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At least 217 records · Page 12

Measurements and mechanisms of localized aqueous corrosion in aluminum-lithium alloys

Like most heat treatable aluminum alloys, localized corrosion and stress corrosion of Al-Li-Cu alloys is strongly dependent on the nature and distribution of second phase particles. To develop a mechanistic understanding of the role of localized corrosion in the stress corrosion process, bulk samples of T(sub 1) (Al2CuLi) and a range of Al-Cu-Fe impurity phases were prepared for electrochemical experiments. Potentiodynamic polarization and galvanic couple experiments were performed in standard 0.6 M NaCl and in simulated crevice solutions to assess corrosion behavior of these particles with respect to the alpha-Al matrix. A comparison of time to failure versus applied potential using a constant load, smooth bar SCC test technique in Cl(-), Cl(-)/CrO4(2-), and Cl(-)/CO3(2-) environments shows that rapid failures are to be expected when applied potentials are more positive than the breakaway potential (E sub br) of T(sub 1) (crack tip) but less than E(sub br) of alpha-Al (crack walls). It is shown that this criterion is not satisfied in aerated Cl(-) solutions. Accordingly, SCC resistance is good. This criterion is satisfied, however, in an alkaline isolated fissure exposed to a CO2 containing atmosphere. Rapid failure induced by these fissures was recently termed preexposure embrittlement. Anodic polarization shows that the corrosion behavior of T(sub 1) is relatively unaffected in alkaline CO3(2-) environments but the alpha-Al phase is rapidly passivated. X ray diffraction of crevice walls from artificial crevices suggests that passivation of alpha-Al occurs as hydrotalcite-type compound (LiAl2(OH)6)2(+) - CO3(2-) - nH2O.

Buchheit, Rudolph G., Jr.↗

Dynamic crystallization characteristics of enstatite chondrite chondrules

Although the chemical properties of enstatite and ordinary chondrites are distinctly different, they both contain chondrules with a similar array of textures. This similarity suggests like origins. Textural studies using chondrule compositions from ordinary chondrites suggest that these chondrules have an igneous origin: either by crystallization from melts or from partial melts of crystalline material. In contrast, the cathodoluminescence (CL) properties of the enstatite from enstatite chondrites were interpreted to mean that mechanical aggregation played an important part in their formation. An alternative interpretation of these CL properties, however, suggests that variations in the minor element content of the enstatite, a probable result of igneous fractionation processes, could also produce different CL colors. An attempt was made to evaluate the two models by performing dynamic crystallization experiments on an average enstatite chondrule composition and by looking at the resultant CL. The textures grown on experimentally crystallized E-chondrite melts confirm that formational processes are similar to those for the ordinary chondrites with the obvious exception of the oxidation state.

Lofgren, Gary E.↗

Cathodoluminescence observations of in situ aqueous destruction of chondrules in the Murchison CM chondrite

A low-power cathodoluminescence (CL) mosaic of a 1x2 cm section of the Murchison CM chondrite contains chondrules of two types: one contains olivines with red CL and is thought to be the equivalent of group A chondrules of Sears et.; and one without observable CL, which is probably equivalent to their group B chondrules. Both types of chondrule contain dust mantles with a characteristic uniform red CL due to very fine-grained forsterites, but the mantles of group A chondrules have a complex internal structure and are much thicker than the relatively thin rims on the group B chondrules. The variety of internal textures and the progressive integration of the objects with the surrounding matrix suggests to us that these features are large group A chondrules in the process of being destroyed by aqueous alteration. Prior to aqueous alteration, group A chondrules in CM chondrites were larger than group B chondrules, which is contrary to the situation in ordinary chondrites and were apparently destroyed more rapidly than group B chondrules by aqueous alteration.

Sears, Derek W. G.↗

Magmatic volatiles and the weathering of Mars

The sources for volatiles on Mars have been the subject of many hypotheses for exogenous influences including late accretion of volatile-enriched material, impact devolatilization to create massive early atmospheres, and even major bombardment by comets. However, the inventory of chemically active volatiles observable at the contemporary surface of Mars is consistent with domination by endogenous, subsequent planetary processes, viz., persistent magmatic outgassing. Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the geochemical similarities are such that the suite of gases emitted from Martian volcanic activity should include H2O, CO2, S-containing gases (e.g. H2S and/or SO2), and Cl-containing gases (e.g., Cl2 and/or HCl). H2O and CO2 exist in the atmosphere of Mars. Both are also present as surface condensates. However, spectroscopic observations of the Martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted, with upper limits of less than or equal to 10(exp -7) the abundance of CO2. Likewise, there is no evidence of polar condensates of compounds of these elements as there is for CO2 and H2O. Within the soil, on the other hand, there has been direct measurement of incorporated H2O and abundant compounds containing S and Cl. Barring some as yet implausible geochemical sequestering process, the S/Cl ratio of about 6:1 in Martian soils implies a limit of 5% on the contribution of matter of solarlike composition (e.g., carbonaceous chondrite or cometary material) to these volatiles. Hence, exogenous sources are minor or not yet observed. From analysis of elemental trends in Martian soils, it has been recently shown that a simple two-component model can satisfy the Viking in situ measurements. Component A includes Si and most or all the Al, Ca, Ti, and Fe. Component B, taken as 16 +/- 3% by weight of the total, contains S and most or all the Cl and Mg. These results constrain several models of Martian soil mineralogy but are consistent with a mixture of silicates (such as Fe-rich clays and accessory minerals and soluble salts). The overall element profile is notably like shergottites, with significant incorporation of chemically reactive atmospheric gases from magmatic degassing.

Clark, B. C.↗

Hydrochloric acid and the chlorine budget of the lower statosphere

Concentrations of HCl measurements in the lower stratosphere in 1993 by the ALIAS instrument on the ER-2 aircraft reveal that only 40% of inorganic chlorine (Cl(y), inferred from in situ measurements of organic chlorinated sources gases) is present as HCl, significantly lower than model predictions. Although the sum of measured HCl, ClO and ClONO2, the latter inferred from measurements of ClO and NO2 equals Cl(y) to within the incertainty of measurement, it is systematically less than Cl(y) by 30-50%. This discrepancy suggests that concentrations of ClONO2 may exceed those of HC; near 20 km altitude, consistent with a slower photolysis rate for ClONO2 than calculated using recommended cross sections. Comparison of profiles of HCl measured during 1992 and 1193 at mid-latitudes by balloon (BLISS and MARKIV), space shuttle (ATMOS), and satellite (HALOE) instruments with the aircraft data reveal an apparent pressure dependence to the HCl to Cl(y) ratio, consistent with a factor of 3-10 reduction in the photolysis rate for ClONO2 at ER-2 altitudes. However, the diurnal variation of ClO is well-simulated by models using the recommended photolysis rate, and simulations measurements of ClONO2 and HCl at mid-latitudes by ATMOS and MARKIV report HCl (HCL+ ClONO2) ratios greater than or equal to 50%. Premliminary measurements by ALIAS in the southern hemisphere report HCl/Cl(y) values of about 75%.

Webster, C. R.↗

EUVS Sounding Rocket Payload

During the first half of this year (CY 1996), the EUVS project began preparations of the EUVS payload for the upcoming NASA sounding rocket flight 36.148CL, slated for launch on July 26, 1996 to observe and record a high-resolution (approx. 2 A FWHM) EUV spectrum of the planet Venus. These preparations were designed to improve the spectral resolution and sensitivity performance of the EUVS payload as well as prepare the payload for this upcoming mission. The following is a list of the EUVS project activities that have taken place since the beginning of this CY: (1) Applied a fresh, new SiC optical coating to our existing 2400 groove/mm grating to boost its reflectivity; (2) modified the Ranicon science detector to boost its detective quantum efficiency with the addition of a repeller grid; (3) constructed a new entrance slit plane to achieve 2 A FWHM spectral resolution; (4) prepared and held the Payload Initiation Conference (PIC) with the assigned NASA support team from Wallops Island for the upcoming 36.148CL flight (PIC held on March 8, 1996; see Attachment A); (5) began wavelength calibration activities of EUVS in the laboratory; (6) made arrangements for travel to WSMR to begin integration activities in preparation for the July 1996 launch; (7) paper detailing our previous EUVS Venus mission (NASA flight 36.117CL) published in Icarus (see Attachment B); and (8) continued data analysis of the previous EUVS mission 36.137CL (Spica occultation flight).

Stern, Alan S.↗

Polyimides and Process for Preparing Polyimides Having Thermal-Oxidative Stability

Polyimides and the process for preparing polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of one or more of the polyamines such as the aromatic diamines, one or more of the tetracarboxylic dianhydrides and a novel dicarboxylic endcap having formula with an R1 group of either hydrogen or an alkyl radical of one to four carbons, an R2 group of either OH, NH2, F, or Cl radical, an R3 group of either H, OH, NH2, F, Cl or an alkylene radical, an R4 group of either an alkyl, aryl, aryloxy, nitro, F, or Cl radical, and/or an R5 group of either H, alkyl, aryl, alkoxy, aryloxy, nitro, F, or Cl radical. The polyimides are useful particularly in the preparation of prepegs and PMR composites.

Meador, Mary Ann B.↗

Polyimides And Process For Preparing Polyimides Having Improved Thermal-Oxidative Stability

Polyimides and the process for preparing polyimides having improved thermal-oxidative stability derived from the polymerization of effective amounts of one or more of the polyamines such as the aromatic diamines, one or more of the tetracarboxylic dianhydrides and a novel dicarboxylic endcap having formula with an R 1 group of either hydrogen or an alkyl radical of one to four carbons, an R 2 group of either OH, NH 2 , F, or Cl radical, an R 3 group of either H, OH, NH 2 , F, Cl or an alkylene radical, an R 4 group of either an alkyl, aryl, aryloxy, nitro, F, or Cl radical, and/or an R 5 group of either H, alkyl, aryl, alkoxy, aryloxy, nitro, F, or Cl radical. The polyimides are useful particularly in the preparation of prepegs and PMR composites.

Mary Ann B Meador↗

Cutaneous Microvascular Flow In the Foot During Simulated Variable Gravities

Our objective was to elucidate how varying gravitational fields affect blood perfusion in the sole of the foot. Human subjects underwent whole-body tilting at four angles: upright (1 G(sub z), 22 deg (.38 G(sub z)), 10 deg (.17 G(sub z)), and supine (0 G(sub z)), simulating the gravitational fields of Earth, Mars, Moon, and microgravity, respectively. Cutaneous capillary blood flow was monitored on the plantar surface of the heel by laser Doppler flowmetry while weight bearing load was measured beneath the same foot with a calibrated scale. Foot mean arterial pressures (MAP) were calculated by adding estimated hydrostatic pressures to continuously recorded heart-level blood pressures for each subject. At each tilt angle, subjects increased weight bearing on one foot in graded load increments of one kilogram beginning with zero. The weight bearing at which null flow first occurred was determined as the closing load (CL). Subsequently, the weight bearing was reduced in reverse steps until blood flow returned (opening load, OL). CL and OL were normalized to each subject's body weight and expressed as percent of body weight. Mean CLs (SD in parentheses) for simulated Earth, Mars, Moon, and micro-gravities were 14 (5), 8 (2), 6 (2), and 5 (2) percent of body weight, respectively. OLs were 12 (3), 6 (1), 5 (2), and 4 (1), respectively. Calculated foot MAPs for each simulated gravitational field were 192 (19), 127 (12), 106 (10), and 87 (9) mm Hg, respectively. CL and OL were significantly correlated with foot MAP (r = 0.70, 0.72, respectively). Overall, CL and OL were significantly different (p is less than 0.001). The data suggest that decreased local arterial pressure in the foot lowers tolerance to external compression. Consequently, the human foot sole may be more prone to cutaneous ischernia during loading in microgravity than on Earth.

Chang, David S.↗

Flash spectroscopic studies of the kinetics of the halorhodopsin photocycle

The photoreactions of halorhodopsin are complicated by the fact that the parent pigment and its photoproducts interact with chloride. Thus, in any photoreaction scheme at least four species have to be accounted for: HR565 and HR578 Cl-, as well as HR640 and HR520 Cl-. A photocycle scheme proposed earlier places the two main photointermediates of halorhodopsin, HR520 Cl- and HR640, into a single photocycle, with a chloride-dependent equilibrium between them [Oesterhelt, D., Hegemann, P., & Tittor, J. (1985) EMBO J. 4, 2351-2356]. This scheme, with the additional feature of direct photoproduction of HR640 from HR565, was tested in this work by using numerical solutions of the appropriate differential equations to simulate flash-induced absorption changes at 500 nm (production of HR520 Cl-) and at 660 nm (production of HR640). The time scale of the simulation was ms following the flash. Comparison of the simulated curves with experimental traces yielded a unique set of three rate constants. The proposed photocycle scheme and these rate constants predict well the shapes and amplitudes of flash traces at various chloride concentrations. It appears from the photocycle scheme, and the numerical values of rate constants, that chloride is bound with high affinity to the parent halorhodopsin molecule, but with much lower affinity to its main photointermediate. This may be the consequence of the fact that in the parent halorhodopsin in the retinal configuration is all-trans, but in the two photointermediates it is 13-cis.

Non-NASA Center↗

The locations and amounts of endogenous ions and elements in the cap and elongating zone of horizontally oriented roots of Zea mays L.: an electron-probe EDS study

We used quantitative electron-probe energy-dispersive x-ray microanalysis to localize endogenous Na, Cl, K, P, S, Mg and Ca in cryofixed and freeze-dried cryosections of the cap (i.e. the putative site of graviperception) and elongating zone (i.e. site of gravicurvature) of horizontally oriented roots of Zea mays. Ca, Na, Cl, K and Mg accumulate along the lower side of caps of horizontally oriented roots. The most dramatic asymmetries of these ions occur in the apoplast, especially the mucilage. We could not detect any significant differences in the concentrations of these ions in the central cytoplasm of columella cells along the upper and lower sides of caps of horizontally-oriented roots. However, the increased amounts of Na, Cl, K and Mg in the longitudinal walls of columella cells along the lower side of the cap suggest that these ions may move down through the columella tissue of horizontally-oriented roots. Ca also accumulates (largely in the mucilage) along the lower side of the elongating zone of horizontally-oriented roots, while Na, P, Cl and K tend to accumulate along the upper side of the elongating zone. Of these ions, only K increases in concentration in the cytoplasm and longitudinal walls of cortical cells in the upper vs lower sides of the elongating zone. These results indicate that (1) gravity-induced asymmetries of ions differ significantly in the cap and elongating zone of graviresponding roots, (2) Ca accumulates along the lower side of the cap and elongating zone of graviresponding roots, (3) increased growth of the upper side of the elongating zone of horizontally-oriented roots correlates positively with increased amounts of K in the cytoplasm and longitudinal walls of cortical cells, and (4) the apoplast (especially the mucilage) may be an important component of the pathway via which ions move in graviresponding rots of Zea mays. These results are discussed relative to mechanisms for graviperception and gravicurvature of roots.

NASA Program Space Biology↗

Effects of Kinetic Roughening and Liquid-Liquid Phase Transition on Lysozyme Crystal Growth Velocities

We measured the growth velocities of the (110) face of tetragonal lysozyme, V (centimeters per second), at four different concentrations, c (milligrams per milliliter), as the solution temperature, T (Centigrade), was reduced. For a broad range of T dependent on c, we find that the growth velocities increased as the solution temperature was reduced. The initial increase in V is well characterized by the 2D nucleation model for crystal growth, yielding the magnitude of an effective barrier for growth, gamma(sub s) = 1.2 plus or minus 0.1 x 10(exp -13) erg/molecule. Below certain temperatures, T(sub cr), dependent on c, however, a kinetic roughening hypothesis that considers the continuous addition of molecules anywhere on the crystal surface better describes the observed growth velocities. The application of the continuous growth model, up to the solution cloud-point temperatures, T(sub cl), enabled the determinations of the crossover concentration, c(sub r), from estimated values of T(sub cr). For all conditions presented, we find that the crossover from growth by 2D nucleation to continuous addition occurs at a supersaturation, sigma (sub c), = 2.0 plus or minus 0.1. Moreover, we find the energy barrier for the continuous addition, E(sub c), within the temperature range T(sub cl) less than T less than T less than T (sub cr), to be 6 plus or minus 1 x 10(exp -13) erg/molecule. Further reduction of T below approximately 2-3 C of T(sub cl), also revealed a rapid slowing of crystal growth velocities. From quasi-elastic light scattering investigations, we find that the rapid diminishment of crystal growth velocities can be accounted for by the phase behavior of lysozyme solutions. Namely, we find the reversible formation of dense fluid proto-droplets comprised of lysozyme molecules to occur below approximately 0.3 C of T(sub cl). Hence, the rapid slowing of growth velocities may occur as a result of the sudden depletion of "mobile" molecules within crystal growth solutions as dense fluid proto-droplets form.

Gorti, Sridhar↗

Prolonged lobar hypoxia in vivo enhances the responsivity of isolated pulmonary veins to hypoxia

The hypoxic response of pulmonary vessels isolated from eight sheep whose right apical lobes (RAL) had inspired 100% N2 for 20 h was studied. The RAL of these conscious sheep inspired hypoxic gas and the remainder of the lung inspired air. During hypoxia, RAL perfusion was 33 +/- 3% of its air value, carotid arterial PO2 averaged 86 +/- 3 mm Hg and pulmonary perfusion pressure was not significantly different from the initial control period when the RAL inspired air. At the end of the hypoxic exposure, the sheep were killed, and pulmonary artery and vein rings (0.5 to 2 mm inner diameter) were isolated from both the RAL and the right cardiac lobe, which served as the control lobe (CL). Arteries from the RAL and CL did not contract in response to 6% O2/6% CO2/88% N2 (hypoxia). In contrast, RAL veins did contract vigorously in response to hypoxia, whereas CL veins did not contract or contracted only minimally. Rubbing of the endothelium or prior incubation of RAL veins with catalase (1,200 units/ml), indomethacin (10(-5) M), or the thromboxane A2/prostaglandin H2 (TxA2/PGH2) receptor antagonist, SQ 29,548 (3 X 10(-6) M) each significantly reduced the response to hypoxia. RAL veins were also found to be more reactive than CL veins to the prostaglandin endoperoxide analogue U46619. We conclude that prolonged lobar hypoxia in vivo increases the responsivity of isolated pulmonary veins to hypoxia. These contractions may result from an increase in reactive O2 species, which in turn modify production of, metabolism of, and/or tissue responsivity to TxA2/PGH2.

NASA Discipline Cardiopulmonary↗

Using Transport Diagnostics to Understand Chemistry Climate Model Ozone Simulations

We demonstrate how observations of N2O and mean age in the tropical and midlatitude lower stratosphere (LS) can be used to identify realistic transport in models. The results are applied to 15 Chemistry Climate Models (CCMs) participating in the 2010 WMO assessment. Comparison of the observed and simulated N2O/mean age relationship identifies models with fast or slow circulations and reveals details of model ascent and tropical isolation. The use of this process-oriented N2O/mean age diagnostic identifies models with compensating transport deficiencies that produce fortuitous agreement with mean age. We compare the diagnosed model transport behavior with a model's ability to produce realistic LS O3 profiles in the tropics and midlatitudes. Models with the greatest tropical transport problems show the poorest agreement with observations. Models with the most realistic LS transport agree more closely with LS observations and each other. We incorporate the results of the chemistry evaluations in the SPARC CCMVal Report (2010) to explain the range of CCM predictions for the return-to-1980 dates for global (60 S-60 N) and Antarctic column ozone. Later (earlier) Antarctic return dates are generally correlated to higher (lower) vortex Cl(sub y) levels in the LS, and vortex Cl(sub y) is generally correlated with the model's circulation although model Cl(sub y) chemistry or Cl(sub y) conservation can have a significant effect. In both regions, models that have good LS transport produce a smaller range of predictions for the return-to-1980 ozone values. This study suggests that the current range of predicted return dates is unnecessarily large due to identifiable model transport deficiencies.

Strahan, S. E.↗

Igneous and Sedimentary Compositions from Four Landing Sites on Mars from the Alpha Particle X-Ray Spectrometer (APXS)

The APXS - supported and promoted strongly by Heinrich Waenke - on all four Mars Rovers has returned compositional data from about 1000 rocks and soil targets along the combined traverses of over 60 kilometers. Providing precise and accurate bulk chemistry with typically 16 quantified elements, the APXS is a powerful and versatile tool that when combined with the ability to traverse to key rocks and soils has provided critical information needed to understand the geologic evolution of Mars. APXS data allow comparisons among landing sites, provide ground truth for orbiters and connections back to SNC meteorites. The soils and dust are basaltic in character and represent the average Mars composition similar to Adirondack basalts from Gusev crater but with unambiguous elevated and correlated S, Cl and Zn contents. At all four landing sites the APXS found several rocks with a felsic composition. The similarity is best assessed in a logarithmic ratio plot of rock normalized to the average soil composition (Fig.1). High alkaline, Al, and low Mg, Fe, low S, Cl and Ni, Zn as well as an Fe/Mn ratio of approximately 50 indicate a likely unaltered and igneous origin. Sediments, e.g. the Burns formation, with approximately 25 wt% SO3 at Meridiani Planum have been documented over 10s of kilometers (Fig. 2). This formation is compositionally homogeneous, but showing the removal of MgSO4 and a threefold increase in Cl downhill in 2 craters. The degraded rim of the Noachian crater Endeavour resembles average Mars crust, with local Ca, Mg and Fe sulfate alteration and elevated Mn, some felsic rocks, and high Al, Si and low Fe rocks, possibly indicating clays. Unusual soils at Gusev crater in the area surrounding Home Plate include some very rich in ferric sulfate salts (up to 35 wt% SO3) and some with 90% wt% SiO2, possibly indicating fumerolic activities. Rocks in the Columbia Hills show significant signs of alteration including elevated S, Cl and Br in the abraded interior. At Gale Crater, mudstones with approximately 20% clay, less than 1% SO3 and overall average Mars composition indicate a former habitable environment with low acidity. A remarkable diversity of compositions was found during Curiosity's traverses, which likely stems from material influx from the northern Gale rim. At Pahrump, the base of Mount Sharp, a homogeneous mudstone with lower Mg and Ca was encountered. The composition of this Murray unit can be traced over several kilometers with smooth trends of higher Fe/Mn and lower soluble trace elements Ni and Zn at higher elevation. The likely aeolian Stimson formation with average Mars crustal composition intersects in several places in sharp contact with the Murray formation. Both units show local alteration halos with highly elevated SiO2 of up to 75%, usually correlated with increase in Ti and often P.

Gellert, R.↗

20 Years of ClO Measurements in the Antarctic Lower Stratosphere

We present 20 years (1996-2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOEl) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004-2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column C1O on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cl(sub y) = HCl + ClONO2 + HOCl + 2 x Cl2 + 2 x Cl2+ ClO + Cl). The resultant trends in Cl(sub y), which determine the long-term trend in ClO, are estimated to be -0.5 +/-0.2, -1.40.9, and -0.60.4% per year, for zonal MLS, Scott Base MLS (both 2004-2015), and ChlOE (1996-2015) respectively. These trends are within 1sigma of trends in stratospheric Cl(sub y) previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

temperature anomalies↗

Apatite-Melt Partitioning of Volatiles in Basaltic Systems: Implications for Determining Volatile Abundances in Planetary Bodies from Apatite

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials, and due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources [i.e., 1]. Experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in basaltic systems [e.g., 2- 3], reporting that apatite-melt partitioning of volatiles is best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, exchange coefficients may vary as a function of temperature, pressure, melt composition, and/or oxygen fugacity. Furthermore, exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite [3]. In these regions of ternary space, we anticipate that crystal chemistry could influence partitioning behavior. Consequently, we conducted experiments to investigate the effect of apatite crystal chemistry on apatite-melt partitioning of F, Cl, and OH.

McCubbin, F. M.↗

Understanding Martian Alteration Processes by Comparing In-Situ Chemical Measurements from Multiple Landing Sites

Characterizing the history of aqueous activity at the martian surface has been an objective of the Mars Exploration Rovers (MER) and the Mars Science Laboratory (MSL). Although the geologic context of the three landing sites are different, comparisons across the datasets can provide greater insight than using data from one mission alone. The Alpha Particle X-ray Spectrometer (APXS) is common to all three rovers (Spirit at Gusev crater, Opportunity at Meridiani Planum, and Curiosity at Gale crater) and provides a consistent basis for these comparisons. Soil and Dust: Fine grained basaltic soils and dust are remarkably uniform in chemical composition across multiple landing sites. These similarities in the concentrations of major, minor, and a few trace elements (Fig. 1) are indicative of planet-wide consistency in the composition of source materials for the soils. S and Cl vary by a factor of two in the soil and dust, but there is no clear association with any bulk cation (e.g., no correlation between S and total Ca, Mg, or Fe in soils). These volatile elements, however, are clearly associated with the nanophase-ferric iron component in the soil established by Mössbauer spectroscopy [1,2]. S and Cl likely originated as acidic species from volcanic out-gassing and subsequently coalesced on dust and sand grain surfaces, possibly with an affinity towards Fe3+ sites. Importantly, given the mobility of S and Cl in aqueous exposures, soil samples maintaining the typical molar S/Cl ratio of ~3.7:1 indicate minimal interactions with liquid water after the addition of S and Cl. In contrast to this well-established baseline, soil samples have been discovered at all three landing sites with atypical S/Cl ratios (e.g., subsurface soils), indicative of a more complex aqueous history.

Yen, A. S.↗