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Optical Properties of Astronomical Silicates with Infrared Techniques (OPASI-T)

Astronomical dust is observed in a variety of astrophysical environments and plays an important role in radiative processes and chemical evolution in the galaxy. Depending upon the environment, dust can be either carbon-rich or oxygen-rich (silicate grains). Both astronomical observations and ground-based data show that the optical properties of silicates can change dramatically with the crystallinity of the material, and recent laboratory research provides evidence that the optical properties of silicate dust vary as a function of temperature as well. Therefore, correct interpretation of a vast array of astronomical data relies on the understanding of the properties of silicate dust as functions of wavelength, temperature, and crystallinity. The OPASI-T (Optical Properties of Astronomical Silicates with Infrared Techniques) project addresses the need for high quality optical characterization of metal-enriched silicate condensates using a variety of techniques. A combination of both new and established experiments are used to measure the extinction, reflection, and emission properties of amorphous silicates across the infrared (near infrared to millimeter wavelengths), providing a comprehensive data set characterizing the optical parameters of dust samples. We present room temperature measurements and the experimental apparatus to be used to investigate and characterize additional metal-silicate materials.

Rinehart, Stephen↗

Crystal Structure and Chemical Composition of a Presolar Silicate from the Queen Elizabeth Range 99177 Meteorite

Mineral characterization of presolar silicate grains, the most abundant stardust phase, has provided valuable information about the formation conditions in circumstellar environments and in super-nova (SN) outflows. Spectroscopic observations of dust around evolved stars suggest a majority of amor-phous, Mg-rich olivine grains, but crystalline silicates, most of which are pyroxene, have also been observed [1]. The chemical compositions of hundreds of presolar silicates have been determined by Auger spectroscopy and reveal high Fe contents and nonstoichiometric compositions intermediate to olivine and pyroxene [2-6]. The unexpectedly high Fe contents can partly be attributed to secondary alteration on the meteorite parent bodies, as some grains have Fe isotopic anomalies from their parent stellar source [7]. Only about 35 presolar silicates have been studied for their mineral structures and chemical compositions by transmission electron microscopy (TEM). These grains display a wide range of compositions and structures, including crystalline forsterite, crystalline pyroxene, nanocrystalline grains, and a majority of amorphous nonstoichiometric grains. Most of these grains were identified in the primitive Acfer 094 meteorite. Presolar silicates from this meteorite show a wide range of Fe-contents, suggestive of secondary processing on the meteorite parent body. The CR chondrite QUE 99177 has not suffered as much alteration [8] and displays the highest presolar silicate abundance to date among carbonaceous chondrites [3, 6]. However, no mineralogical studies of presolar silicates from this meteorite have been performed. Here we examine the mineralogy of a presolar silicate from QUE 99177.

Nguyen, A. N.↗

Layer silicates in a chondritic porous interplanetary dust particle

Analytical electron microscopy on individual grains from a portion of a chondritic porous interplanetary dust particle (aggregate W7029C1 from the NASA Johnson Space Center Cosmic Dust Collection) shows that layer silicates compose 50 percent of the silicate fraction examined. These layer silicates can be classified into two distinct crystallochemical groups: (1) fine-grained, polycrystalline smectite minerals; and (2) well-ordered, single crystals of kaolinite and Mg-poor talc. The layer silicates in this portion of sample W7029(asterisk)A are dissimilar to those described in other chondritic porous aggregates. The predominant layer silicate assemblage in W7029(asterisk)A indicates that heating of the aggregate during atmospheric entry was brief and probably to a temperature less than 300 C. Comparison with terrestrial phyllosilicate occurrences suggests that some layer silicates in aggregate W7029(asterisk)A may have been formed by alteratiton from preexisting silicate minerals at low temperatures (less than 25 C) after aggregate formation.

Rietmeijer, F. J. M.↗

Physical processes affecting availability of dissolved silicate for diatom production in the Arabian Sea

A passive tracer to represent dissolved silicate concentrations, with biologically realistic uptake kinetics, is successfully incorporated into a three-dimensional, eddy-resolving, ocean circulation model of the Indian Ocean. Hypotheses are tested to evaluate physical processes which potentially affect the availability of silicate for diatom production in the Arabian Sea. An alternative mechanism is offered to the idea that open ocean upwelling is primarily responsible for the high, vertical nutrient flux and consequent large-scale phytoplankton bloom in the northwestern Arabian Sea during the southwest monsoon. Model results show that dissolved silicate in surface waters available for uptake by diatoms is primarily influenced by the intensity of nearshore upwelling from soutwest monsoonal wind forcing and by the offshore advective transport of surface waters. The upwelling, which in the model occurs within 200 +/- 50 km of the coast, appears to be a result of a combination of coastal upwelling, Elkman pumping, and divergence of the coastal flow as it turns offshore. Localized intensifications of silicate concentrations appear to be hydrodynamically driven and geographically correlated to coastal topographic features. The absence of diatoms in sediments of the eastern Arabian Basin is consistent with modeled distributional patterns of dissolved silicate resulting from limited westward advection of upwelled coastal waters from the western continental margin of India and rapid uptake of available silicate by diatoms. Concentrations of modeled silicate become sufficiently low to become unavailable for diatom production in the eastern Arabian Sea, a region between 61 deg E and 70 deg E at 8 deg N on the south, with the east and west boundaries converging on the north at approximately 67 deg E, 20 deg N.

Young, David K.↗

Chronology and Petrology of Silicates From IIE Iron Meteorites: Evidence of a Complex Parent Body Evolution

IIE iron meteorites contain silicate inclusions whose characteristics suggest a parent body similar to that of H-chondrites. However, these silicates show a wide range of alteration, ranging from Netschadvo and Techado, whose inclusions are little altered. to highly differentiated silicates like-those in Kodaikanal, Weekeroo Station and Colomera, which have lost metal and sulfur and are enriched in feldspar. We find these inclusions to show varying degrees of shock alteration. Because only a limited amount of data on - isotopic ages of HE silicates were available, we made Ar-39 - Ar-40 age determinations of Watson, Techado, miles Colomera, and Sombrerete. Watson has an Ar-Ar age of 3.653 +/- 0.012 Gyr, similar to previously reported ages for Kodaikanal and Netschadvo. We suggest that the various determined radiometric ages of these three meteorites were probably reset by a common impact event. The space exposure ages for these three meteorites are also similar to each other and are considerably younger than exposure ages of other IIEs. Ar-39 - Ar-40 ages inferred for the other four meteorites analyzed are considerably older than Watson and are: Techado =4.49 +/- 0.01 Gyr, Miles =4.412 +/- 0.016 Gyr, Colomera =4.469 +/- 0.012 Gyr, and Sombrerete =4.535 +/- 0.005 Gyr. These ages are in fair agreement with previously reported Rb-Sr isochron ages for Colomera and Weekeroo Station. Although several mechanisms to form HE meteorites previously were suggested, it is not obvious that a single mechanism could produce a suite of meteorites with very different degrees of silicate differentiation and with isotopic ages that differ by >0.8 Gyr. We suggest that those IIEs with older isotopic ages are a product of partial melting and differentiation within the parent body, followed by mixing of silicate and metal while both were relatively hot. Netschadvo and Watson may have formed by this same process or by impact mixing about 4.5 Gyr ago, but their isotopic ages were subsequently reset by shock heating. Kodaikanal apparently is required to have formed more recently, in which case impact melting and differentiation seems the only viable process. We see no compelling reasons to believe that IIE silicate and metal derived from different parent bodies or that the parent body of IIEs was the same as that of H-chondrites.

Bogard, Donald D.↗

High Silicate Crystalline-to-Amorphous Ratios in Comets C/2001 Q4 (NEAT) and Hale-Bopp

Crystalline silicates, by their apparent absence in the ISM, are dust grains that experienced high temperatures in the solar nebula. Mg-rich crystalline silicates formed either by condensation from hot nebular gases (1450 K) or by the annealing of Mg-rich amorphous silicates (approx. 1000 K) in shocks in the 5-10 AU region or by radial transport into and out of the hot inner zones, e.g., T(sub d) > 1000 K at r(sub h) < 5 AU, 10(exp -6) - 10(exp -5) M(sub O)/yr, alpha = 10(exp -4) of the early solar nebula. Mg-rich crystalline silicates are found in interplanetary dust particles (IDPs) and produce IR spectral features in many Oort cloud comets. In May 2004, we discovered strong crystalline silicate features in the dynamically new Oort cloud comet C/2001 Q4 (NEAT). Thermal emission modeling of comets Q4 and C/1995 O1 (Hale-Bopp) demonstrate that both these comets have similar, high silicate crystalline-to-amorphous ratios of 2.4 and 2.1, respectively, indicating that these icy planetesimals aggregated from similar reservoirs of material or that crystalline silicates were widely distributed within the comet-forming zone. This argues for efficient annealing mechanisms and radial mixing.

Wooden, D. H.↗

High Silicate Crystalline-to-Amorphous Ratios in Comets C/2001 Q4 (NEAT) and Hale-Bopp

Crystalline silicates, by their apparent absence in the ISM, are dust grains that experienced high temperatures in the solar nebula. Mg-rich crystalline silicates formed either by condensation from hot nebular gases (1450 K) or by the annealing of Mg-rich amorphous silicates (approximately 1000 K) in shocks in the 5-10AU region or by radial transport into and out of the hot inner zones, e.g., T(sub d) greater than 1000K at r(sub h) less than 5AU, 10(exp -6) -10(exp -5) solar mass per year, alpha = 10(exp -4) of the early solar nebula. Mg-rich crystalline silicates are found in interplanetary dust particles (IDPs) and produce IR spectral features in many Oort cloud comets. In May 2004, we discovered strong crystalline silicate features in the dynamically new Oort cloud comet C/2001 Q4 (NEAT). Thermal emission modeling of comets Q4 and C/1995 O1 (Hale-Bopp) demonstrate that both these comets have similar, high silicate crystalline-toamorphous ratios of 2.4 and 2.1, respectively, indicating that these icy planetesimals aggregated from similar reservoirs of material or that crystalline silicates were widely distributed within the comet-forming zone. This argues for efficient annealing mechanisms and radial mixing.

Wooden, D. H.↗

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

Nguyen, A. N.↗

Thermochemistry of Protective Coatings and Molten Silicate Debris

The durability of gas-turbine engine components can be significantly affected by the ingestion of siliceous particles, which can melt at high temperature and corrode protective coatings that are essential for long life requirements. The silicate debris consists mainly of CaO-MgO-Al2O3-SiO2 (CMAS) and is usually ingested by aircraft engines during and after take-off, sticking to their hot surfaces and resulting in the formation of calcium rare-earth silicate oxyapatites. The thermochemistry of coatings and their reaction products with molten silicate debris are crucial to understand in order to improve the durability of gas-turbine engines. Here we discuss results of high temperature drop solution calorimetry, drop-and-catch calorimetry (DnC) and differential thermal analysis (DTA) techniques for the thermodynamic properties of both thermal barrier coatings (TBCs) and environmental barrier coatings (EBCs) and their reaction with CMAS compositions. The enthalpies of solution of Y2Si2O7, Yb2Si2O7, 31YSZ, and 16RESZ based coatings and the oxyapatite are moderately positive. However, oxyapatite formation is only favorable over coating dissolution in terms of enthalpy for 7YSZ. The enthalpies of mixing between the coatings and the molten silicate are less exothermic for Yb2Si2O7 and CaYb4Si3O13 than for 7YSZ, indicating lower energetic stability of the latter against molten silicate corrosion. We also report for the first time the calorimetric measurements of the enthalpies of formation of rare-earth silicate based EBC coatings and oxyapatites (rare-earth, RE = Y, Yb, Gd, Dy, Er, Nd and Sm).

Costa, Gustavo↗

The Mid-IR Spectral Effects of Darkening Agents and Porosity on the Silicate Surface Features of Airless Bodies

We systematically measured the mid-IR spectra of different mixtures of three silicates (antigorite, lizardite, and pure silica) with varying effective porosities and amounts of darkening agent (iron oxide and carbon). These spectra have broad implications for interpretation of current and future mission data for airless bodies, as well as for testing the capabilities of new instruments. Serpentines, such as antigorite and lizardite, are common to airless surfaces, and their mid-IR spectra in the presence of darkening agents and different surface porosities would be typical for those measured by spacecraft. Silica has only been measured in the plumes of Enceladus and presents exciting possibilities for other Saturn-system surfaces due to long range transport of E-ring material. Results show that the addition of the IR-transparent salt, KBr, to simulate surface porosity affected silicate spectra in ways that were not predictable from linear mixing models. The strengthening of silicate bands with increasing pore space, even when only trace amounts of KBr were added, indicates that spectral features of porous surfaces are more detectable in the mid-IR. Combining iron oxide with the pure silicates seemed to flatten most of the silicate features, but strengthened the reststrahlen band of the silica. Incorporating carbon with the silicates weakened all silicate features, but the silica bands were more resistant to being diminished, indicating silica may be more detectable in the mid-IR than the serpentines. We show how incorporating darkening agents and porosity provides a more complete explanation of the mid-IR spectral features previously reported on worlds such as Iapetus.

Young, Cindy L.↗

Estimation of Sorption Behavior of Europium to Calcium Silicate Hydrate by Thermal Analysis - 20172

High-level radioactive waste generated from reprocessing processes will be disposed in a geological disposal that is deep underground. Calcium silicate hydrate is formed as a secondary mineral in the repository via the reaction of calcium ions leaching from the cement and the silicic acid dissolved from the host rocks. In this study, the sorption behavior of europium, which is also known as a chemical analog of americium, on calcium silicate hydrate was examined. The solid phase was analyzed via thermogravimetry- differential thermal analysis, differential scanning calorimetry, Raman spectroscopy, fluorescence spectroscopy, and fluorescence lifetime analysis. To understand the behavior of calcium silicate hydrate under conditions saturated with groundwater, the study samples were analyzed using the above methods, except for deferential scanning calorimetry, without a drying process. The results of the differential scanning calorimetry analyses showed that the temperatures for the endothermic peaks of calcium silicate hydrate for the lower Ca/Si ratios were larger than those for the higher Ca/Si ratios for coexistent conditions of europium ions. Hence, the relationships of the temperatures of the endothermic peaks and the Ca/Si ratios were reversed by the addition of europium ions. These study results suggest that calcium silicate hydrate can immobilize europium ions, thus preventing the production of colloidal forms. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evidence of formation of an amorphous magnesium silicate (AMS) phase during alkali activation of (Na-Mg) aluminosilicate glasses

Highlights: • No hydrotalcite-group phase is formed as Al preferentially incorporates into zeolites. • Mg forms an amorphous Mg silicate (AMS) phase. • AMS is a more depolymerized phase when compared to Mg silicate hydrate (M-S-H). • High charge density of Mg effectively stabilizes depolymerized silicates in AMS phase. • Existence of AMS phase should be considered as possibility in Mg-rich AAMs. There is some ambiguity regarding the fate of Mg during the alkali activation of Mg-rich precursors within the broader field of alkali activated materials (AAMs). The present work addresses this issue by studying the reaction products in AAMs synthesized from (Na-Mg) aluminosilicate glasses. Here, instead of magnesium silicate hydrate (M-S-H) phase, Mg exclusively forms an amorphous magnesium silicate (AMS) phase. Compared to M-S-H, AMS is a more depolymerized phase, which has not previously been well documented. The formation of AMS seems to be driven by the high charge density of the Mg cation which effectively stabilizes the depolymerized silicate species. We also show that the lack of hydrotalcite-group phases is due to aluminum depletion by zeolite formation. This work highlights the need to consider the existence of the AMS phase in Mg-containing AAMs, especially in complex systems, where its identification may be difficult.

36 MATERIALS SCIENCE↗

A numerical examination of the effect of sulfide dissolution on silicate weathering

Silicate weathering regulates climate on geological time scales as a net, climate-sensitive sink of atmospheric CO 2 . On the other hand, sulfuric acid produced through sulfide dissolution affects silicate weathering, diminishing its effectiveness as a climate regulator based on evidence from river chemistry. This study takes a theoretical approach to quantitatively examine the effect of sulfide dissolution, coupling a one-dimensional model of pyrite weathering to that of albite transformation to kaolinite. The coupled model reveals that when the reaction front of sulfide is deeper than that of silicates reacting with CO 2 , the silicate-weathering feedback on climate is not directly affected by sulfide dissolution, but only indirectly through oceanic processes such as reverse weathering and carbonate deposition. In turn, when sulfide dissolution occurs within zones of CO 2 -silicate reactions close to the surface, the feedback between climate and silicate weathering can be significantly weakened because sulfuric acid competes effectively with carbonic acid in mineral dissolution. As the depth of the sulfide reaction front can be changed by variations in water table depth, the latter feedback weakening could have occurred in concert with climate-change-driven water table fluctuations, amplifying atmospheric CO 2 variations during the Phanerozoic.

58 GEOSCIENCES↗

In situ X-ray diffraction of silicate liquids and glasses under dynamic and static compression to megabar pressures

Properties of liquid silicates under high-pressure and high-temperature conditions are critical for modeling the dynamics and solidification mechanisms of the magma ocean in the early Earth, as well as for constraining entrainment of melts in the mantle and in the present-day core–mantle boundary. In this paper, we present in situ structural measurements by X-ray diffraction of selected amorphous silicates compressed statically in diamond anvil cells (up to 157 GPa at room temperature) or dynamically by laser-generated shock compression (up to 130 GPa and 6,000 K along the MgSiO 3 glass Hugoniot). The X-ray diffraction patterns of silicate glasses and liquids reveal similar characteristics over a wide pressure and temperature range. Beyond the increase in Si coordination observed at 20 GPa, we find no evidence for major structural changes occurring in the silicate melts studied up to pressures and temperatures exceeding Earth’s core mantle boundary conditions. This result is supported by molecular dynamics calculations. Our findings reinforce the widely used assumption that the silicate glasses studies are appropriate structural analogs for understanding the atomic arrangement of silicate liquids at these high pressures.

58 GEOSCIENCES↗

Machine Learning Approaches for Rare-Earth Silicate Environmental Barrier Coating Thermochemical and Thermomechanical Property Predictions

Environmental barrier coatings (EBCs) are a necessary enabling technology for the transition from superalloys to silicon carbide (SiC) ceramic matrix composites (CMCs) in gas turbine engines for increased efficiency and decreased fuel costs. SiC-based CMCs are prone to oxidation-based degradation in the engine hot section, and rare-earth (RE) silicates are promising candidates for EBCs due to their close thermal expansion match to the composite substrate and oxidation resistance. However, the design of EBCs is hindered by the large chemical space of candidate materials and the difficulty in obtaining material properties for engineering optimization. This is especially difficult as research continues into mixed-cation or “high-entropy” RE silicates. First-principles computational methods such as density functional theory (DFT) are highly effective at calculating material properties to guide coating design but are limited by their computational cost. Atomistic simulations have the potential to both accelerate property calculations and expand the properties able to be calculated due to their lower computational compared to DFT. However, they require interatomic potentials (IAPs) specific to the material system of interest, and, to our knowledge, there are no suitable IAPs for RE silicates. Machine learning (ML) is a promising technique to accelerate material property predictions indirectly by generating IAPs for atomistic simulations or via direct prediction. In this work, we present two ML approaches to accelerate the calculation of RE silicate properties relevant to EBC design: 1) a ML-derived interatomic potential (IAP) for atomistic simulations of yttrium disilicate (Y2Si2O7) from DFT training data, and 2) a neural network (NN) model to directly predict thermochemical properties of RE silicates and oxides directly from easily obtainable unit cell parameters. Classical MD simulations using the IAP yield lattice properties and bond lengths in good agreement with both DFT and experimental results from x-ray diffraction. Thermodynamic properties calculated using the finite-displacement phonon method and quasi-harmonic approximation were orders of magnitude faster than DFT with good agreement to the DFT results. The IAP was also used to calculate properties such as coefficient of thermal expansion (CTE) that require large simulation supercells and are therefore difficult with DFT. The IAP correctly predicted the anisotropic nature of the CTE in three different phases of Y2Si2O7. The NN model predicts constant pressure heat capacity, Cp, orders of magnitude faster than DFT calculations, which can enable its use as a surrogate model for multiscale simulations. The two methods presented in this work demonstrate the utility of ML for accelerating the prediction of RE silicate properties, which can in turn accelerate EBC design and optimization.

machine learning↗

The Sm-Nd systematics of silicate inclusions in iron meteorites: Results from Caddo (IAB)

The timing of events leading to the formation of silicate-rich and metal-rich regions in planetesimals remains an important problem in the study of planetary formation and differentiation in the early solar system. The IAB irons are especially important as they are considered to represent a magmatic differentiation series. Iron meteorites present a particular challenge for chronological studies, due to the relative paucity of phases serving as hosts for radioactive parent-daughter nuclides. Recent work using the Re-Os system, following on the pioneering work by Herr et al. and Luck and Allegre, appears promising, but investigators up to now have concentrated on whole rock isochrons. Silicate clasts enclosed within iron meteorites can provide information about the chronology and thermal history of irons. Extensive work on Rb-Sr, K-Ar, and I-Xe has been reported on silicate inclusions in iron meteorites. We report the initial results from our Sm-Nd study of an inclusion with the Caddo IAB iron, the first Sm-Nd isotopic study of a silicate clast embedded within an iron meteorite. Our results include measurements of the standard long-lived Sm-147/Nd-143 (tau = 152 AE) system, as well as the shorter-lived SM-146/Nd-142 (tau = 0.149 AE) system, which has been shown to be very useful in deciphering the history of the early solar system. The Caddo silicate clast was described by Palme et al., who kindly provided us with a major part of the inclusion. The inclusion is coarse-grained consisting predominantly of olivine, clinopyroxene, and plagioclase, with lesser amounts of orthopyroxene, Fe-Ni metal, sulfide, and phosphate. The relatively large grain size (up to 3 mm) and 120 degree grain boundaries suggest extensive metamorphism at high temperatures. Based on study of a thin section, there is evidence for metal invading along grain boundaries in some regions of the inclusion, suggesting that the Fe-Ni metal was molten when the silicate clast was incorporated. Metamorphic recrystallization may have occurred during this event.

Stewart, Brian W.↗

Genesis of the IIICD iron meteorites - Evidence from silicate-bearing inclusions

Our studies of the silicate-bearing inclusions in the IIICD iron meteorites Maltahohe, Carlton, and Dayton suggest that their mineralogy and mineral compositions are related to the composition of the metal in the host meteorites. An inclusion in the low-Ni Maltahohe is similar in mineralogy to those in IAB irons, which contain olivine, pyroxene, plagioclase, graphite, and troilite. With increasing Ni concentration of the metal, silicate inclusions become poorer in graphite, richer in phosphates, and the phosphate and silicate assemblages become more complex. Dayton contains pyroxene, plagioclase, SiO2, brianite, panethite, and whitlockite, without graphite. In addition, mafic silicates become more FeO-rich with increasing Ni concentration of the hosts. In contrast, silicates in IAB irons show no such correlation with host Ni concentration, nor do they have the complex mineral assemblages of Dayton. These trends in inclusion composition and mineralogy in IIICD iron meteorites have been established by reactions between the S-rich metallic magma and the silicates, but the physical setting is uncertain. Of the two processes invoked by other authors to account for groups IAB and IIICD, fractional crystallization of S-rich cores and impact generation of melt pools, we prefer core crystallization. We suggest that the solidification of the IIICD core may have been very complex, involving fractional crystallization, nucleation effects and, possibly, liquid immiscibility.

Mccoy, Timothy J.↗

Silicate Mineralogy of the Dust in the Inner Coma of Comet C/1995 01 (Hale-Bopp) Pre- and Post-Perihelion

We present 7.6 - 13.3 microns infrared (IR) spectrophotometry (R approx. = 180 - 350) of the 10 microns silicate emission from dust in the inner coma (i.e., within a diameter of 3in.) of comet C/1995 O1 (Hale-Bopp) at four temporal epochs from 1996 October through 1997 June during Hale-Bopp s approach to, arrival at, and recession from perihelion. The HIFOGS spectra at large heliocentric distances exhibit strong emission peaks from 9.9 - 10.1 microns and at 11.2 microns. The HIFOGS spectra of Hale-Bopp taken 1996 October 07 - 14 UT are identical in shape to the ISO SWS spectrum at 2.8 AU obtained on 1996 October 06 UT. Magnesium-rich olivine was unambiguously identified due to presence of the expected 11.2 microns peak along with the matching far-IR 18 microns, 23 microns, and 33 microns peaks in the ISO SWS spectrum. In contrast, to large heliocentric distances, we find that the silicate feature at small heliocentric distances (tau(sub lambda) less than or = 1.7 AU) exhibits strong peaks at 9.3 microns, 9.9 - 10.1 microns, and 11.2 microns, and weak at 10.5 microns and 11.8 microns. We will show that the dramatic increase of the 9.3 microns and 10.0 microns peaks close to perihelion leads to the hypothesis that there are two crystalline grain components with significantly different temperatures. The hotter mineral species (including olivines) radiate over a large range of heliocentric distances at detectable leve!s. The cooler mineral species (pyroxenes) radiate on the Wien side of the blackbody, too faint to detect in the mid-infrared spectra, until close to the sun when this species radiates on the Reyleigh-Jeans tail and becomes apparent. Decomposition of the observed silicate emission features into mineral components through comparison of the height and shape of the silicate feature ("Flux/cont") derived from the cometary spectra, to optical extinctions (Qext) derived from laboratory measurements of terrestrial silicate minerals and interplanetary dust particles (IDPs) is successful for a combination of warm grains (consisting of olivines, amorphous olivines, amorphous pyroxenes, and layer-lattice silicates) and cool grains (crystalline pyroxenes).

Wooden, Diane H.↗