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The occurrence of blue luminescing enstatite in E3 and E4 chondrites

Two compositional types of enstatite that emit cathodoluminescence (CL) are known to exist in E3 and E4 chondrites. The first type consists of the most common enstatites that are relatively FeO-poor and emit a red CL. Their CL is apparently activated by the presence of MnO and Cr2O3 in concentrations of 0.2 and 0.6 weight percent. The second type of enstatite is nearly FeO-free, contains no MnO or Cr2O3 and emits a blue CL. The origin of these two types of enstatite and their accompanying chemical and CL differences has long been a subject of discussion. Leitch and Smith first observed to two types and felt the compositional differences were too great to have formed under the same conditions. They postulated the two types of enstatite formed on separate parent bodies and were mixed when these bodies collided. McKinley et al. observed a continuous range of compositions between blue luminescing and red luminescing enstatites and concluded the two types of enstatite formed evidence that blue luminescing pyroxenes were relics that did not completely melt during the heating event which melted other precursor grains, and are distinct from the red CL pyroxene in the chondrules in E chondrites. In order to further clarify the nature and origin of the pyroxene that emits blue CL, the sections listed in another work were examined for the occurrence of blue luminescing enstatite.

Dehart, John M.↗

Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

NASA Discipline Environmental Health↗

Effect of ammonium sulfate, ammonium chloride and root-zone acidity on inorganic ion content of tobacco

Tobacco plants (Nicotiana tabacum L. cv NC82) were supplied with (NH4)2SO4 or NH4Cl at root-zone pH of 6.0 and 4.5 in hydroponic culture for 28 days. Dry matter accumulation, total N and C content, and leaf area and number were not affected by the NH4+ source or root-zone pH. Plants supplied with NH4Cl accumulated up to 1.2 mM Cl g DW-1, but accumulated 37% less inorganic H2PO4- and 47% less SO4(2-) than plants supplied with (NH4)2SO4. The large Cl- accumulation resulted in NH4Cl- supplied plants having a 31% higher inorganic anion (NO3-, H2, PO4-, SO4(2-), and Cl-) charge. This higher inorganic anion charge in the NH4Cl-supplied plants was balanced by a similar increase in K+ charge. Plants supplied with NH4Cl accumulated greater concentrations of Cl- in leaves (up to 5.1% of DW) than plants supplied with (NH4)2SO4 (less than -% DW). Despite the high Cl- concentration of leaves in NH4Cl supplied plants, these plants showed no symptoms of Cl- toxicity. This demonstrates that toxicity symptoms are not due solely to an interaction between high Cl- concentration in tissue and NH4+ nutrition. The increase in root-zone acidity to pH 4.5 from 6.0 did not induce toxicity symptoms.

NASA Program CELSS↗

Stable Chlorine Isotope Study: Application to Early Solar System Materials

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Mala,ira. M/↗

Effects of Zoledronate and Mechanical Loading during Simulated Weightlessness on Bone Structure and Mechanical Properties

Space flight modulates bone remodeling to favor bone resorption. Current countermeasures include an anti-resorptive drug class, bisphosphonates (BP), and high-force loading regimens. Does the combination of anti-resorptives and high-force exercise during weightlessness have negative effects on the mechanical and structural properties of bone? In this study, we implemented an integrated model to mimic mechanical strain of exercise via cyclical loading (CL) in mice treated with the BP Zoledronate (ZOL) combined with hindlimb unloading (HU). Our working hypothesis is that CL combined with ZOL in the HU model induces additive structural and mechanical changes. Thirty-two C57BL6 mice (male,16 weeks old, n8group) were exposed to 3 weeks of either HU or normal ambulation (NA). Cohorts of mice received one subcutaneous injection of ZOL (45gkg), or saline vehicle, prior to experiment. The right tibia was axially loaded in vivo, 60xday to 9N in compression, repeated 3xweek during HU. During the application of compression, secant stiffness (SEC), a linear estimate of slope of the force displacement curve from rest (0.5N) to max load (9.0N), was calculated for each cycle once per week. Ex vivo CT was conducted on all subjects. For ex vivo mechanical properties, non-CL left femurs underwent 3-point bending. In the proximal tibial metaphysis, HU decreased, CL increased, and ZOL increased the cancellous bone volume to total volume ratio by -26, +21, and +33, respectively. Similar trends held for trabecular thickness and number. Ex vivo left femur mechanical properties revealed HU decreased stiffness (-37),and ZOL mitigated the HU stiffness losses (+78). Data on the ex vivo Ultimate Force followed similar trends. After 3 weeks, HU decreased in vivo SEC (-16). The combination of CL+HU appeared additive in bone structure and mechanical properties. However, when HU + CL + ZOL were combined, ZOL had no additional effect (p0.05) on in vivo SEC. Structural data followed this trend with ZOL not modulating trabecular thickness in CL + NAHU mice. In summary, our integrated model simulates the combination of weightlessness, exercise-induced mechanical strain, and anti-resorptive treatment that astronauts experience during space missions. Based on these results, we conclude that, at the structural and stiffness level, zoledronate treatment during simulated spaceflight does not impede the skeletal response to axial compression. In contrast to our hypothesis, our data show that zoledronate confers no additional mechanical or structural benefit beyond those gained from cyclical loading.

Mechanical Loading↗

Chlorine in Lunar Basalts

In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-37~0 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

Barnes, J. J.↗

The Abundance and Isotopic Signature of Chlorine in UrKREEP: Implications for the Early Degassing of the Moon

Initally, the elevated delta-37 Cl values of lunar materials were attributed to volcanic degassing[1]. However, chlorine isotope ratios of apatite in lunarmare basalts appear to reflect mixing between two reservoirs.One component, with elevated delta-37 Cl is greater than or equal to + (25%) ([2] may represent the urKREEP--the final product of the crystallization of the lunar magma ocean. The second component, with delta-37 Cl is approximately (0%), is inferred to represent either a mare basalt reservoir or meteoritic materials. The idea that high delta-37 Cl is related to urKREEP suggest a global enrichment that occurred earlier in the lunar history [2,3]. Here we test this urKREEP-mixing hypothesis more rigorously, and report the observed limits of the model. We then use the results to calculate the Cl content of the urKREEP component and use those results to update estimates of the bulk Cl content of the Moon. This allows us to speculate on the mechanisms of loss of Cl from the lunar magma ocean.

Boyce, J. W.↗

Stability and photochemistry of ClO dimers formed at low temperature in the gas phase

The recent observations of elevated concentrations of the ClO radical in the austral spring over Antarctica have implicated catalytic destruction by chlorine in the large depletions seen in the total ozone column. One of the chemical theories consistent with an elevated concentration of the ClO is a cycle involving the formation of the ClO dimer through the association reaction: ClO + ClO = Cl2O2 and the photolysis of the dimer to give the active Cl species necessary for O3 depletion. Here, researchers report experimental studies designed to characterize the dimer of ClO formed by the association reaction at low temperatures. ClO was produced by static photolysis of several different precursor systems: Cl sub 2 + O sub 3; Cl sub 2 O sub 2; OClO + Cl sub 2 O spectroscopy in the U.V. region, which allowed the time dependence of Cl sub 2, Cl sub 2 O, ClO, OClO, O sub 3 and other absorbing molecules to be determined.

Cox, R. A.↗

Electron Backscatter Diffraction (EBSD) Analysis and U-Pb Geochronology of the Oldest Lunar Zircon: Constraining Early Lunar Differentiation and Dating Impact-Related Deformation

The evolution of the early moon was dominated by two processes (i) crystallization of the Lunar Magma Ocean (LMO) and differentiation of potassium-rare earth element-phosphorous-rich residual magma reservoir referred to as KREEP, and (ii) an intense meteorite bombardment referred to as lunar cataclysm . The exact timing of these processes is disputed, and resolution relies on collection and interpretation of precise age data. This study examines the microstructure and geochronology of zircon from lunar impact breccias collected during the Apollo 17 mission. A large zircon clast within lunar breccia 72215,195 shows sector zoning in optical microscopy, cathodoluminescence (CL) imaging and Raman mapping, and indicates that it was a relict fragment of a much larger magmatic grain. Sensitive high resolution ion microprobe (SHRIMP) U-Pb analysis of the zircon shows that U and Th concentration correlate with sector zoning, with darkest CL domains corresponding with high-U and Th (approx.150 and approx.100 ppm respectively), and the brightest-CL sectors containing approx.30-50 ppm U and approx.10-20 ppm Th. This indicates that variations in optical CL and Raman properties correspond to differential accumulation of alpha-radiation damage in each sector. Electron backscatter diffraction (EBSD) mapping shows that the quality of electron backscatter patterns (band contrast) varies with sector zoning, with the poorest quality patterns obtained from high-U and Th, dark-CL zones. EBSD mapping also reveals a deformation microstructure that is cryptic in optical, CL and Raman imaging. Two orthogonal sets of straight discrete and gradational low-angle boundaries accommodate approx.12 misorientation across the grain. The deformation bands are parallel to the crystallographic {a}-planes of the zircon, have misorientation axes parallel to the c-axis, and are geometrically consistent with formation by dislocation creep associated with <100>{010} slip. The deformation bands are unlike curved morphology of crystal-plastic microstructures in tectonically deformed terrestrial zircon, and geometrically similar to dislocation microstructures reported in experimentally shocked zircon. We interpret these crystal-plastic deformation microstructures to have resulted from a significant impact, either directly from impact shock, or during ductile flow directly following the impact. The deformation bands appear to continue undeflected through the non-indexed, radiation-damaged areas of the grain, which suggests that the orientation variation predates any significant mechanical weakening from radiation damage in the grain, and therefore occurred early in its history.

Timms, Nick↗

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

Shearer, C. K.↗

Matrix spectroscopic studies of chlorine atom-ozone reaction products

A spectroscopic study is presented of the matrix-isolated products of the direct combination reaction of chlorine atoms with ozone and of the microwave discharge reaction of chlorine and oxygen. Infrared spectra in the wavenumber range 2000 to 200 per cm were recorded for reaction products trapped by the condensation of a matrix of solid argon. Evidence for the formation of the ClO radical as well as the ClOO and ClClO radicals during the direct chlorine-ozone reaction is obtained, however no evidence is found for the presence of asymmetric ClO3 under conditions thought favorable for its formation. The ClO molecule is also observed following the microwave discharge reaction of chlorine and oxygen in argon in the isotopic forms (Cl-35)(O-16), (Cl-37)(O-16), (Cl-35)(O-18), and (Cl-37)(O-18). It is noted that the vibrational frequency for the (Cl-35)(O-16) radical at 849.2 per cm is blue-shifted 5 per cm above its gas-phase fundamental.

Carter, R. O., III↗

Solar-system abundances of the elements

Elemental analyses of the Ogueil Cl meteorite and all previous Cl chondrite analyses were employed to develop a new solar system abundance table, including the standard deviation and number of analyses for each element. The table also comprises the abundances of radioactive and radiogenic nuclides at the present and 4.55 AE ago, as well as abundances by weight in a typical Cl chondrite. The new abundances were within 20% of those determined by Cameron (1982), except for 14 cases in the range 20-50%, and 5 over 50%. The solar abundances were compared with the Cl abundances, showing a total of only 7 disagreements. No significant discrepancies were detected in the major cosmochemical groups, and a smooth trend was found in the abundances of odd-A nuclides. The new set is interpreted as accurate to 10%, with the Cl chondrites matching the primordial solar system abundances to at most 10% deviation.

Anders, E.↗

An analysis for crack layer stability

The problem of uncontrolled crack propagation and crack arrest is considered with respect to crack layer (CL) translational stability. CL propagation is determined by the difference between the energy release rate and the amount of energy required for material transformation, and necessary and sufficient conditions for CL instability are derived. CL propagation in polystyrene is studied for two cases. For the case of remotely applied fixed load fatigue, the sufficient condition of instability is shown to be met before the necessary condition, and the necessary condition controls the stability. For the fixed displacement case, neither of the instability conditions are met, and CL propagation remains stable, resulting in crack arrest.

Sehanobish, K.↗

Airborne intercomparison of nitric oxide measurement techniques

Results from an airborne intercomparison of techniques to measure tropospheric levels of nitric oxide (NO) are discussed. The intercomparison was part of the National Aeronautics and Space Administration's Global Tropospheric Experiment and was conducted during missions flown in the fall of 1983 and spring of 1984. Instruments intercompared included a laser-induced fluorescence (LIF) system and two chemiluminescence instruments (CL). NO mixing ratios from below 5 pptv (parts per trillion by volume) to greater than 100 pptv were reported, with the majority less than 20 pptv. Good correlation was observed between the measurements reported by the CL and LIF techniques. The general level of agreement observed for the ensemble of measurements obtained during the two missions provides the basis from which one can conclude that equally 'valid' measurements of background levels of NO can be expected from either CL or LIF instruments. At the same time the periods of disagreement that were observed between the CL and LIF instruments as well as between the two CL instruments highlight the difficulty of obtaining reliable measurements with NO mixing ratios in the 5-20 pptv range and emphasize the vigilance that should be maintained in future NO measurements.

Hoell, James M., Jr.↗

Chemistry of the CO dimer at low temperatures

Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.

Demore, W. B.↗

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30 deg North latitude

Results are presented of an investigation of the Cl and F inventories derived from the concentrations of eleven Cl- and F-bearing organic and inorganic species throughout the atmosphere, based on observations with the Atmospheric Trace Molecule Spectroscopy instrument aboard the Space Shuttle during the Spacelab 3 mission of April 29 to May 6, 1985. It was found that, in April-May 1985, near 30 deg N, the mean total stratospheric concentrations of Cl and F were 2.58 +/-0.10 ppbv and 1.15 +/-0.12 ppbv, respectively. Partitioning among the source, sink, and reservoir species was consistent with the conservation of the F and Cl budgets throughout the stratosphere. It is shown that the budgets of Cl and F above about 45 km altitude can be determined accurately by measuring only HCl, HF, and CF4 and provide a straightforward timely reference point for future inventories and trends evaluations.

Zander, R.↗

A spectral method determination of the first critical Rayleigh number for a low-Prandtl number crystal melt in a cylindrical container

The onset of laminar axisymmetric Rayleigh-Benard convection is investigated for a low-Prandtl number liquid metal in a cylindrical container. All surfaces are considered to be solid and no-slip. Two separate cases are examined for the thermal boundary conditions at the side wall, one with conducting and the other with insulated surface. The governing Boussinesq system is first perturbed and then simplified by introducing a Stokes stream function. Subsequently, a Chebyshev Galerkin spectral model is employed to reduce the simplified system to a system of first-order nonlinear ordinary differential equations. A local stability analysis determines the two values of the first critical Rayleigh number, Ra(sub cl), for the insulated and conducting side walls. As expected, the conducting Ra(sub cl) value of 2882.5 obtained from the present approach exceeded the corresponding insulated Ra(sub cl) value of 2331.6. For the insulated case, an earlier study using a different numerical approach suggests that Ra(sub cl) = 2261.9, while an experimental study measured Ra(sub cl) = 2700.

Dietz, C. M., Jr.↗

Th-230 - U-238 series disequilibrium of the Olkaria rhyolites Gregory Rift Valley, Kenya: Petrogenesis

Positive correlations of (U-238/Th-230) versus Th show the rhyolites to be products of partial melting. Positive correlations of U and Cl and U and F show that the U enrichment in the rhyolites is associated with the halogen contents which may be related to the minor phenocryst phase fractionation. Instantaneous Th/U ratios exceed time integrated Th/U ratios providing further evidence of the hydrous nature of the Olkaria rhyolite source. Excess (U-238/Th-230) in the subduction related rocks has been associated to the preferential incorporation of uranium in slab derived fluids, but no evaluation of the size of this flux has been made. The majority of the Naivasha samples show a (U-238/Th-230) less than 1 and plot close to the subduction related samples indicating the Naivasha rhyolites may also have been influenced by fluids during their formation. In general samples with high (U-238/Th-230) ratios reflecting recent enrichment of uranium relative to thorium have high thorium contents, thereby the high (U-238/Th-230) ratios are restricted to the most incompatible element enriched magmas and, hence, are a good indication that the rhyolites were formed by partial melting. If a fluid phase had some influence on the formation of the rhyolites then the uranium and thorium may have some correlation with F and Cl contents which can be mirrored by the peralkalinity. Plots of uranium against F and Cl contents are shown. The positive correlation indicates that the uranium enrichments are associated with the halogen contents. There seems to be a greater correlation for U against Cl than F indicating that the U may be transported preferentially as Cl complexes.

Black, S.↗