Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Volatilization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,099 records · Page 61

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

Rubidium and potassium isotopic variations in chondrites and Mars: Accretion signatures and planetary overprints

As moderately volatile elements, isotopes of Rb and K can trace volatilization processes in planetary bodies. Rubidium isotopic data are however very scarce, especially for non-carbonaceous meteorites. Here, in this study, we report combined Rb and K isotopic data (δ 87/85 Rb and δ 41/39 Κ) for 7 ordinary, 6 enstatite, and 4 Martian meteorite falls to understand the causes for the variations in volatile abundances and isotopic compositions. Bulk Rb and K isotopic compositions of planetary bodies are estimated to be (Table 1): Mars +0.10 ± 0.03 ‰ for Rb and -0.26 ± 0.05 ‰ for K, bulk OCs $-0.12^{+0.15}_{-0.24}$ ‰ for Rb and $-0.72^{+0.28}_{-0.41}$ ‰ for K, bulk ECs $-0.02^{+0.29}_{-0.26}$ ‰ for Rb and $-0.33^{+0.37}_{-0.23}$ ‰ for K. The bulk K isotopic compositions of subgroup OCs are estimated to be $-0.72^{+0.26}_{-0.55}$ ‰ for H chondrites, $-0.71^{+0.23}_{-0.39}$ ‰ for L chondrites, and $-0.77^{+0.63}_{-0.30}$ ‰ for LL chondrites. A broad correlation between the Rb and K isotopic compositions of planetary bodies is observed. The correlation follows a slope that is consistent with kinetic evaporation and condensation processes, suggesting volatility-controlled mass-dependent isotope fractionation (as opposed to nucleosynthetic anomalies). Individual ordinary and enstatite chondrites show large Rb and K isotopic variations (-1.02 to +0.29 ‰ for Rb and -0.91 to -0.15 ‰ for K). Samples of lower metamorphic grades display correlated elemental and isotopic fractionations between Rb and K, while samples of higher metamorphic grades show great scatter, suggesting that chondrite parent-body processes have decoupled the two elements and their isotopes at the sample scale. Several processes could have contributed to the observed isotopic variations of Rb and K, including (i) chondrule “nugget effect”, (ii) volatilization during parent-body thermal metamorphism (heat-induced vaporization and gas transport within parent bodies), (iii) thermal diffusion during parent-body metamorphism, and (iv) impact/shock heating. Quantitative modeling of the first two processes suggests that neither of them could produce isotopic variations large enough to explain the observed isotopic variations. Volatilization during parent-body thermal metamorphism [the scenario (ii)], which has been commonly invoked to explain the isotopic variations of volatile elements, is gas transport-limited and its effect on isotopic fractionations of moderately volatile elements should be negligible. Modeling of diffusion processes suggests that (iii) could produce K isotopic variation comparable to the observed variation. The large isotopic variations in non-carbonaceous meteorites are thus most likely due to diffusive redistribution of K and Rb during metamorphism and/or shock-induced heating and vaporization.

58 GEOSCIENCES↗

Oxygenated Molecules measured with a Nitrate Chemical Ionization Mass Spectrometer

These files contain selected oxygenated compounds detected by chemical ionization mass spectrometry with nitrate reagent ion. Detected compounds were grouped by volatility and the time series of the most intense ions in each volatility class are provided here. Volatility (C*) in units of μg m^-3 was calculated using log_10(C*)=(n_ref -n_C)*b_C - (n_O - 3*n_N)*b_O - 2*(((n_O - 3n_N)*n_C) / (n_C + n_O - 3*n_N))*b_CO - n_N* b_N where n_ref = 25, b_c = 0.475m b_O = 0.2, b_N = -0.5, b_CO = 0.9, n_C is the number of carbon atoms in the ion formula, n_O is the number of oxygen atoms in the ion formula, and n_N is the number of nitrogen atoms in the ion formula. Volatility was calculated for each formula (with the nitrate anion excluded) and compounds were assigned into extremely low volatility (ELVOCs, C* < 10^−4.5 μg m^-3), low volatility (LVOCs, 10^−4.5 μg m^-3 ≤ C* < 10^−0.5 μg m^-3), or semi-volatile (SVOCs, 10^−0.5 μg m^-3 ≤ C* < 10^2.5 μg m^-3) bins. All ions were assumed to be detected with a collision-limited sensitivity and thus represent lower bound values. Values are reported as parts per trillion by volume mixing ratio.

Extremely low-volatility organic compounds↗

Energy efficient photonic memory based on electrically programmable embedded III-V/Si memristors: switches and filters

Abstract Over the past few years, extensive work on optical neural networks has been investigated in hopes of achieving orders of magnitude improvement in energy efficiency and compute density via all-optical matrix-vector multiplication. However, these solutions are limited by a lack of high-speed power power-efficient phase tuners, on-chip non-volatile memory, and a proper material platform that can heterogeneously integrate all the necessary components needed onto a single chip. We address these issues by demonstrating embedded multi-layer HfO 2 /Al 2 O 3 memristors with III-V/Si photonics which facilitate non-volatile optical functionality for a variety of devices such as Mach-Zehnder Interferometers, and (de-)interleaver filters. The Mach-Zehnder optical memristor exhibits non-volatile optical phase shifts > π with ~33 dB signal extinction while consuming 0 electrical power consumption. We demonstrate 6 non-volatile states each capable of 4 Gbps modulation. (De-) interleaver filters were demonstrated to exhibit memristive non-volatile passband transformation with full set/reset states. Time duration tests were performed on all devices and indicated non-volatility up to 24 hours and beyond. We demonstrate non-volatile III-V/Si optical memristors with large electric-field driven phase shifts and reconfigurable filters with true 0 static power consumption. As a result, co-integrated photonic memristors offer a pathway for in-memory optical computing and large-scale non-volatile photonic circuits.

Cheung, Stanley (ORCID:0000000248860013)↗

Cloud response to co-condensation of water and organic vapors over the boreal forest

Abstract. Accounting for the condensation of organic vapors along with water vapor (co-condensation) has been shown in adiabatic cloud parcel model (CPM) simulations to enhance the number of aerosol particles that activate to form cloud droplets. The boreal forest is an important source of biogenic organic vapors, but the role of these vapors in co-condensation has not been systematically investigated. In this work, the environmental conditions under which strong co-condensation-driven cloud droplet number enhancements would be expected over the boreal biome are identified. Recent measurement technology, specifically the Filter Inlet for Gases and AEROsols (FIGAERO) coupled to an iodide-adduct chemical ionization mass spectrometer (I-CIMS), is utilized to construct volatility distributions of the boreal atmospheric organics. Then, a suite of CPM simulations initialized with a comprehensive set of concurrent aerosol observations collected in the boreal forest of Finland during spring 2014 is performed. The degree to which co-condensation impacts droplet formation in the model is shown to be dependent on the initialization of temperature, relative humidity, updraft velocity, aerosol size distribution, organic vapor concentration, and the volatility distribution. The predicted median enhancements in cloud droplet number concentration (CDNC) due to accounting for the co-condensation of water and organics fall on average between 16 % and 22 %. This corresponds to activating particles 10–16 nm smaller in dry diameter that would otherwise remain as interstitial aerosol. The highest CDNC enhancements (ΔCDNC) are predicted in the presence of a nascent ultrafine aerosol mode with a geometric mean diameter of ∼ 40 nm and no clear Hoppel minimum, indicative of pristine environments with a source of ultrafine particles (e.g., via new particle formation processes). Such aerosol size distributions are observed 30 %–40 % of the time in the studied boreal forest environment in spring and fall when new particle formation frequency is the highest. To evaluate the frequencies with which such distributions are experienced by an Earth system model over the whole boreal biome, 5 years of UK Earth System Model (UKESM1) simulations are further used. The frequencies are substantially lower than those observed at the boreal forest measurement site (< 6 % of the time), and the positive values, peaking in spring, are modeled only over Fennoscandia and the western parts of Siberia. Overall, the similarities in the size distributions between observed and modeled (UKESM1) are limited, which would limit the ability of this model, or any model with a similar aerosol representation, to project the climate relevance of co-condensation over the boreal forest. For the critical aerosol size distribution regime, ΔCDNC is shown to be sensitive to the concentrations of semi-volatile and some intermediate-volatility organic compounds (SVOCs and IVOCs), especially when the overall particle surface area is low. The magnitudes of ΔCDNC remain less affected by the more volatile vapors such as formic acid and extremely low- and low-volatility organic compounds (ELVOCs and LVOCs). The reasons for this are that most volatile organic vapors condense inefficiently due to their high volatility below the cloud base, and the concentrations of LVOCs and ELVOCs are too low to gain significant concentrations of soluble mass to reduce the critical supersaturations enough for droplet activation to occur. A reduction in the critical supersaturation caused by organic condensation emerges as the main driver of the modeled ΔCDNC. The results highlight the potential significance of co-condensation in pristine boreal environments close to sources of fresh ultrafine particles. For accurate predictions of co-condensation effects on CDNC, also in larger-scale models, an accurate representation of the aerosol size distribution is critical. Further studies targeted at finding observational evidence and constraints for co-condensation in the field are encouraged.

54 ENVIRONMENTAL SCIENCES↗

A Moderate D/H Ratio for a Surficial Water Reservoir on Mars

Martian surface morphology implies that Mars was once warm enough to maintain persistent liquid water on its surface and that water played a significant role in the formation of weathered/altered terrains [e.g., 1, 2, 3]. Volatiles exhaled by volcanic activity would have been the dominant greenhouse gases and would have significantly affected the Martian climate. The enrichment of some volatile elements in the atmosphere, which would have dissolved in surface water, could also have influenced water chemistry (e.g., acidity) and played a significant role in weathering and aqueous alteration processes. While much of this picture is qualitative, Martian meteorites contain records of major Martian volatile reservoirs. This study characterizes Martian surficial volatile reservoirs based on in situ ion microprobe analyses of volatile abundances and H-isotopes of glassy phases (groundmass glass [GG] and impact melt [IM]) in Martian basalts (shergottites). Although these meteorites are of igneous origin, some glassy phases underwent impact-induced modification that trapped surficial and atmospheric volatile components [4, 5]; e.g., inert gases contained in IMs from EETA79001 (EETA79) match the relative abundances of modern Martian atmosphere [6]. Analyses of these glassy phases demonstrate that surficial volatile reservoirs have distinct D/H ratios from their magmatic volatiles.

Usui, Tomohiro↗

Switchable system for high-salinity brine desalination and fractional precipitation

A saline feed stream flows into a liquid-liquid extraction system; and a volatile organic solvent flows through a main compressor. The compressed volatile organic solvent then flows through a solvent regenerator, which can be a heat exchanger or a combination of a vaporization device and a condenser, to cool the volatile organic solvent. The cooled volatile organic solvent in liquid phase then flows into the liquid-liquid extraction system, where the saline feed stream contacts the volatile organic solvent to selectively extract water from the saline feed stream into the volatile organic solvent, producing a concentrated brine and an organic-rich mixture of water and the volatile organic solvent. The organic-rich mixture flows from the liquid-liquid extraction system into the solvent regenerator, where the organic-rich mixture is heated to produce an organic-rich vapor and desalinated water; and the organic-rich vapor is recycled as volatile organic solvent back into the liquid-liquid extraction system.

Wilson, Aaron D.↗

Dynamic Evolution of Mass and Physical Properties of Atmospheric Organic Aerosol under Solar Irradiance

Organic aerosol (OA) particles constitute a substantial fraction of sub-micron particulate mass in the atmosphere and play a critical role in climate system. OA undergoes dynamic aging processes in the atmosphere, with photolytic aging induced by ultraviolet solar irradiance being an important yet poorly characterized mechanism. Knowledge gaps persist regarding the role of volatility transformations during photolytic aging on the OA mass decay kinetics and the evolution of climate-relevant properties, such as hygroscopicity, hindering the model evaluation of OA spatiotemporal distributions and atmospheric budgets. In this study, we conduct isothermal photolytic aging experiments on both laboratory-generated secondary organic aerosols and ambient-collected particles from urban Atlanta, utilizing a high-sensitivity Quartz Crystal Microbalance. Our results reveal that photolytic aging reduces 40–66% of the low-volatility OA mass with lifetimes ranging from 8 to 200 hours under solar irradiance, and 44–92% of the photolytic mass loss is through slow evaporation of semi- or intermediate-volatile products, kinetically limited by their volatility. We observe up to ±50% changes in OA hygroscopicity with the transformation of fresh OA to photo-recalcitrant low-volatility products, associated with changes in oxygen-to-carbon ratio and molecular weight. A kinetic model incorporating photolytic volatility transformation provides a cohesive explanation for the observed photolysis-induced changes in mass, volatility, and hygroscopicity. Our results can help constrain model representation of the dynamic evolutions of mass and climate-relevant properties during photolytic aging processes of the ambient OA, improving our understanding of OA atmospheric behavior and climate impact.

Bai, Bin↗

Generating Novel Aroma Phenotypes Using Commercial Wine Samples to Characterize an F1 Population

Due to their disease tolerance and cold hardy nature, interspecific hybrid grapes are widely grown in the Midwestern and Northeastern United States, with additional interest worldwide in the face of increased abiotic and biotic stresses from climate change. However, the aroma profile of these hybrids is unique and generally less popular in comparison with Vitis vinifera grapes. One of the challenges in any phenotyping project is first defining the traits of interest. As wine quality was our ultimate metric of interest, the aroma profile of commercial wines produced from the parents of a breeding population ( Vitis aestivalis derived ‘Norton’ x V. vinifera . ‘Cabernet Sauvignon’) was first assessed for traits of interest. We investigated 11 commercial wines each of Norton, a popular hybrid in Missouri and Cabernet Sauvignon (Cab) for their volatile profiles using the more inclusive metabolomics-based workflow. We then analyzed 21 Norton and 21 Cab grapes from different sites and vintages for the free and bound volatile compounds using HS-SPME-GCMS to validate the differences in wine. The GCMS data was processed using XCMS software to find features that were different between the two cultivars. The two cultivars were found to have differences in their volatile profiles, with 304 features different for wine volatiles, 418 features different for free volatiles, and 302 features different for bound volatiles at 0.05 significance level and with at least a 1.5-fold change between the two cultivars. Those features were used to identify several odor-active compounds in both grapes and wines, including β-damascenone, β-ionone, eugenol, 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN), and methyl salicylate. Some of the identified compounds were higher in Norton than Cab; however, several features were higher in Cab. Using the identified aroma compounds as markers, we phenotyped an F1 population of Norton and Cab. The F1 population was found to be segregating for many aroma compounds with some genotypes demonstrating an even higher concentration of aroma volatiles than either of the parents. Ultimately, using commercially available samples paired with untargeted analysis proved to be an efficient way to determine phenotypes of interest for further analysis and may offer an easy way to choose potential parents with desired traits for breeding.

59 BASIC BIOLOGICAL SCIENCES↗

The effect of wind and currents on gas exchange in an estuarine system

The objectives were to develop a non-volatile tracer to use in gas exchange experiments in laterally unconfined systems and to study applications of deliberate tracers in limnology and oceanography. Progress was made on both fronts but work on the development of the non-volatile tracer proved to be more difficult and labor intensive that anticipated so no field experiments using non-volatile tracers was performed as yet. In the search for a suitable non-volatile tracer for an ocean scale gas exchange experiment a tracer was discovered which does not have the required sensitivity for a large scale experiment, but is very easy to analyze and will be well suited for smaller experiments such as gas exchange determinations on rivers and streams. Sulfur hexafluoride, SF6, was used successfully as a volatile tracer along with tritium as a non-volatile tracer to study gas exchange rates from a primary stream. This is the first gas exchange experiment in which gas exchange rates were determined on a head water stream where significant groundwater input occurs along the reach. In conjunction with SF6, Radon-222 measurements were performed on the groundwater and in the stream. The feasibility of using a combination of SF6 and radon is being studied to determine groundwater inputs and gas exchange of rates in streams with significant groundwater input without using a non-volatile tracer.

Broecker, W. S.↗

Short-period comets

The spacecraft flybys of Comet Halley in 1986 confirmed Whipple's icy conglomerate hypothesis for cometary nuclei and showed that comets are far richer in volatiles than any other class of solar system bodies. Water is the most abundant volatile, comprising roughly 80 percent of the gas flowing out from the nucleus. Carbon monoxide is next with a content of 15 percent relative to water, though with approximately half of that coming from an extended source in the cometary coma, i.e., hydrocarbon dust grains. The detection of large numbers of hydrocarbon CHON grains was one of the more significant discoveries of the Halley flybys, as was the ground-based observation that CN occurs in jets, again indicating an extended source. Evidence was also found for more complex hydrocarbons. Estimates of the total dust-to-gas ratio for Halley range as high as 2:1, indicating that a substantial fraction of the volatile material may be tied up in solid hydrocarbons rather than ices. The role of clathrates in trapping more volatile ices is not yet understood. If Halley can be taken to be representative of all short-period comets, then the short-period comets may provide a significant source of volatiles in near-earth space. This resource is more difficult to reach dynamically than the near-earth asteriods, but the high volatile content may justify the additional effort necessary. In addition, there is considerable evidence that at least some fraction of the near-earth asteriods are extinct cometary nuclei which have evolved into asteroid orbits, and which may contain significant volatiles buried beneath an insulating lag-deposit crust of nonvolatiles. Knowledge of comets will be greatly enhanced in the near future by the Comet Rendezvous Flyby mission now under development by NASA, and by the proposed Rosetta mission.

Weissman, Paul R.↗

Thermally Mobile Trace Elements in Carbonaceous Chondrites from Cold and Hot Deserts

Some decades ago, Anders and co-workers used RNAA to classify a number of trace elements as being volatile during nebular condensation and accretion into primitive objects based upon their strong depletion in (equilibrated) ordinary chondrites relative to C1 chondrites. Such elements, e.g. Ag, Bi, Cd, Cs, In, Se, Te, Tl, Zn and others, exhibit nearly constant, C1-normalized atomic abundances in C2 (CM2) and in C3 chondrites. They interpreted the near-constancy of these abundances according to a 2-component model in which volatiles were introduced into carbonaceous (and other) chondrites as Cl material which was diluted with differing proportions of high-temperature (i.e. volatile-free) components. In this view, mean volatile element abundances of 0.48 in C2 and 0.24-0.29 x C1 in C3 chondrites indicated that C2 and C3 chondrites are, respectively, about 1:1 and 1:2-3 mixtures of Cl-like and high temperature materials. More recently, C1 normalized abundances of such volatile elements are nearly constant in most C2-6 chondrites (i.e. 25 non-Antarctic meteorites, nearly all falls, and 36 Antarctic finds) consistent with a 2- component mixing model. However, rather than being quantized, mean volatile element contents in each chondrite define a continuum from 0.92-0.14 x Cl for these 61 chondrites. A few carbonaceous chondrites - the first having been the NIPR consortium samples B-7904, Y-82162 and Y-86720 - show an altered pattern: many of the volatile elements in each exhibit the usual constancy of C1-normalized atomic abundances, but modified by further depletion of Cd and other elements like Tl and Bi. These are the most mobile trace elements, i.e. those most readily vaporized and lost from primitive meteorites during week-long heating at greater than or equal to 400 C under low ambient pressures (initially 10 (exp -5) atm H2), simulating metamorphic conditions in a primitive parent body. Similarities between mobile element data for B-7904, Y-82162 and Y-86720 with those for Murchison heated at 500-700 C suggest that these Antarctic C1 and C2-like chondrites were metamorphosed at temperatures like these in the interiors of their parent bodies. Metamorphic temperatures inferred from RNAA data and textural/mineralogic alterations are internally consistent, agreeing with those evident in heated Murchison samples. These 3 chondrites were also heated late in their histories since all have lost cosmogenic 3-He, presumably during close solar approach, and B-7904 and Y-86720 seem also to have lost substantial proportions of radiogenic He-4 and Ar-40, cf. data. Similarities in spectral reflectance data for C-, G-, B- and F- asteroids, for these meteorites and for heated Murchison samples suggest that thermally metamorphosed interior materials in these asteroids were excavated by impacts and re-deposited on them, forming their present surfaces. Establishment of the thermal metamorphic histories of carbonaceouis chondrites, then, is essential to establishing the evolution and present-day nature of C-type and related asteroids.

Lipschutz, M. E.↗

Thermally Mobile Trace Elements in Carbonaceous Chondrites From Cold and Hot Deserts

Some decades ago, Anders and co-workers used RNAA to classify a number of trace elements as being volatile during nebular condensation and accretion into primitive objects based upon their strong depletion in (equilibrated) ordinary chondrites relative to C1 chondrites. Such elements, e.g. Ag, Bi, Cd, Cs, In, Se, Te, Tl, Zn and others, exhibit nearly constant, C1-normalized atomic abundances in C2 (CM2) and in C3 chondrites. They interpreted the near-constancy of these abundances according to a 2-component model in which volatiles were introduced into carbonaceous (and other) chondrites as C1 material which was diluted with differing proportions of high-temperature (i.e. volatile-free) components. In this view, mean volatile element abundances of 0.48 in C2 and 0.24-0.29 x C1 in C3 chondrites indicated that C2 and C3 chondrites are, respectively, about 1:1 and 1:2-3 mixtures of C1-like and high temperature materials. More recently, Xiao and Lipschutz found that C-normalized abundances of such volatile elements are nearly constant in most C2-6 chondrites (i.e. 25 non-Antarctic meteorites, nearly all falls, and 36 Antarctic finds) consistent with a 2-component mixing model. However, rather than being quantized, mean volatile element contents in each chondrite define a continuum from 0.92-0.14 x C1 for these 61 chondrites. A few carbonaceous chondrites, the first having been the NIPR consortium samples B-7904, Y-82162 and Y-86720, show an altered pattern: many of the volatile elements in each exhibit the usual constancy of C1-normalized atomic abundances, but modified by further depletion of Cd and other elements like Tl and Bi. These are the most mobile trace elements, i.e. those most readily vaporized and lost from primitive meteorites during week-long heating at greater than or equal to 400 C under low ambient pressures (initially 10(exp -5) atm H2), simulating metamorphic conditions in a primitive parent body. Similarities between mobile element data for B-7904, Y-82162 and Y-86720 with those for Murchison heated at 500-700 C, suggest that these Antarctic C1 - and C2-like chondrites were metamorphosed at temperatures like these in the interiors of their parent bodies. Metamorphic temperatures inferred from RNAA data and textural/mineralogic alterations are internally consistent, agreeing., with those evident in heated Murchison samples. These 3 chondrites were also heated late in their histories since all have lost cosmogenic He-3, presumably during close solar approach, and B-7904 and Y-86720 seem also to have lost substantial proportions of radiogenic He-4 and Ar-40 cf. data in. Similarities in spectral reflectance data for C-, G-, B- and F- asteroids, for these meteorites and for heated Murchison samples suggest that thermally metamorphosed interior materials in these asteroids were excavated by impacts and re-deposited on them, forming their present surfaces. Establishment of the thermal metamorphic histories of carbonaceous chondrites, then, is essential to establishing the evolution and present-day nature of C-type and related asteroids.

Lipschutz, M. E.↗

VIPER’s Mass Spectrometer observing lunar operations (MSolo)

The Volatiles Investigating Polar Exploration Rover (VIPER) is a lunar volatiles detection and measurement mission that will land on Mons Mouton near Nobile crater, close to the Moon’s south pole. One of the analytical instruments embedded within the rover is the Mass Spectrometer observing lunar operations (MSolo) instrument. VIPER’s data will ultimately be used to create lunar water resource maps that may enable a sustained presence on the lunar surface. As VIPER navigates several kilometers of terrain, its onboard analytical instrumentation will characterize the presence of volatiles along the traverse path and identify candidate locations for drilling. Upon selection of a drilling site, the rover will position itself and deploy an auguring, percussive drill down to a meter depth. Upon extraction, regolith cuttings captured by the auger are deposited on the surface; an activity that will initiate the release of any volatile gases that are subsequently detected and quantified by MSolo. MSolo is designed to identify low-molecular-weight volatiles (between m/z 1-100) with unit mass resolution. Volatiles of interest include D/H and O18/O16 bearing species, including possible water contained within the lunar regolith. MSolo is a modified, commercial off-the-shelf (COTS) system, meaning the instrument is based on a commercially available unit that has been ruggedized for space applications.

MSolo↗

Off-Gas Design and Testing from Advanced Chlorination Process

Chlorination of Zr alloy cladding with sulfur-chloride reagents is being considered as a means of separating the main metal from alloying elements, imbedded U, actinides, and fission and activation products to purify the Zr. This would allow the Zr to be disposed of as low-level nuclear waste or possibly be recycled. A multistage process was developed that involves several steps and waste streams. Recycling of sulfur-chloride reagents S 2 Cl 2 and SOCl 2 is planned to minimize the waste stream. The generation of off-gas and entrainment of volatiles is anticipated to be minimized. However, given the complex nature of spent nuclear fuel (SNF), some volatile components will be generated, including the solvents themselves; Cl 2 used for the regeneration of S 2 Cl 2 ; volatile fission product chlorides, such as Sb and 3 H; and chlorinated alloying components, such as Sn, Nb, Fe, and Mo. This report discusses the chemical phenomena that might give rise to volatile species and their planned capture. The volatility of the transition metals will depend on their oxidation state and the compounds that are formed, such as Zr tritide. Loading radionuclides in the process off-gas will depend on the inputs to the process. For instance, processing separated Zr to reduce waste will have a much lower loading of radionuclides than if alternative chlorination were used for decladding SNF. Much of the volatile process streams will be part of the solvent recycling, which may involve online scrubbing. Generally, a caustic scrubber should be included in the off-gas to remove acidic vapors (e.g., Cl 2 , SOCl 2 ). The decontamination procedures for removing these species could involve pretreatment (i.e., heating) options or reduction by contact with H 2 . This report discusses these options along with a framework for testing these alternatives in future experiments. Technologies for off-gas capture will leverage those developed in the Materials Recovery and Waste Forms program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Molecular understanding of new-particle formation from α-pinene between -50 and +25 °C

Abstract. Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to -50°C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25°C to 0.7 % at -50°C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at -50°C compared with 25°C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

54 ENVIRONMENTAL SCIENCES↗

A petrogenetic model of the relationships among achondritic meteorites

Petrological evidence is used to support the hypothesis that although the magma source regions and parent bodies of basaltic achondrite, shergottite, nakhlite, and chassignite meteorites are clearly distinct, they may be simply related. It is proposed that the peridotites which on partial melting generated the parent magmas of the shergottite meteorites differed from those which gave rise to eucritic magmas by being enriched in a component rich in alkalis and other volatiles. Similarly, the source regions of the parent magmas of the nakhlite and chassignite meteorites differed from those on the shergottite parent body by being still richer in this volatile-rich component. These regions could have been related by processes such as mixture of variable amounts of volatile-rich and volatile-poor components in planetary or nebular settings, or alternatively by variable varying degrees of volatile loss from volatile-rich materials.

Stolper, E.↗

The Fe/Mn constraint on precursors of basaltic achondrites

Most achondritic meteorites have Fe/Mn ratios that are lower than those of carbonaceous chondrites and of course are lower than the solar system abundance ratio of these elements. Models of the origin of achondritic assemblages must, therefore, account for these ratios. Fe/Mn ratios are suggested to be distinctive for samples from each achondrite parent body and for the Earth and Moon, but the correspondence between the Fe/Mn systematics of achondrites and chondritic precursors is unclear. Most models of achondrite genesis involve magmatic differentiation of chondritic precursors. The Fe/Mn difference between achondrites and chondrites is particularly significant since Fe and Mn are geochemically similar elements with similar partitioning behavior in familiar magmatic systems and are generally coupled during crystal-liquid fractionation. In contrast, however, Mn is more volatile than Fe in a nebular setting. Variation of Fe/Mn ratios based on the relative volatility of these elements in the early nebula provides a constraint for models by which the basaltic achondrites (with Fe/Mn ratios approximately = 25-50) are derived from mixtures of nebular components that were enriched in volatile components such as Mn. However, such volatile enriched components have not been identified in chondrites. When the abundance in achondrites of elements of similar volatility is examined, anomalies appear. For example, Na is massively depleted in basaltic achondrites when compared to Mn. These anomalies might be explained using current models but the alternative hypothesis, that Fe/Mn ratio is controlled not by nebular volatility constraints, but by planetary differentiation should be explored.

Delaney, Jeremy S.↗