nutritional iron and lunar dust. The contribution of fluid shift is addressed by a study using rats subjected to hindlimb suspension. The hypothesis to be tested in this study is that the mechanical stress imparted by the pressure differential across the optic disc and lamina cribosa will impact oxygenation (therefore causing oxidative stress and hypoxia) and cell survival. This study also includes the assessment of two nutritional antioxidant countermeasures: epigallocatechin gallate (green tea) and resveratrol. Finally, as a result of two successful tissue sharing efforts, we are proceeding with the analysis of eye samples of mice aboard two shuttle missions: STS-133 and STS-135. Results from the STS-133 study are presented in an independent abstract. Briefly, the results show that spaceflight represents a source of environmental stress that directly translates into oxidative and cellular stress in the retina. Similar analysis is also planned for the cornea. These samples add large value to our current vision research as they provide data on the direct effects of low-earth orbit spaceflight on eye structures and physiology.

Zanello, Susana B.↗

Hindlimb unloading induces a collagen isoform shift in the soleus muscle of the rat

To determine whether hindlimb unloading (HU) alters the extracellular matrix of skeletal muscle, male Sprague-Dawley rats were subjected to 0 (n = 11), 1 (n = 11), 14 (n = 13), or 28 (n = 11) days of unloading. Remodeling of the soleus and plantaris muscles was examined biochemically for collagen abundance via measurement of hydroxyproline, and the percentage of cross-sectional area of collagen was determined histologically with picrosirius red staining. Total hydroxyproline content in the soleus and plantaris muscles was unaltered by HU at any time point. However, the relative proportions of type I collagen in the soleus muscle decreased relative to control (Con) with 14 and 28 days HU (Con 68 +/- 5%; 14 days HU 53 +/- 4%; 28 days HU 53 +/- 7%). Correspondingly, type III collagen increased in soleus muscle with 14 and 28 days HU (Con 32 +/- 5%; 14 days HU 47 +/- 4%; 28 days HU 48 +/- 7%). The proportion of type I muscle fibers in soleus muscle was diminished with HU (Con 96 +/- 2%; 14 days HU 86 +/- 1%; 28 days HU 83 +/- 1%), and the proportion of hybrid type I/IIB fibers increased (Con 0%; 14 days HU 8 +/- 2%; 28 days HU 14 +/- 2%). HU had no effect on the proportion of type I and III collagen or muscle fiber composition in plantaris muscle. The data demonstrate that HU induces a shift in the relative proportion of collagen isoform (type I to III) in the antigravity soleus muscle, which occurs concomitantly with a slow-to-fast myofiber transformation.

Non-NASA Center↗

The timing of galvanic vestibular stimulation affects responses to platform translation

We compared the effects of galvanic vestibular stimulation applied at 0, 0.5, 1.5 and 2.5 s prior to a backward platform translation on postural responses. The effect of the galvanic stimulation was largest on the final equilibrium position of the center of pressure (CoP). The largest effects occurred for the 0.5 and 0-s pre-period, when the dynamic CoP pressure changes in response to both the galvanic stimulus and the platform translation coincided. The shift in the final equilibrium position was also larger than the sum of the shifts for the galvanic stimulus and the platform translation alone for the 0.5 and 0-s pre-periods. The initial rate of change of the CoP response to the platform translation was not significantly affected in any condition. Changes in the peak CoP position could be accounted for by local interaction of CoP velocity changes induced by the galvanic and translation responses alone, but the changes in final equilibrium position could only be accounted for by a change in global body orientation. These findings suggest that the contribution of vestibulospinal information is greatest during the dynamic phase of the postural response, and that the vestibular system contributes most to the later components of the postural response, particularly to the final equilibrium position. These findings suggest that a nonlinear interaction between the vestibular signal induced by the galvanic current and the sensory stimuli produced by the platform translation occurs when the two stimuli are presented within 1 s, during the dynamic phase of the postural response to the galvanic stimulus. When presented at greater separations in time, the stimuli appear to be treated as independent events, such that no interaction occurs. Copyright 1999 Elsevier Science B.V.

Non-NASA Center↗

Sky-wave backscatter - A means for observing our environment at great distances.

During the last five years, much progress has been made in the understanding of sky-wave backscatter. An explanation of the various interacting phenomena is presented, as is a review of the current state of knowledge reflecting recent advances in observational methods and analytic techniques. New narrow-beam antennas, coupled with signal modulations that permit fine resolution in time delay, are beginning to yield information concerning the character of the scatterers, which now can be separately discerned. These narrow beams also permit study of polarization fading from small regions, and this shows promise as a means for learning the distant sea state. Doppler shifts of a fraction of a hertz on signals of tens of megahertz are separable, permitting isolation of sea returns from ground returns by virtue of the Doppler effect resulting from sea-wave speed; this also suggests a potential sea-monitoring principle. Despite these advances, there is little practical application of sky-wave backscatter as a means of environmental monitoring. This lack is attributed to the large remaining gaps in our understanding of the echoes and our inability to interpret the forms of data that can be acquired with equipment of reasonable cost.

Croft, T. A.↗

Spectral parameter estimation of CAT radar echoes in the presence of fading clutter

The analysis technique and a part of the results obtained from CAT radar echoes from higher troposphere and lower stratosphere are presented. First, the effect of processing distortion caused by the periodogram method using FFT algorithm on the slowly fading ground clutter echo is discussed. It is shown that an extremely narrow clutter spectrum can spill over the entire frequency range if the data are truncated at a tie sorter than their correlation time affecting largely the estimation of the CAT spectrum contribution, especially when the latter is a few tens of dB weaker than the former. A nonlinear least squares fitting procedure is used to parameterize the observed power spectrum in terms of CAT echo power, Doppler shift, spectral width, and the parameters which specify the shape of the clutter component.

Sato, T.↗

Separation of time-averaged turbulence components by laser-induced fluorescence

A resonant Doppler velocimeter technique is introduced for time averaged gas flow turbulence fluctuation measurements. A monochrome laser beam is shone through a flow seeded with an atomic or molecular species that has an absorption frequency to which the laser is tuned. The resulting fluorescence is recorded by a detector, and the Doppler shift of the absorption frequency yields the velocity component of the flow in the direction of the beam. Static temperature and pressure data are available from the spectroscopic absoption line broadening. An analytical formulation of the laser-induced fluorescence intensity is defined and related to the velocity, temperature, and pressure. Comparison with data from a Na-seeded laminar supersonic jet demonstrates the accuracy of both the technique and model. Varying the pump laser frequency allows determination of the mean square velocity, temperature, and pressure fluctuations.

Cheng, S.↗

Horizons and Opportunities in Lunar Sample Science

The Moon is the cornerstone of planetary science. Lunar sample studies were fundamental in developing an understanding of the early evolution and continued development of planetary bodies, and have led to major revisions in understanding of processes for the accumulation of planetesimals and the formation of planets. Studies of lunar samples have increased an understanding of impact cratering, meteoroid and micrometeoroid fluxes, the interaction of planetary surfaces with radiations and particles, and even the history of the Sun. The lunar sample research program was especially productive, but by no means have all the important answers been determined; continued study of lunar samples will further illuminate the shadows of our knowledge about the solar system. Further, the treasures returned through the Apollo program provide information that is required for a return to the Moon, beginning with new exploration (Lunar Geoscience Observer (LGO)), followed by intensive study (new sample return missions), and eventually culminating in a lunar base and lunar resource utilization. The few years during and following Apollo were a hectic time for lunar science. Since then, considerable maturation of the science and distinct changes in the mode of operation have developed. Funding (and hence the number of investigators) has naturally declined. Studies have become far more problem-oriented than descriptive. Many sample investigators have shifted their sights away from planetary evolution, for which the Moon holds considerable information, toward processes and materials in the pre-planetary solar nebula, for which the Moon has no direct evidence. Nonetheless, unique scientific opportunities are still supplied by the samples returned from the Apollo and Luna missions and by lunar meteorites. These 382 kg of samples constitute a priceless resource that still has enormous scientific potential. Continued interaction between NASA and the scientific community, especially through the advice of groups such as the Lunar and Planetary Sample Team (LAPST), is essential in maintaining the current level of excellence of the program. LAPST has reviewed its role, the role of the sample research community, and the perceived role of future researchers over the next decade in ensuring the effective use of lunar sample studies in space exploration and exploitation. The review encompasses: (I) lunar sample science; (2) lunar materials applications; (3) lunar sample studies and their relation to future space missions; and (4) lunar sample curation. Plans in all four areas are summarized in this document.

Source record↗

Immune Response and Function: Exercise Conditioning Versus Bed-Rest and Spaceflight Deconditioning

Immune responses measured at rest immediately or some hours after exercise training (some with and some without increase in maximal oxygen uptake) gave variable and sometimes conflicting results; therefore, no general conclusions can be drawn. On the other hand, most immune responses were either unchanged (immunoglobulin, T cells, CD4+, and natural killer activity) or decreased (blood properdin, neutrophil phagocytic activity, salivary lysozymes, brain immunoglobulin A and G, and liver B lymphocytes and phytohemagglutinin activity) during prolonged bed rest. Some data suggested that exercise training during bed rest may partially ameliorate the decreased functioning of the immune system. Exercise and change in body position, especially during prolonged bed rest with plasma fluid shifts and diuresis, may induce a change in plasma protein concentration and content, which can influence drug metabolism as well as immune function. Leukocytosis, accompanied by lymphopenia and a depressed lymphocyte response, occurs in astronauts on return to Earth from spaceflight; recovery may depend on time of exposure to microgravity. It is clear that the effect of drugs and exercise used as countermeasures for microgravity deconditioning should be evaluated for their effect on an astronaut's immune system to assure optimal health and performance on long-duration space missions.

Greenleaf, J. E.↗

Far Ultraviolet Imaging from the Image Spacecraft: Wideband FUV Imaging - 2

The Far Ultraviolet Wideband Imaging Camera (WIC) complements the magnetospheric images taken by the IMAGE satellite instruments with simultaneous global maps of the terrestrial aurora. Thus, a primary requirement of WIC is to image the total intensity of the aurora in wavelength regions most representative of the aurora] source and least contaminated by dayglow, have sufficient field of view to cover the entire polar region from spacecraft apogee and have resolution that is Sufficient to resolve auroras on a scale of 1 to 2 latitude degrees, The instrument is sensitive in the spectral region from 140- 190 nm. The WIC is mounted on the rotating, IMAGE spacecraft viewing radially outward and has a field of view of 17 deg in the direction parallel to the spacecraft spin axis. Its field of view is 30 deg in the direction perpendicular to the spin axis, although only a 17 deg x 17 deg image of the Earth is recorded. The optics was an all-reflective, inverted Cassegrain Burch camera using concentric optics with a small convex primary and a large concave secondary mirror. The mirrors were coated by a special multi-layer coating, which has low reflectivity in the visible and near UV region, The detector consists of a MCP-Intensified CCD. The MCP is curved to accommodate the focal surface of the concentric optics. Tile phosphor of the image intensifier is deposited on a concave fiberoptic window, which is then Coupled to the CCD with a fiberoptic taper. The camera head operates in a fast frame transfer mode with the CCD being read approximately 30 full frames (512 by 256 pixel) per second with an exposure time of 0.033 s. The image motion (file to the satellite spin is minimal during such a short exposure. Each image is electronically distortion corrected using the look up table scheme. An offset is added to each memory address that is proportional to the image shift due to satellite rotation, and the charge signal is digitally summed in memory. On orbit, approximately 300 frames will be added to produce one WIC image in memory. The advantage of the electronic motion compensation and distortion correction is that it is extremely flexible, permitting several kinds of corrections including motions parallel and perpendicular to the predicted axis of rotation. File instrument was calibrated by applying ultraviolet light through a vacuum monochromator and measuring the absolute responsivity of the instrument. To obtain the data for the distortion look up table the camera was turned through various angles and the input angles corresponding to a pixel matrix were recorded. It was found that the spectral response peaked at 150 nm and fell off in either direction. The equivalent aperture of the camera, including mirror reflectivities and effective photocathode quantum efficiency, is about 0.04 sq cm. Thus, a 100 Rayleigh LBH aurora is expected to produce 23 equivalent counts per pixel per 10 s exposure at the peak of instrument response.

Mende, S. B.↗

A Historical Perspective on Dynamics Testing at the Langley Research Center

The history of structural dynamics testing research over the past four decades at the Langley Research Center of the National Aeronautics and Space Administration is reviewed. Beginning in the early sixties, Langley investigated several scale model and full-scale spacecraft including the NIMBUS and various concepts for Apollo and Viking landers. Langley engineers pioneered the use of scaled models to study the dynamics of launch vehicles including Saturn I, Saturn V, and Titan III. In the seventies, work emphasized the Space Shuttle and advanced test and data analysis methods. In the eighties, the possibility of delivering large structures to orbit by the Space Shuttle shifted focus towards understanding the interaction of flexible space structures with attitude control systems. Although Langley has maintained a tradition of laboratory-based research, some flight experiments were supported. This review emphasizes work that, in some way, advanced the state of knowledge at the time.

Horta, Lucas G.↗

Architecture and System Engineering Development Study of Space-Based Satellite Networks for NASA Missions

Traditional NASA missions, both near Earth and deep space, have been stovepipe in nature and point-to-point in architecture. Recently, NASA and others have conceptualized missions that required space-based networking. The notion of networks in space is a drastic shift in thinking and requires entirely new architectures, radio systems (antennas, modems, and media access), and possibly even new protocols. A full system engineering approach for some key mission architectures will occur that considers issues such as the science being performed, stationkeeping, antenna size, contact time, data rates, radio-link power requirements, media access techniques, and appropriate networking and transport protocols. This report highlights preliminary architecture concepts and key technologies that will be investigated.

Ivancic, William D.↗

Crew-Centered Operations: What HAL 9000 Should Have Been

To date, manned space flight has maintained the locus of control for the mission on the ground. Mission control performs tasks such as activity planning, system health management, resource allocation, and astronaut health monitoring. Future exploration missions require the locus of control to shift to on-board due light speed constraints and potential loss of communication. The lunar campaign must begin to utilize a shared control approach to validate and understand the limitations of the technology allowing astronauts to oversee and direct aspects of operation that require timely decision making. Crew-centered Operations require a system-level approach that integrates multiple technologies together to allow a crew-prime concept of operations. This paper will provide an overview of the driving mission requirements, highlighting the limitations of existing approaches to mission operations and identifying the critical technologies necessary to enable a crew-centered mode of operations. The paper will focus on the requirements, trade spaces, and concepts for fulfillment of this capability. The paper will provide a broad overview of relevant technologies including: Activity Planning and Scheduling; System Monitoring; Repair and Recovery; Crew Work Practices.

Korsmeyer, David J.↗

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

Zhang, Bo↗