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Ar-Ar and I-Xe Ages and the Thermal History of IAB Meteorites

Studies of several samples of the large Caddo County IAB iron meteorite reveal andesitic material, enriched in Si, Na, Al and Ca, which is essentially unique among meteorites. This material is believed to have formed from a chondritic source by partial melting and to have further segregated by grain coarsening. Such an origin implies extended metamorphism of the IAB parent body. New Ar-39- Ar-40 ages for silicate from three different Caddo samples are consistent with a common age of 4.50-4.51 Gyr ago. Less well defined Ar-Ar degassing ages for inclusions from two other IABs, EET8333 and Udei Station, are approx.4.32 Gyr, whereas the age for Campo del Cielo varies considerably over approx.3.23-4.56 Gyr. New I-129-Xe-129 ages for Caddo County and EET8333 are 4557.9+/-0.1 Myr and 4557-4560 Myr, respectively, relative to an age of 4562.3 Myr for Shallowater. Considering all reported Ar-Ar degassing ages for IABs and related winonaites, the range is approx.4.32-4.53 Gyr, but several IABs give similar Ar ages of 4.50-4.52 Gyr. We interpret these older Ar ages to represent cooling after the time of last significant metamorphism on the parent body, and the younger ages to represent later 40Ar diffusion loss. The older Ar-Ar ages for IABs are similar to Sm-Nd and Rb-Sr isochron ages reported in the literature for Caddo County. Considering the possibility that IAB parent body formation was followed by impact disruption, reassembly, and metamorphism (e.g., Benedix et al. 2000), the Ar-Ar ages and IAB cooling rates deduced from Ni concentration profiles in IAB metal (Herpfer et al., 1994) are consistent if the time of the post-assembly metamorphism was as late as approx.4.53 Gyr ago. However, I-Xe ages reported for some IABs define much older ages of approx.4558-4566 Myr, which cannot easily be reconciled with the much younger Ar-Ar and Sm-Nd ages. An explanation for the difference in radiometric ages of IABs may reside in combinations of the following: a) I-Xe ages have very high closure temperatures and were not reset during metamorphism approx.4.53 Gyr ago; b) a bias exists in the 40K decay constants which makes these Ar-Ar ages approx.30 Myr too young; c) the reported Sm-Nd and Rb-Sr ages for Caddo are in error by amounts equal to or exceeding their reported 2-sigma uncertainties; and d) about 30 Myr after the initial heating that produced differentiation of Caddo silicate and mixing of silicate and metal, a mild metamorphism of the IAB parent body reset the Ar-Ar ages.

Bogard, Donald D.↗

Investigation of Pore Size Effect On Spray Cooling Heat Transfer With Porous Tunnels

Previous studies have shown that spray cooling heat flux enhancement may be attained by using enhanced surface structures. However, most enhanced surface spray cooling studies have been limited to extended surfaces relative to the base surface. In this study, experiments were conducted to study the effects of pore size on spray cooling heat flux when using porous tunnels. The porous tunnels where placed sub-surface relative to the top of the heater block. Pores of varying size were machined in the top of the heater block leading into the sub-surface tunnels. Pore diameters varied between 0.25 mm and 1.0 mm. Each copper block had a projected cross-sectional area of 2.0 cm(sup 2). Measurements were also obtained on a heater block with a flat surface for baseline comparison purposes. A 2x2 nozzle array was used with PF-5060 as the working fluid. Thermal performance data was obtained under nominally degassed (chamber pressure of 41.4 kPa) conditions with a bulk fluid temperature of 20.5 "C. Results for both the study show that the highest critical heat flux (CHF) attained was 141 w/cm2 using pores 1.0 mm in diameter. This gave an enhancement of 75% relative to the flat surface case under nominally degassed conditions.

Silk, Eric A.↗

Provenance and Concentration of Water in the Shergottite Mantle

The water content of the martian mantle is controversial. In particular, the role of water in the petrogenesis of the shergottites has been much debated. Although the shergottites, collectively, contain very little water [e.g., 1,2], some experiments have been interpreted to show that percent levels of water are required for the petrogenesis of shergottites such as Shergotty and Zagami [3]. In this latter interpretation, the general paucity of water in the shergottites and their constituent minerals is attributed to late-stage degassing. Y980459 (Y98) is a very primitive, perhaps even parental, martian basalt, with a one-bar liquidus temperature of approx.1400 C. Olivine is the liquidus phase, and olivine core compositions are in equilibrium with the bulk rock [e.g., 4]. Petrogenetically, therefore, Y98 has had a rather simple history and can potentially help constrain the role of water in martian igneous processes. In particular, once trapped, melt inclusions should not be affected by subsequent degassing.

Jones, J. H.↗

Capture of Hydrogen Using ZrNi

Water, as ice, is thought to reside in craters at the lunar poles along with CH4 and H2 . A proposed robotic mission for 2012 will utilize metal/metal hydrides for H2 recovery. Specifications are 99% capture of H2 initially at 5 bar and 100C (or greater), and degassing completely at 300C. Of 47-systems examined using the van't Hoff equation, 4 systems, Mg/MgH2, Mg2Ni/Mg2NiH4, ZrNi/ZrNiH2.8, and Pd/PdH0.77, were considered likely candidates for further examination. It is essential, when selecting a system, to also examine questions regarding activation, kinetics, cyclic stability, and gas impurity effects. After considering those issues, ZrN1 was selected as the most promising candidate, as it is easily activated and rapidly forms ZrNiH 2.8 . In addition, it resists oxide poisoning by CO2, and H2O, while some oxidation by O2 is recommended for improved activation . The presence of hydrogen in the as received Zr-Ni alloy from Alfa Aesar posed additional technical problems. X-ray diffraction of the Zr-Ni powder (-325 mesh), with a Zr:Ni wt% ratio of 70:30, was found to consist of ZrH2, ZrNiH2.8, and ZrNi. ZrH2 in the alloy presented the risk that after degassing that both Zr and ZrNi would be present, and thus lead to erroneous results regarding the reactivity of ZrNi with H2 . Fortunately, ZrH2 is a highly stable hydride that does not degas H2 to any significant extent at temperatures below 300C. Based on equilibrium calculations for the decomposition of ZrH2, only 1 millionth of the hydride decomposed at 300C under a N2 atmosphere flowing at 25 ccm for 64 hours, the longest time for pretreatment employed in the investigation. It was possible, from the X-ray results and knowledge of the Zr:Ni ratio, to compute the composition of a pretreated specimen as being 76 wt% ZrNi and the balance ZrH2.

Patton, Lisa↗

Water Content of Lunar Alkali Fedlspar

Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites crystallized between 4.3-3.8 Ga from relatively wet melts that degassed upon crystallization. The formation of these granites likely removed significant amounts of water from some mantle source regions, e.g. later mare basalts predicting derivation from a mantle with <10 ppm water. However, this would have been a heterogeneous pro-cess based on K distribution. Thus some, if not most of the mantle may not have been devolatilized by this process; as seen by water in volcanic glasses and melt inclusions.

Mills, R. D.↗

Cooling Rates of Lunar Volcanic Glass Beads

It is widely accepted that the Apollo 15 green and Apollo 17 orange glass beads are of volcanic origin. The diffusion profiles of volatiles in these glass beads are believed to be due to degassing during eruption (Saal et al., 2008). The degree of degassing depends on the initial temperature and cooling rate. Therefore, the estimations of volatiles in parental magmas of lunar pyroclastic deposits depend on melt cooling rates. Furthermore, lunar glass beads may have cooled in volcanic environments on the moon. Therefore, the cooling rates may be used to assess the atmospheric condition in an early moon, when volcanic activities were common. The cooling rates of glasses can be inferred from direct heat capacity measurements on the glasses themselves (Wilding et al., 1995, 1996a,b). This method does not require knowledge of glass cooling environments and has been applied to calculate the cooling rates of natural silicate glasses formed in different terrestrial environments. We have carried out heat capacity measurements on hand-picked lunar glass beads using a Netzsch DSC 404C Pegasus differential scanning calorimeter at University of Munich. Our preliminary results suggest that the cooling rate of Apollo 17 orange glass beads may be ~12 K/min, based on the correlation between temperature of the heat capacity curve peak in the glass transition range and glass cooling rate. The results imply that the parental magmas of lunar pyroclastic deposits may have contained more water initially than the early estimations (Saal et al., 2008), which used higher cooling rates, 60-180 K/min in the modeling. Furthermore, lunar volcanic glass beads could have been cooled in a hot gaseous medium released from volcanic eruptions, not during free flight. Therefore, our results may shed light on atmospheric condition in an early moon.

Hui, Hejiu↗

A Global Catalogue of Large SO2 Sources and Emissions Derived from the Ozone Monitoring Instrument

Sulfur dioxide (SO2) measurements from the Ozone Monitoring Instrument (OMI) satellite sensor processed with the new principal component analysis (PCA) algorithm were used to detect large point emission sources or clusters of sources. The total of 491 continuously emitting point sources releasing from about 30 kt yr(exp -1) to more than 4000 kt yr(exp -1) of SO2 per year have been identified and grouped by country and by primary source origin: volcanoes (76 sources); power plants (297); smelters (53); and sources related to the oil and gas industry (65). The sources were identified using different methods, including through OMI measurements themselves applied to a new emission detection algorithm, and their evolution during the 2005- 2014 period was traced by estimating annual emissions from each source. For volcanic sources, the study focused on continuous degassing, and emissions from explosive eruptions were excluded. Emissions from degassing volcanic sources were measured, many for the first time, and collectively they account for about 30% of total SO2 emissions estimated from OMI measurements, but that fraction has increased in recent years given that cumulative global emissions from power plants and smelters are declining while emissions from oil and gas industry remained nearly constant. Anthropogenic emissions from the USA declined by 80% over the 2005-2014 period as did emissions from western and central Europe, whereas emissions from India nearly doubled, and emissions from other large SO2-emitting regions (South Africa, Russia, Mexico, and the Middle East) remained fairly constant. In total, OMI-based estimates account for about a half of total reported anthropogenic SO2 emissions; the remaining half is likely related to sources emitting less than 30 kt yr(exp -1) and not detected by OMI.

Emissions↗

Mapping the Iron Oxidation State in Martian Meteorites

Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

Martin, A. M.↗

Volatiles in High-K Lunar Basalts

Chlorine is an unusual isotopic system, being essentially unfractionated ((delta)Cl-37 approximately 0 per mille ) between bulk terrestrial samples and chondritic meteorites and yet showing large variations in lunar (approximately -4 to +81 per mille), martian, and vestan (HED) samples. Among lunar samples, the volatile-bearing mineral apatite (Ca5(PO4)3[F,Cl,OH]) has been studied for volatiles in K-, REE-, and P (KREEP), very high potassium (VHK), low-Ti and high-Ti basalts, as well as samples from the lunar highlands. These studies revealed a positive correlation between in-situ (delta)Cl-37 measurements and bulk incompatible trace elements (ITEs) and ratios. Such trends were interpreted to originate from Cl isotopic fractionation during the degassing of metal chlorides during or shortly after the differentiation of the Moon via a magma ocean. In this study, we investigate the volatile inventories of a group of samples for which new-era volatile data have yet to be reported - the high-K (greater than 2000 ppm bulk K2O), high-Ti, trace element-rich mare basalts. We used isotope imaging on the Cameca NanoSIMS 50L at JSC to obtain the Cl isotopic composition [((Cl-37/(35)Clsample/C-37l/(35)Clstandard)-1)×1000, to get a value in per thousand (per mille)] which ranges from approximately -2.7 +/- 2 per mille to +16.1 +/- 2 per mille (2sigma), as well as volatile abundances (F & Cl) of apatite in samples 10017, 10024 & 10049. Simply following prior models, as lunar rocks with high bulk-rock abundances of ITEs we might expect the high-K, high-Ti basalts to contain apatite characterized by heavily fractionated (delta)Cl-37 values, i.e., Cl obtained from mixing between unfractionated mantle Cl (approximately 0 per mille) and the urKREEP reservoir (possibly fractionated to greater than +25 per mille.). However, the data obtained for the studied samples do not conform to either the early degassing or mixing models. Existing petrogentic models for the origin of the high-K, high-Ti basalts do not include urKREEP assimilation into their LMO cumulate sources. Therefore, Cl in these basalts either originated from source region heterogeneity or through assimilation or metasomatism by volatile and incompatible trace element rich materials. The new data presented here could provide evidence for the existence of region(s) in the lunar interior that are ITE-enriched and contain Cl that does not share isotopic affinities with lunar urKREEP, possibly representing the composition of the purported 'neuKREEP'.

Barnes, Jessica J.↗

The Cl isotope composition and halogen contents of Apollo-return samples

Lunar mare basalts are depleted in F and Cl by approximately an order of magnitude relative to mid-ocean ridge basalts and contain two Cl-bearing components with elevated isotopic compositions relative to the bulk-Earth value of ∼0‰. The first is a watersoluble chloride constituting 65 ± 10% of total Cl with δ37Cl values averaging 3.0 ± 4.3‰. The second is structurally bound chloride with δ37Cl values averaging 7.3 ± 3.5‰. These high and distinctly different isotopic values are inconsistent with equilibrium fractionation processes and instead suggest early and extensive degassing of an isotopically light vapor. No relationship is observed between F/Cl ratios and δ37Cl values, which suggests that lunar halogen depletion largely resulted from the Moon-forming Giant Impact. The δ37Cl values of apatite are generally higher than the structurally bound Cl, and ubiquitously higher than the calculated bulk δ37Cl values of 4.1 ± 4.0‰. The apatite grains are not representative of the bulk rock, and instead record localized degassing during the final stages of lunar magma ocean (LMO) or later melt crystallization. The large variability in the δ37Cl values of apatite within individual thin sections further supports this conclusion. While urKREEP (primeval KREEP [potassium/rare-earth elements/phosphorus]) has been proposed to be the source of the Moon’s high Cl isotope values, the ferroan anorthosites (FANs) have the highest δ37Cl values and have a positive correlation with Cl content, and yet do not contain apatite, nor evidence of a KREEP component. The high δ37Cl values in this lithology are explained by the incorporation of a >30‰ HCl vapor from a highly evolved LMO.

The Moon↗

The abundances of F, Cl, and H2O in eucrites: Implications for the origin of volatile depletion in the asteroid 4 Vesta

We conducted a petrologic study of apatite within eight unbrecciated, non-cumulate eucrites and two monomict, non-cumulate eucrites. These data were combined with previously published data to quantify the abundances of F, Cl, and H2O in the bulk silicate portion of asteroid 4 Vesta (BSV). Using a combination of apatite-based melt hygrometry/chlorometry and appropriately paired volatile/refractory element ratios, we determined that BSV has 3.0–7.2 ppm F, 0.39–1.8 ppm Cl, and 3.6–22 ppm H2O. The abundances of F and H2O are depleted in BSV relative to CI chondrites to a similar degree as F and H2O in the bulk silicate portion of the Moon. This degree of volatile depletion in BSV is similar to what has been determined previously for many moderately volatile elements in 4 Vesta (e.g., Na, K, Zn, Rb, Cs, and Pb). In contrast, Cl is depleted in 4 Vesta by a greater degree than what is recorded in samples from Earth or the Moon. Based on the Cl-isotopic compositions of eucrites and the bulk rock Cl/F ratios determined in this study, the eucrites likely formed through serial magmatism of a mantle with heterogeneous δ37Cl and Cl/F, not as extracts from a partially crystallized global magma ocean. Furthermore, the volatile depletion and Cl-isotopic heterogeneity recorded in eucrites is likely inherited, at least in part, from the precursor materials that accreted to form 4 Vesta and is unlikely to have resulted solely from degassing of a global magma ocean, magmatic degassing of eucrite melts, and/or volatile loss during thermal metamorphism. Although our results can be reconciled with the past presence of wide-scale melting on 4 Vesta (i.e., a partial magma ocean), any future models for eucrite petrogenesis involving a global magma ocean would need to account for the preservation of a heterogeneous eucrite source with respect to Cl/F ratios and Cl isotopes.

Francis M. Mccubbin↗

Location, location: deciphering the significance of in-situ hydrogen analyses of Martian meteorite phases

Understanding how inner planets acquired their volatiles such as hydrogen (H) is fundamental to constrain models of solar system formation [e.g. 1]. One avenue of estimating the H content and isotopic characteristics of differentiated planets is to analyze the samples we have from them as meteorites. Ideally, the H content and isotopic characteristic of the mantle sources of these igneous rocks should give insight into the volatile origin of each planetary body. The mantle H signatures can be estimated from that of the parent melt, which in turn may be derived from that of the first crystallized phases. However, we will illustrate the processes that can modify the H content and D/H ratios of pyroxene, olivine and feldspar in selected Martian meteorites relative to those of their mantle sources, with two key protocols for SIMS analysis. The first key is to put each analysis in textural context ("location, location"). In particular, of prime importance is whether an analysis is done at the center or the edge of a mineral grain, close or far from a shock disturbed area, and in a mineral crystallized at the beginning or late in the differentiation sequence. Accompanying the H analyses done by SIMS with major and trace element data at the same analysis locations allows to constrain the history of crystallization, cooling, alteration and shock of the meteorite. For example, volcanic degassing can be evidenced by decreasing water contents and increasing D/H ratios from core to edge of nakhlite pyroxenes [2]. Traverses of H analyses in pyroxene and maskelynite in shergottite LAR 06319 provide examples of H contents and D/H ratios modified during degassing following shock [3]. The second key is to assess if the area analyzed by SIMS has shock generated damage of the mineral structure, as will be shown in pyroxene and olivine from shergottite RBT 04262. Olivine in shergottites have too high water contents to be explained with an igneous origin and their D/H ratios are more consistent with terrestrial alteration, as observed before [4]. A review of all these processes shows how careful one has to be prior to using H measurements in meteorites to infer the origin and amount of water in differentiated planetary interiors.

A.H. Peslier↗

Comparison of Alternative Configurations of an Integrated Open-Loop Carbon Dioxide Removal System using Liquid Amine

Several carbon dioxide removal systems are being investigated for applications in microgravity. The liquid amine wedge system utilizes the capillary action of liquids to prevent the mixing of the air and liquid while still allowing for carbon dioxide capture at their interface. A one crew mission requires approximately 1 kg per day of carbon dioxide removal to prevent adverse health effects. A proposed design of a wedge tray system can be improved from the initial testing parameters to achieve the required carbon dioxide capture for one crew. The wedge trays in the contactor can be organized in either a parallel configuration to accumulate less CO2 in the liquid but at a higher flow rate or a series configuration to yield a higher weight percentage of CO2 in the liquid but at a lower flow rate. The gas flow rate and composition were held constant at 26scfm and 2600ppm, respectively, due to constraints of other proposed systems but the liquid flow rate was adjusted between 0.1mL/min and 10mL/min. The flow rate that yielded the best carbon dioxide capture was X mL/min and Y mL/min for the parallel and series configurations, respectively. The degasser temperature and pressure were varied from 80 to 100°C and 0 and -3 inHg. The largest carbon dioxide flux of Z kg/day/m2 was observed at a contactor liquid flow rate of X mL/min and a degasser temperature and pressure of T°C and P inHg.

Adrian Cortez↗

Design Concepts for an Optimized, Modular, and Scalable Liquid Amine Test Stand

The Air Revitalization Labs at NASA Ames Research Center (ARC) is investigating liquid amines to for their performance removing spacecraft carbon dioxide (CO2) for crewed space missions. Development of the current one-crew scale amine test stand stems from several modifications to a test stand initially built at NASA Johnson Space Center (JSC) This sub-scale system has been modified to incorporate a flow spreader for the inlet air stream, an updated contactor design for CO2 capture, a degasser to regenerate the liquid sorbent and recover the captured CO2, and a condenser to reduce water loss. Results from the existing integrated liquid amine test stand have provided valuable insight, but continued performance optimization requires design and build of a new integrated test system. New design concepts will institute a modular configuration to allow for interfacing with novel contactor and degasser architecture, parallel or series flow pathways for the air stream and liquid sorbent, and scaling up to a 4-crew CO2 removal system.

Tiago Faria Costa↗

Thermal Cycle and Capacitance Testing of Mezzo Industries Phase Change Material Heat Capacitor

A phase change material heat capacitor prototype, designed and built under a NASA Small Business Innovation Research grant by Mezzo Technologies, was tested through coolant thermal cycling within the expected flow rates and temperature range of the Orion spacecraft’s propylene glycol-water mixture coolant system. Testing was performed with the phase change material contained under sealed conditions after a degassing procedure and exposed to atmosphere without prior degassing. The useful heat storage capacitance was measured and compared to Orion spacecraft requirements and theoretical N-Pentadecane storage capacity.

Propylene Glycol Water↗

Convection in the earth's mantle.

Convection currents in Earth mantle and role of convection in degassing processes, noting continental drift and ocean floor evidence

CONVECTION CURRENT↗