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Designing an Exploration Atmosphere Prebreathe Protocol

Extravehicular activities (EVAs) at remote locations must maximize limited resources such as oxygen (O2) and also minimize the risk of decompression sickness (DCS). A proposed remote denitrogenation (prebreathe) protocol requires astronauts to live in a mildly hypoxic atmosphere at 8.2 psia while periodically performing EVAs at 4.3 psia. Empirical data are required to confirm that the protocol meets the current accept requirements: less than or equal to 15% incidence of Type I DCS, less than or equal to 20% incidence of Grade IV venous gas emboli (VGE), both at 95% statistical confidence, with no Type II DCS symptom during the validation trial. METHODS: A repeated measures statistical design is proposed in which groups of 6 subjects with physical characteristics similar to active-duty astronauts would first become equilibrated to an 8.2 psia atmosphere in a hypobaric chamber containing 34% O2 and 66% N2, over 48 h, and then perform 4 simulated EVAs at 4.3 psia over the next 9 days. In the equilibration phase, subjects undergo a 3-h 100% O2 mask prebreathe prior to and during a 5-min ascent to 8.2 psia to prevent significant tissue N2 supersaturation on reaching 8.2 psia. Masks would be removed once 34% O2 is established at 8.2 psia, and subjects would then equilibrate to this atmosphere for 48 h. The hypoxia is equivalent to breathing air at 1,220 meters (4,000 ft) altitude, just as was experienced in the shuttle 10.2 psia - 26.5% O2 staged denitrogenation protocol and the current ISS campout denitrogenation protocol. For simulated EVAs, each subject dons a mask and breathes 85% O2 and 15% N2 during a 3-min depressurization to 6.0 psia, holds for 15 min, and then completes a 3-min depressurization to 4.3 psia. The simulated EVA period starts when 6.0 psia is reached and continues for a total of 240 min (222 min at 4.3 psia). During this time, subjects will follow a prescribed repetitive activity against loads in the upper and lower body with mean metabolic rate approaching 1500 BTU/hr [378 kcal/hr (O2 consumption about 1.3 l(sub STPD)/min)] in ambulatory subjects. Noninvasive Doppler ultrasound bubble monitoring for VGE in the pulmonary artery will be performed on subjects by 2 Doppler Technicians at about 15 min intervals while at 4.3 psia. At the end of this period, a 15-min repressurization returns all subjects back to 8.2 psia and the cycle is repeated 3 additional times with a day of rest between simulated EVAs. RESULTS: With an assumed 1.5% probability of DCS [P(DCS)] and accounting for within-subject correlation, running the proposed study with 20 subjects has a 95% probability of meeting the accept criterion for DCS. But if the true probability of DCS is 3.0%, then 30 subjects would be needed to achieve about the same probability to meet our accept criterion. These results assume a standard deviation of 1.4 for the between-subjects random component of P(DCS) on a logit scale, which was estimated from a previous study.

Conkin, Johnny↗

An Iron-Rain Model for Core Formation on Asteroid 4 Vesta

Asteroid 4 Vesta is differentiated into a crust, mantle, and core, as demonstrated by studies of the eucrite and diogenite meteorites and by data from NASA's Dawn spacecraft. Most models for the differentiation and thermal evolution of Vesta assume that the metal phase completely melts within 20 degrees of the eutectic temperature, well before the onset of silicate melting. In such a model, core formation initially happens by Darcy flow, but this is an inefficient process for liquid metal and solid silicate. However, the likely chemical composition of Vesta, similar to H chondrites with perhaps some CM or CV chondrite, has 13-16 weight percent S. For such compositions, metal-sulfide melting will not be complete until a temperature of at least 1350 degrees Centigrade. The silicate solidus for Vesta's composition is between 1100 and 1150 degrees Centigrade, and thus metal and silicate melting must have substantially overlapped in time on Vesta. In this chemically and physically more likely view of Vesta's evolution, metal sulfide drops will sink by Stokes flow through the partially molten silicate magma ocean in a process that can be envisioned as "iron rain". Measurements of eucrites show that moderately siderophile elements such as Ni, Mo, and W reached chemical equilibrium between the metal and silicate phases, which is an important test for any Vesta differentiation model. The equilibration time is a function of the initial metal grain size, which we take to be 25-45 microns based on recent measurements of H6 chondrites. For these sizes and reasonable silicate magma viscosities, equilibration occurs after a fall distance of just a few meters through the magma ocean. Although metal drops may grow in size by merger with other drops, which increases their settling velocities and decreases the total core formation time, the short equilibration distance ensures that the moderately siderophile elements will reach chemical equilibrium between metal and silicate before metal drop merger becomes important. In this model, there must be at least 30 percent melting of the silicate phase when metal melting is complete, corresponding to a crust thickness of at least 30 kilometers on Vesta, consistent with Dawn gravity observations. Greater degrees of silicate melting and a correspondingly thicker crust are possible if Vesta accreted sufficiently rapidly.

Kiefer, Walter S.↗

LongRunMIP - Motivation and Design for a Large Collection of Millennial-Length AO-GCM Simulations

LongRunMIP is the first collection of millennial-length simulations of complex coupled climate models and enables investigations of how these models equilibrate in response to radiative perturbations.We present a model intercomparison project, LongRunMIP, the first collection of millennial-length (1000+ year) simulations of complex coupled climate models with a representation of ocean, atmosphere, sea ice, and land surface, and their interactions. Standard model simulations are generally only a few hundred years long. However, modeling the long-term equilibration in response to radiative forcing perturbation is important for understanding many climate phenomena, such as the evolution of ocean circulation, time-and temperature-dependent feedbacks, and the differentiation of forced signal and internal variability. The aim of LongRunMIP is to facilitate research into these questions by serving as an archive for simulations that capture as much of this equilibration as possible. The only requirement to participate in LongRunMIP is to contribute a simulation with elevated, constant CO2 forcing that lasts at least 1000 years. LongRunMIP is a MIP of opportunity in that the simulations were mostly performed prior to the conception of the archive without an agreed-upon set of experiments. For most models, the archive contains a preindustrial control simulation and simulations with an idealized (typically abrupt) CO2 forcing. We collect 2D surface and top-of-atmosphere fields, and 3D ocean temperature and salinity fields. Here, we document the collection of simulations and discuss initial results, including the evolution of surface and deep ocean temperature and cloud radiative effects. As of summer 2019, the collection includes 50 simulations of 15 models by 10 modeling centers. The data of LongRunMIP are publicly available. We encourage submission of more simulations in the future.

Maria Rugenstein↗

Thermodynamic and Diffusion Model Estimates on Metamorphic Temperatures and Timescales for Basaltic Eucrite GRA 98098

Introduction: HED meteorites are thought to rep-resent igneous rocks from Vesta’s basaltic crust and preserve evidence of early crustal metamorphism. Determining the temperatures and timescales of thermal metamorphism is important for reconstructing crustal evolution in the early solar system. Here, we study basaltic eucrite Graves Nunataks (GRA) 98098, which has been identified as a highly metamorphosed eucrite [1]. We present new estimates on metamorphic temperatures determined via thermodynamic modeling as well as the initial results from diffusion models constraining timescales of thermal metamorphism. Sample Description: GRA 98098 is an unbrecciated eucrite with a granoblastic plagioclase and pyroxene mineralogy. Millimeter to cm-long lathes of tridymite cross-cut and poikilitically enclose plagioclase and pyroxene [1,this work]. Pyroxene grains have exsolved into Ca-rich (~Wo38En29Fs33) and Ca-poor (~Wo4.5En36Fs59.5) lamellae. Both unzoned and zoned plagioclase grains are observed. Unzoned plagioclase grains are found solely with tridymite laths. These grains have ~An92 compositions. The cores of the zoned plagioclase grains have the same composition and thin, relatively sodic rims (~An67), (Fig. 1). The bulk sample is unusually enriched in highly in-compatible elements and has one of the most fractionated REE patterns reported [1]. Maximum metamorphic temperatures of 985±78°C have been estimated using two-pyroxene thermometry [2]. Methods: Thermodynamic modeling. Thermodynamic models were constructed using the software Perple_X, which employs a Gibbs free energy minimization in order to determine the most stable phase assemblage for a given bulk rock composition [3]. Bulk composition was calculated using mineral com-positions acquired via EMPA (this study) and the observed abundancies present in the thin section. Two bulk compositions were estimated; 1) includes all phases present in the thin section, (assumes that all phases are present during metamorphism), 2) excludes tridymite from the bulk calculation (assumes that tridymite was not present during metamorphism). In order to determine whether metamorphic equilibria was achieved and estimate temperatures of metamorphism, we compared measured pyroxene compositions with thermodynamically predicted compositions [4, Fig. 2]. Diffusion Modeling. Several time-temperature de-pendent diffusion profiles were calculated in order to determine the best match for XAn chemical profiles observed at the edges of the zoned plagioclase (Fig. 3). We assumed that the start condition was a stepwise gradient at the plagioclase/pyroxene interface. We also assumed an average diffusion coefficient (D) and a constant temperature using the equation in [5]. D was determined for two temperatures (T = 1060ºC; near eucrite solidus [6] and T = 985ºC; metamorphism reported in [4]) and then XAn was calculated as a function of distance from plagioclase core to rim using an error function solution to Fick’s second law. Results: Thermodynamic model results are summarized in Fig. 2. For a bulk composition that includes all phases in the thin section, pyroxene endmember compositions plot in the following temperature ranges: Fs ~660-860ºC, En~1000ºC & 1150ºC, and Wo~760-900ºC (Fig. 2a). For a bulk composition that excludes tridymite from the peak metamorphic assemblage (i.e., the bulk composition minus the contribution from tridymite), a temperature range could not be determined for the Fs component of pyroxene. For Wo, T~760-900ºC and En, T~1000ºC & 1150ºC (Fig. 2b). Fig. 3 summarizes the diffusion model results. For T = 1060°C & 985°C, the most appropriate time interval was estimated based on which diffusion curve most matched (solid lines, Fig. 3) the EMPA data. For T = 1060°C, the best looking match was t = 500 ka. For T = 985°C, the best match was t = 7 Ma. Discussion and future work: Temperature estimates from thermodynamic models are not conclusive because the temperature ranges determined for pyroxene endmember stability do not overlap (colored fields in Fig. 2), thus implying that there is disequilibrium between pyroxene crystals and the bulk composition considered [4]. Thus, additional exploration is needed to define a metamorphically equilibrated do-main that accurately records peak temperature. The utility of defining metamorphically equilibrated do-mains to improve the accuracy and level of detail elucidated regarding the petrogenetic history of metamorphose samples has been demonstrated previously [4,7]. We suggest that in the case of Fig. 2a, the thin section composition is not representative of the length scales over which metamorphic equilibrium was achieve and in the case of Fig. 2b, the assumption that tridymite was not present during metamorphism was incorrect. However, results from thermodynamic models can provide insight into the relative timing of mineral and compositional textures. For example from texture alone, it is unclear whether tridymite was igneous in origin and represents the last bits of melt in a crystallizing magma chamber, or if it formed during (and possibly initiated) open system thermal metamorphism. The latter could be consistent with a partial melt hypothesis [8,9] while the former implies that simple fractional crystallization can yield the textures present in GRA 98098. The lack of coincidence be-tween pyroxene endmember compositions in Fig. 2b suggest that the bulk composition minus tridymite was not the assemblage in equilibrium with the pyroxene, suggesting that tridymite was present during metamorphism and formed during igneous crystallization. We conclude that the development of the Na-rich plagioclase rims likely occurred during or immediately after peak thermal metamorphism, because eucrites of similar metamorphic grade and texture have unzoned plagioclase (~An92) [2,4,8], and Na zoning is only observed in the plagioclase not included in the tridymite. This suggests that the zoning formed after tridymite formation, and therefore after igneous crystallization. Thus, the timescales calculated via diffusion modeling possibly represent the time interval over which thermal metamorphism occurred. Cooling rates approximated for the Vestan crust predict that the crust cooled below 300°C around 35-40 Ma after formation[10]. This is consistent with our modeling results that predict formation of the Na rich plagioclase rims occurring at higher temperatures over a period of 0.5 to 7 Ma years. Future work. Additional thermodynamic modeling work will focus on selecting an equilibrated bulk rock domain in which to elucidate metamorphic conditions. Diffusion models currently provide a minimum time-scale, since diffusion slows down as the system cools. Future work with will focus on integrating cooling into the diffusion models and constraining the depth at which thermal metamorphism occurs because it could be used to determine whether the range of time-scales calculated for thermal metamorphism are consistent with the geologic environment.

J S Gorce↗

Shock-tube measurements of rotational relaxation in hydrogen.

Density profiles in hydrogen shock waves have been measured with an electron beam densitometer for Mach numbers from 1.2 to 3.0. The translational and rotational relaxation processes were found to be uncoupled in the shock wave allowing for a simple determination of the relatively large (from approximately 270 to approximately 30) number of collisions required for equilibration of the rotational degrees of freedom over the temperature range from 410-1240 K. An intermediate relaxation point and subsequent increase in the number of collisions required above 600 K was attributed to the participation of additional excited rotational quantum levels in the equilibration process.

Boitnott, C. A.↗

Metamorphism of Apollo 14 breccias.

All Apollo 14 breccias for which thin sections are available (27 rocks) were studied petrographically. From one sample in each of six groups, electron microprobe analyses were performed on matrix (less than 25 microns) plagioclase, pyroxene, and olivine and of rims and cores of plagioclase and pyroxene clasts (50 to 300 microns). Matrix plagioclase, pyroxene, and olivine in the high-grade rocks display a narrow range of compositions, suggesting an equilibrated or metamorphic origin. However, in the low-grade rocks a wide range of compositions, suggesting a detrital or unequilibrated origin, is observed. Partially equilibrated states are observed in medium-grade samples. It is concluded that the Apollo 14 breccias formed as part of the Imbrium Basin ejecta blanket - the Fra Mauro formation. The continuous nature of the metamorphic series suggests that the medium- and high-grade breccias were derived from unmetamorphosed equivalents by autometamorphism in the thick, hot Fra Mauro formation at the Apollo 14 site.

Warner, J. L.↗

Gallium and germanium in the metal and silicates of L- and LL-chondrites.

Concentrations of Ga and Ge in the metal of 31 L-, 8 LL- and 2 H-chondrites, and in the silicates of 12 L- and LL-chondrites have been determined by spectrophotometric methods. The ranges of Ga contents in the metal of L- and LL-chondrites are 1.1 to 36.9 ppm and 1.0 to 34.1 ppm, respectively. The Ge content in the metal is positively correlated with Ga and ranges from 89.1 to 160 ppm and from 126 to 308 ppm for L- and LL-chondrites, respectively. The Ga content in the silicates of L-chondrites varies from 4.0 to 8.9 ppm. The Ga and Ge contents in the metal are clearly lower in unequilibrated than in equilibrated L- and LL-group chondrites. Unequilibrated and equilibrated chondrites are well separated in the plots of Ga vs Ge in the metal, and the L- and LL-groups are also well resolved. The Ga and Ge in the metal are well correlated with petrologic grade. This suggests that Ga and Ge variations in the metal are related to thermal metamorphism. There is evidence of an enrichment of Ga in the metal due to shock reheating.

Chou, C.-L.↗

Apollo 16 rocks - Classification and petrogenetic model

The Apollo 16 rocks include cataclastic anorthosites, two varieties of unequilibrated breccia, two varieties of partly to fully equilibrated breccia, and a sequence of partially melted breccias. The latter, which dominate the Apollo 16 collection, include glass, divitrified glass, mesostasis-olivine-plagioclase rock, mesostasis-rich basalt, basalt, and poikilitic rocks. All sequence members contain vesicles and relics of plagioclase, olivine, pink spinel, and lithic fragments. Their equilibrated matrices define a series from glass, to a plagioclase-olivine-mesostasis assemblage displaying spherulitic and skeletal shaped crystals, through a plagioclase-pyroxene-olivine assemblage displaying euhedral shaped crystals. Such data suggest that the sequence lithologies were derived from breccias or soils that were partially melted in an impact event.

Warner, J. L.↗

Melting behavior and phase relations of lunar samples

An attempt was made to show that feldspar would float during melting. Large anorthite crystals were placed beneath a silicate glass representative of liquid in which plagioclase accumulation is thought to have occurred. In less than 3 hours at 1,300 C, the crystals rose to the top in a Pt crucible 3 cm deep equilibrated in air and in a Mo crucible 1.5 cm deep equilibrated in an H2/CO2 gas stream of log PO2 = -10.9 (below Fe/FeO). These results suggest that lunar crustal formation by feldspar flotation is possible without special recourse to differential sinking of plagioclase versus mafic minerals or selective elutriation of plagioclase.

Hays, J. F.↗

Stability of chromium (III) sulfate in atmospheres containing oxygen and sulfur

The stability of chromium sulfate in the temperature range from 880 K to 1040 K was determined by employing a dynamic gas-solid equilibration technique. The solid chromium sulfate was equilibrated in a gas stream of controlled SO3 potential. Thermogravimetric and differential thermal analyses were used to follow the decomposition of chromium sulfate. X-ray diffraction analysis indicated that the decomposition product was crystalline Cr2O3 and that the mutual solubility between Cr2(SO4)3 and Cr2O3 was negligible. Over the temperature range investigated, the decomposition pressure were significantly high so that chromium sulfate is not expected to form on commercial alloys containing chromium when exposed to gaseous environments containing oxygen and sulfur (such as those encountered in coal gasification).

Jacob, K. T.↗

More on Rb-Sr in lunar breccia 14321

The reported Rb-Sr studies demonstrate a complex heterogeneity of lunar polymict breccia 14321 and exclude significant thermal metamorphism of 14321 in a hot ejecta blanket. While basalt clast 14321,371 is found to have an age of about 4.0 b.y., corresponding to the previously determined time of internal equilibration for another sample, the results for two microbreccia clasts from 14321,554 and 14321,220 indicate the lack of complete equilibration at that time. Light matrix samples are indistinguishable from the basalt with respect to K, Rb, and Sr, and, in contrast to the matrix from subsample 14321,184, the light matrix samples contain no appreciable KREEP-rich component.

Mark, R. K.↗

Metamorphism of brecciated ANT rocks - Anorthositic troctolite 72559 and norite 78527

Rake samples 72559 and 78527 are annealed rocks of ANT-suite mineralogy and bulk composition. The rocks were presumably derived from ancient lunar highland ANT rocks of cumulate origin. Sample 72559 is polymict and its precursors were anorthositic-troctolitic in composition. Sample 78527 is monomict and of noritic derivation. The precursors were brecciated due to impact processes; 72559 shows evidence of some impact melting. The samples were thermally metamorphosed forming rocks with granoblastic matrix textures. Coexisting matrix pyroxenes indicate equilibration temperatures of 950-1000 C for both rocks. Accessory opaque oxide minerals in the rocks show rather wide compositional variations. These probably primarily reflect compositional ranges inherited from the precursor/s with little integranular equilibration among them during metamorphism.

Nehru, C. E.↗

Relaxation to photochemical equilibrium of charged species within displaced air parcels in the D-region

The effects of the relaxation to photochemical equilibrium are investigated for the electrons and NO(+) ions in the upper D-region and for the electrons and several species of positive and negative ions present in the lower D-region. In the upper D-region the photochemical model includes electrons, nitric oxide, and NO(+). A self-consisting model of the equilibrium concentrations is developed for the lower D-region, which includes electrons, nitric oxide, O2(-), heavy negative and positive ions, and the oxygen species O, O3, and O2(1 delta g). At altitudes of 75 and 80 km the time dependence of the oxygen species has a significant effect on the equilibration of the electron and O2(-) concentrations. The relaxation to photochemical equilibrium proceeds by five e-folding time scales in the lower D-region, where the time required for final equilibration due to recombination is very long.

Hill, R. J.↗

Deuterium in carbonaceous chondrites

Hydrogen isotopic compositions in seven carbonaceous chondrites lie in the range -70 to +771 per thousand relative to standard mean ocean water. These values decrease, to a range from -145 to +219 per thousand, after low-temperature oxidation in an oxygen plasma. Deuterium enrichment is therefore concentrated in the organic matter, the hydrous silicates probably lying close to the terrestrial range for such material. Calculated values for delta D of the organic fraction are +450 per thousand for Orgueil and Ivuna and up to +1600 per thousand for Renazzo. These enrichments, at least for Orgueil and Ivuna, suggest equilibration with protosolar hydrogen at very low temperatures. Assuming a value of 2.5 x 10 to the -5th for the protosolar D/H ratio, nominal equilibration temperatures of 230 K for silicates and 180 K for organic matter may be derived.

Kolodny, Y.↗

Composition of the metal phases in ordinary chondrites - Implications regarding classification and metamorphism

The paper examines the composition of metal phases and metamorphism in ordinary chondrites. It is shown that below 550 C increasing Co decreases the equilibrium kamacite Ni concentration of an alpha to gamma system, and that the equilibrated L chondrites have kamacite and taenite Co concentrations in the L-group range. Metal-phase studies of petrologic type-3 ordinary chondrites with highly unequilibrated silicates showed a wide range in the degree of matrix kamacite equilibration; in the three most unequilibrated chondrites most taenite is clear, and the high Ni content shows that metamorphic temperatures were lower than 400 C in these meteorites.

Afiattalab, F.↗

Metamorphism of the H-group chondrites - Implications from compositional and textural trends in chondrules

The paper discusses element bulk compositions of 373 chondrules from 18 H3 to H6 chondrites determined by broad-beam electron probe analysis. Bulk chondrule FeO and Al2O3 amounts increase and TiO2 and Cr2O3 decrease with increasing petrologic type; normative faylite, albite, and plagioclase amounts increase through the petrologic sequence. Chondrule diameters correlate with phenocryst sizes in porphyritic chondrules of type 3 chondrites, but this correlation is diminished in the higher petrologic types. The compositional trends in chondrules through the petrologic sequence are attributed to diffusion and equilibration among chondrules, and between chondrules and matrix in response to increasing degrees of thermal metamorphism. It is suggested that H-group chondrites are formed by accretion of high-temperature (chondrules) and low-temperature (matrix) materials. Internal reheating of the parent materials to different temperatures caused compositional equilibration, grain coarsening, and reduction of FeO to Fe(0) by carbon.

Lux, G.↗

Alkaline electrochemical cells and method of making

Equilibrated cellulose ether membranes of increased electrolytic conductivity for use as separators in concentrated alkaline electrochemical cells are investigated. The method of making such membranes by equilibration to the degree desired in an aqueous alkali solution mantained at a temperature below about 10 C is described.

Hoyt, H. E.↗

Origin of volatile-rich H chondrites with light/dark structures

The light and dark fractions of four gas-rich, brecciated H chondrites are studied in terms of petrography and volatile element chemistry in an investigation of the origin of light/dark chondrites. Petrographic constraints on the nature of the light and dark fractions of the meteorites are presented. Light clasts within the brecciated H chondrites are more highly metamorphosed than dark host material, and olivine, pyroxene and metal compositions suggest that dark fractions consist of mixtures of unequilibrated material and pulverized equilibrated H chondrite similar to the light clasts. Volatile element concentrations in the dark fractions are similar to those in the least equilibrated H3 chondrites, and no petrographic evidence for admixture of significant amounts of carbonaceous chondrite was noted. It is concluded that volatile-rich H chondrite breccias may not have incorporated carbonaceous chondrite dust as the volatile element carrier.

Mcsween, H. Y., Jr.↗