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The role of volume scattering in reducing spectral contrast of reststrahlen bands in spectra of powdered minerals

The first high-resolution quantitative directional hemispherical reflectance spectra of minerals were obtained for different particle sizes, and were used to develop an accurate prediction of the particles' spectral emissivity, using Kirchhoff's law (Nicodemus, 1965) and to interpret the nature and causes of changes in the spectral contrast of reststrahlen bands. It was found that the reststrahlen bands change in shape as well as intensity; this is explained by the occurrence of substantial volume scattering at fine particle sizes. The implication of this finding for remote sensing of the earth, moon, Mercury, Mars, and the asteroids is discussed.

Salisbury, John W.↗

Observations of silicate reststrahlen bands in lunar infrared spectra

Thermal emission spectra of three lunar sites (Apollo 11, Descartes Formation, and Tycho central peak) are measured in the 8-14 micron spectral range. Transmission and instrument effects are accounted for by forming ratios of the Descartes and Tycho spectra to the Apollo 11 spectrum. The ratio spectra are compared with ratios of published laboratory spectra of returned lunar samples and also with ratio spectra calculated using the Aronson-Emslie (1975) model. The comparisons show pyroxene bands in the Descartes ratio spectrum and plagioclase bands in the Tycho ratio spectrum. The Tycho spectrum is found to be consistent with the existence of fine plagioclase dust (approximately 1 micron) at the rock surface and a higher-than-usual sodium content of the plagioclase.

Potter, A. E., Jr.↗

Mineralogy and Thermal Properties of V-Type Asteroid 956 Elisa: Evidence for Diogenitic Material from the Spitzer IRS (5-35 Micrometers) Spectrum

We present the thermal infrared (5-35 micrometer) spectrum of 956 Elisa as measured by the Spitzer Infrared Spectrograph ("IRS"; Houck,1.R. et .11. [20041. Astrophys, 1. SuppL 154, 18-24) together with new ground-based lightcurve data and near-IR spectra. From the visible lightcurve photometry, we determine a rotation period of 16.494 +/- 0.001 h, identify the rotational phase of the Spitzer observations, and estimate the visible absolute magnitude (Hv) at that rotational phase to be 12.58 +/- 0.04. From radiometric analysis of the thermal flux spectrum, we find that at the time of observation 956 Elisa had a projected radius of 5.3 +/- 0.4 km with a visible albedo pv = 0.142+/- 0.022, significantly lower than that of the prototype V-type asteroid, 4 Vesta. (This corresponds to a radius of 5.2 +/- 0.4 km at lightcurve mean.) Analysis with the standard thermal model (STM) results in a sub-solar temperature of 292.3 +/- 2.8 K and beaming parameter eta = 1.16 +/- 0.05. Thermophysical modeling places a lower limit of 20 J m(exp -2)K(exp -1)s(exp -1/2) on the thermal inertia of the asteroid's surface layer (if the surface is very smooth) but more likely values fall between 30 and 150 J m(exp -2)K(exp -1)s(exp -1/2) depending on the sense of rotation. The emissivity spectrum, calculated by dividing the measured thermal flux spectrum by the modeled thermal continuum, exhibits mineralogically interpretable spectral features within the 9-12 micrometer reststrahlen band, the 15-16.5 micrometer Si-O-Si stretching region, and the 16-25 micrometer reststrahlen region that are consistent with pyroxene of diogenitic composition: extant diogenitic pyroxenes fall within the narrow compositional range W0(sub 2+/-1)En(sub 74+/-2)Fs(sub 24+/-1). Spectral deconvolution of the 9-12 micrometer reststrahlen features indicates that up to approximately 20% olivine may also be present, suggesting an olivine-diogenite-like mineralogy. The mid-IR spectrum is inconsistent with non-cumulate eucrite as the major component on the surface of 956 Elisa, although cumulate eucrite material may be present at abundances lower than that of the diogenite component. Analysis of new near-IR spectra of 956 Elisa with the Modified Gaussian Model (MGM; Sunshine, J,M., Pieters, C.M., Pratt, S.F.[1990]. J. Geophys. Res, 95 (May), 6955-6966) results in two pyroxene compositions: 75% magnesian low-Ca pyroxene and 25% high-Ca pyroxene. High-Ca pyroxene is not evident in the mid-IR data, but may belong to a component that is underrepresented in the mid-IR spectrum either because of its spatial distribution on the asteroid or because of its particle size. High-Ca pyroxenes that occur as exsolution lamellae may also be more evident spectrally in the NIR than in the mid-IR. In any case, we find that the mid-IR spectrum of 956 Elisa is dominated by emission from material of diogenite- like composition, which has very rarely been observed among asteroids.

Lim, Lucy F.↗

Infrared (2.08-14 micron) spectra of powered stony meteorites

Infrared biconical reflectance spectra of 60 powdered meteorite samples, representing 50 different stony meteorites, were measured as analogues of asteroidal regolith. Representative samples were measured in directional hemispherical reflectance to assure that Kirchhoff's Law can be used to predict relative emissivity from the reflectance spectra. These spectral data confirm that the O-H fundamental absorption band near 2.9 microns is an extremely sensitive indicator of incipient alteration, which often has taken place in powdered meteorite samples exposed only to water vapor in the air. Such non-carbonaceous samples typically contain less than 1 percent water by weight. Likewise, the C-H fundamental absorption bands near 3.4 and 3.5 microns are equally sensitive indicators of contamination with volatile hydrocarbons, which can also be absorbed from the air. The heavy, macromolecular hydrocarbons native to chondrites do not display such heavy bands, making detection of these bands in remote sensing of asteroids unlikely. Despite the spectral artifacts introduced by alteration and hydrocarbon contamination, powdered stony meteorites display a wide variety of real spectral features that can be used for their identification, including residual reststrahlen bands, absorption bands, and the Christiansen feature. Researchers found that the wavelengths of the peaks or troughs of each of these spectral features can be used independently to infer meteorite composition, but the best results are obtained when the entire spectral curve is used, or at least the portion of it encompassed by the 8 to 14 micron atmospheric window, in a digital search library.

Salisbury, J. W.↗

Elimination of cloud effects in sensing ozone from 9.6 micron band.

Description of an objective method for extracting the spectral information from the 9.6 micron region pertaining to atmospheric ozone. This method has been developed by examining a large number of Nimbus 4 infrared interferometer-spectrometer spectra. The method is capable of eliminating, not only the effects of clouds, but also those of interference from the reststrahlen bands of desert sands.

Prabhakara, C.↗

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.↗

Spectral analysis of ALH 84001, a meteorite from Mars

ALH 84001 has recently been reclassified as a meteorite from Mars (SNC) and contains more than 90% orthopyroxene with minor chromite and accessory phases of augite, maskelynite, and carbonate. This meteorite represents a new class of igneous material from Mars. We have measured reflectance spectra of ALH 84001 as a chip as a powder, dry sieved to less than 125 microns to compare with previous spectral analyses of SNCs and remote observations of Mars. Spectra of the chip and powder in the visible-to-near-infrared region are shown. These spectra are composites of data measured with the RELAB bidirectional spectrometer from 0.3 to 2.55 microns and a Nicolet FTIR for longer wavelengths. As expected, the spectra of the chip have negative slopes and are significantly darker than the spectrum of the particulate sample, which has a positive slope. The strong absorptions near 1 micron and 2 microns are characteristic of low-Ca pyroxene and have band rninima of 0.925 microns and 1.930 microns. The strong absorption near 3 microns is characteristic of water. There is a distinct flattening in the spectrum between 1.0 and 1.5 microns indicating the presence of an additional absorption. This is interpreted to be the result of Fe(2+) in the M1 site of low-Ca pyroxene. Mid-infrared spectra showing the Christiansen feature and the reststrahlen bands are shown for spectra of the powder and of three different locations on the chip. These spectra exhibit several features in this range, some of which are associated with a specific region on the chip. Each of the spectra includes a doublet reststrahlen peak near 1100/cm, and peaks near 880 and 500/cm, which are typical for low-Ca pyroxenes. Weaker features at 940-1000/cm, 600-750/cm, and 530-560/cm are present in spectra from some locations on the chip, but not others, implying compositional and textural variation.

Bishop, J.↗

Comparison of thermal emission spectroscopic measurements of the lunar surface - 1968-1990

Four sets of spectra of resolved locations on the lunar surface obtained by Earth-based telescopes since 1968 are compared. The results obtained show that there is good consistency among the datasets within limits of signal-to-noise, and that ranges of overlap in wavelength and major spectral differences due to both the Christiansen emission peak and reststrahlen bands can be detected in remote measurements of the moon in the thermal infrared wavelength region. The conclusion of Goetz (1968) that only minor differences exist on the lunar surface in the region of thermal emission is found to be incorrect. Direct comparison of the four highest quality spectroscopic experiments in the region of thermal emission from 7 to 14 microns, which collected spectra of spatially resolved locations on the lunar surface, shows that this wavelength region reveals major spectral differences among lunar locations.

Lucey, P. G.↗

Infrared (8-14 microns) remote sensing of soil particle size

Particle size of soils plays a significant role in erosion potential and other mechanical properties. Most soils are dominated by the residual mineral quartz, which displays prominent reststrahlen bands in the 8-14 microns atmospheric window. The Earth Observing System will likely provide world-wide multispectral imagery in the 8-14 microns region via the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) instrument. The ratio of ASTER bands 10/14 can be used to estimate particle size in soils, if other ASTER bands are used to minimize the confusion factors provided by soil moisture, vegetation cover, soil organic content, and the presence of abundant minerals other than quartz. Use of band ratios minimizes the effects of poor surface temperature estimates, but maximizes the need for high signal-to-noise data.

Salisbury, John W.↗

Mapping variations in weight percent silica measured from multispectral thermal infrared imagery - Examples from the Hiller Mountains, Nevada, USA and Tres Virgenes-La Reforma, Baja California Sur, Mexico

Remotely sensed multispectral thermal infrared (8-13 mu m) images are increasingly being used to map variations in surface silicate mineralogy. These studies utilize the shift to longer wavelengths in the main spectral feature in minerals in this wavelength region (reststrahlen band) as the mineralogy changes from felsic to mafic. An approach is described for determining the amount of this shift and then using the shift with a reference curve, derived from laboratory data, to remotely determine the weight percent SiO2 of the surface. The approach has broad applicability to many study areas and can also be fine-tuned to give greater accuracy in a particular study area if field samples are available. The approach was assessed using airborne multispectral thermal infrared images from the Hiller Mountains, Nevada, USA and the Tres Virgenes-La Reforma, Baja California Sur, Mexico. Results indicate the general approach slightly overestimates the weight percent SiO2 of low silica rocks (e.g. basalt) and underestimates the weight percent SiO2 of high silica rocks (e.g. granite). Fine tuning the general approach with measurements from field samples provided good results for both areas with errors in the recovered weight percent SiO2 of a few percent. The map units identified by these techniques and traditional mapping at the Hiller Mountains demonstrate the continuity of the crystalline rocks from the Hiller Mountains southward to the White Hills supporting the idea that these ranges represent an essentially continuous footwall block

Stock, Joann M.↗

Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC)

METRIC is a robotic science laboratory that can determine the mineralogy, elemental chemistry, micromorphology, and thermophysical properties of planetary regolith. The METRIC suite comprises METRIC XRD/F, an X-ray diffraction/X-ray fluorescence instrument that can determine the mineralogy and elemental chemistry of regolith samples; METRIC XCT, a micro X-ray computed tomography instrument that can be used to evaluate grain/crystallite sizes and textures; METRIC IRS, an imaging spectrometer mounted on a rover that can determine mineralogy and thermophysical properties at the landing site; and a pneumatic sample collection, processing, distribution system developed by Honeybee Robotics. The payload elements could be deployed on a static lander or a rover. Data returned from the METRIC payload would inform origin, formation, and evolution of rocky planetary bodies. METRIC XRD/F draws on heritage from the CheMin instrument on the Mars Science Laboratory (MSL) Curiosity rover [1], with a few important improvements. Like CheMin, METRIC XRD/F operates in transmission geometry and uses piezoelectric actuators on sample cells in a tuning fork geometry to induce convective grain motion of the regolith to create a randomly oriented powder. MSL CheMin uses an energy-sensitive CCD to collect XRD patterns and XRF spectra simultaneously from the same sample cell, resulting in qualitative XRF data. METRIC XRD/F uses two different sample cells, one optimized for XRD and one optimized for XRF, and a silicon drift detector to detect fluoresced X-rays. This improvement to the XRF capabilities provides quantitative geochemical data of major elements down to Z = 11 and allows for the detection of minor and trace elements that are critical for evaluating geologic evolution of the Moon (e.g., P and Th). Modest improvements to the XRD geometry and hardware allow for better angular resolution and the ability to distinguish between members of the pyroxene group. METRIC XCT uses the same geometry and much of the same hardware as METRIC XRD/F, where a CCD would capture images of a regolith sample in a 3 mm diameter sample tube that is rotated 360° in steps <1°. Image brightness can be used to infer compositional data, where brighter materials indicate a higher Z, much like scanning electron microscopy. Data from METRIC XCT complement those from METRIC XRD/F. Particle size, shape, and texture can provide petrologic and provenance information, whereas vesicle size and morphology in volcanic or impact melt lithologies can inform cooling rates. METRIC IRS is a hyperspectral thermal imager that can be mounted to a lander or rover to provide mineralogical data from the broader landing site and help determine whether the samples analyzed by METRIC XRD/F and XCT are representative. The METRIC IRS spectral range (8–14 μm) and resolution (10.8 cm-1) allow for quantitative mineralogy from modelling Reststrahlen bands of major rock-forming minerals (e.g., silicates, phosphates). Radiance cubes can be processed and modelled with an onboard high-performance computer to determine mineral abundances of plagioclase, high-Ca pyroxene, pigeonite, orthopyroxene, olivine, and glass. Regolith samples can be acquired, processed, and delivered to the X-ray instruments via multiple sample handling systems, but the pneumatic sampling systems developed by Honeybee Robotics [e.g., 2] are best suited for relatively low-cost missions that are being competed for the Moon (e.g., NASA’s Payloads and Research Investigations for the Surface of the Moon program). There are pneumatic sampling systems that collect surface material and other systems that pneumatically drill up to ~1 m below the surface, providing material that has not been space weathered and has not been affected by the lander’s exhaust. [1] Blake, D. F., Vaniman, D., Achilles, C., Anderson, R., Bish, D., et al. (2012). Space Sci. Rev. 170, 341-478. https://doi.org/10.1007/s11214-012-9905-1. [2] Zacny, K., Betts, B., Hedlund, M., Long, P., Gramlich, M., Tura, K., Chu, P., Jacob, A., Garcia, A. (2014). IEEE Aerospace Conference, 3-7 March 2014, Big Sky, MT, U.S.A.

X-ray diffraction↗

Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC): A Payload Designed for Exploration of Terrestrial Planetary Bodies

Geological materials (indeed, all solid objects) are characterized by their crystal structure, elemental composition, and morphology. The Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC) instrument suite quantifies all three. These measurements address fundamental science questions (e.g., the origin and evolution of planetary bodies) and support the human exploration of space (e.g., the characterization of regolith for ISRU and the constraint of its geotechnical properties). METRIC comprises an X-ray Diffraction/X-ray Fluorescence instrument (XRD: mineral structure and XRF: elemental composition), an X-ray micro-Computed Tomography instrument (XCT: 3D internal micromorphology), and a hyperspectral imaging infrared spectrometer (IRS) to provide local/regional mineralogic context for these measurements. METRIC XRD/F draws heritage from the highly successful Mars Science Laboratory CheMin instrument. The METRIC XRD/F employs two separate sample cells, one optimized for XRD and one for XRF, resulting in more rapid XRD analysis (tens of minutes vs. tens of hours for CheMin) and an orders-of-magnitude improvement in XRF detection. XCT has not been deployed in space, so the METRIC XCT represents a new capability for solar system exploration. The XCT uses the same basic high-TRL components as METRIC XRD/F, decreasing its development cost for flight. The METRIC IRS is a derivative of the NASA Earth Science Technology Office funded Hyperspectral Thermal Imager instrument and utilizes the NASA Technology Transfer Program to incorporate a commercial-of-the-shelf infrared camera ruggedized for space by NASA Marshall Space Flight Center. The IRS spectral range (8–14 µm) and resolution (10.8 cm -1 ) are tailored to quantify mineralogy in rocks using their characteristic Reststrahlen bands and to characterize mineralogy of soils using the position of the Christensen Feature. The METRIC payload is currently designed for deployment to the Moon on a Commercial Lunar Payload Services (CLPS) mission, where the XRD/F and XCT would be located on a lander and the IRS would be on deployed on a companion rover to evaluate the mineralogical diversity of the landing site. A pneumatic drill designed by Honeybee Robotics would excavate regolith up to 50 cm below the lander and deliver multiple aliquots of regolith to the XRD/F and XCT. The METRIC payload could also be deployed on a rover. In this case, a sample handling system on a robotic arm could scoop regolith and/or drill rocks and deliver powder to the XRD/F and XCT located in the rover’s interior. Alternatively, METRIC instruments could be used singly or in combination on human space missions. The XRD/F and XCT could be used to characterize samples in a rover or in a science laboratory within a habitat. These data could help astronauts identify resource-enriched rocks and regolith and triage geologic samples to return samples of high interest for analysis in terrestrial laboratories. The IRS could be attached to a human-navigated rover to collect mineralogical data along a traverse and identify high-priority science samples.

E. B. Rampe↗

The physical basis for spectral variations in thermal infrared emittance of silicates and application to remote sensing

The use of infrared spectroscopy for the remote characterization of planetary surfaces has received attention due to efforts in the investigation of these bodies from space. In the 8 to 14 micron region, a depression in the emittance spectra of rocks (sometimes called reststrahlen) is related to the fundamental stretching vibrations of Si-O bonds and shifts in the locations of this feature are ascribed to variations in rock composition. Thus, it should be possible to investigate, quantify, and model the relationships of reststrahlen spectral band location through silicate mineralogical composition to rock classification. This concept will be tested first through the use of laboratory-acquired data on the infrared spectra and mineralogy of selected mineral and rock samples. As a suitable classification model is developed, it will be tested through overflights of appropriate rock outcrops using the Thermal Infrared Multispectral Scanner (TIMS).

Walter, Louis S.↗

Applications of an Energy Transfer Model to Three Problems in Planetary Regoliths: The Solid-State Greenhouse, Thermal Beaming, and Emittance Spectra

Several problems of interest in planetary infrared remote sensing are investigated using a new radiative-conductive model of energy transfer in regoliths: the solid-state greenhouse effect, thermal beaming, and reststrahlen spectra. The results of the analysis are as follows: (1) The solid-state greenhouse effect is self-limiting to a rise of a few tens of degrees in bodies of the outer solar system. (2) Non-Lambertian directional emissivity can account for only about 20% of the observed thermal beaming factor. The remainder must have another cause, presumably surface roughness effects. (3) The maximum in a reststrahlen emissivity spectrum does not occur exactly at the Christiansen wavelength where, by definition, the real part of the refractive index equals one, but rather at the first transition minimum in reflectance associated with the transition from particle scattering being dominated by volume scattering to that dominated by strong surface scattering. The transparency feature is at the second transition minimum and does not require the presence of a second band at longer wavelength for its occurance. Subsurface temperature gradients have only a small effect on emissivity bands.

Hapke, Bruce↗

Composite Reflective Absorptive IR-Blocking Filters Embedded in Metamaterial Antireflection Coated Silicon

Infrared (IR)-blocking filters are crucial for controlling the radiative loading on cryogenic systems and for optimizing the sensitivity of bolometric detectors in the far-IR. We present a new IR filter approach based on a combination of patterned frequency-selective structures on silicon and a thin (2575 micron thick) absorptive composite based on powdered reststrahlen absorbing materials. For a 300 K blackbody, this combination reflects approximately 50% of the incoming light and blocks greater than.99.8% of the total power with negligible thermal gradients and excellent low-frequency transmission. This allows a reduction in the IR thermal loading to negligible levels in a single cold filter. These composite filters are fabricated on silicon substrates, which provide excellent thermal transport laterally through the filter and ensure that the entire area of the absorptive filter stays near the bath temperature. A metamaterial antireflection coating cut into these substrates reduces in-band reflections to below 1%, and the in-band absorption of the powder mix is below 1% for signal bands below 750 GHz. This type of filter can be directly incorporated into silicon refractive optical elements.

Munson, C. D.↗