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Organic Molecules On the Surfaces of Iapetus and Phoebe

Absorption bands of both aliphatic and aromatic organic molecules are found in the reflectance spectra of Saturn satellites Iapetus, Phoebe, and Hyperion obtained with the Cassini Visible-Infrared Mapping Spectrometer (VIMS). The VIMS data do not fully resolve the individual bands of C-H functional groups specific to particular molecules, but instead show absorption envelopes representing blended clusters of the bands of aromatic (approximately 3.28 microns) and aliphatic (approximately 3.4 microns) hydrocarbons known in spectra of interstellar dust. In Cruikshank et al. (2014), we matched components of the unresolved hydrocarbon band envelopes with clusters of bands of a range of functional groups in specific types of organic compounds (e.g., normal and N-substituted polycyclic aromatic hydrocarbons, olefins, cycloalkanes, and molecules with lone-pair interactions of N and O with CH3+). In the work reported here, we revisit the spectra of Iapetus and Phoebe using VIMS data processed with improved radiometric and wavelength calibration (denoted RC19). The band envelopes of both aromatic and aliphatic hydrocarbons are now more clearly defined, corroborating the provisional assignment of specific classes of molecules in Cruikshank et al. 2014, but permitting a more reliable quantitative assessment of the relative contributions of those classes, and a revision to the earlier estimate of the ratio of the abundances of aromatic to aliphatic molecules.

Phoeb↗

Manufacturing of HEAs at Different Scales

The knowledge gained from melting and processing of high-entropy alloys (HEAs) at different scales is discussed with respect to melt parameters and characteristics. The melting techniques considered are button melting, vacuum induction melting (VIM) and electroslag remelting (ESR). While VIM produces HEAs with enhanced chemical homogeneity, particularly after being subjected to a homogenization heat treatment, and refined grain structure, other concerns arise from elemental contaminants associated with industrial-grade melt stock. Although ESR of the VIM product decreases the concentration of tramp elements, the narrow melt range typically found in HEAs or medium entropy alloys was found to decrease the melt efficiency. The experiments presented were performed on ingots ranging from 100 g to 75 kg.

Detrois, Martin↗

The Atmospheres of Saturn and Titan in the Near-Infrared: First Results of Cassini/VIMS

The wide spectral coverage and extensive spatial, temporal, and phase-angle mapping capabilities of the Visual Infrared Mapping Spectrometer (VIMS) onboard the Cassini-Huygens Orbiter are producing fundamental new insights into the nature of the atmospheres of Saturn and Titan. For both bodies, VIMS maps over time and solar phase angles provide information for a multitude of atmospheric constituents and aerosol layers, providing new insights into atmospheric structure and dynamical and chemical processes. For Saturn, salient early results include evidence for phosphine depletion in relatively dark and less cloudy belts at temperate and mid-latitudes compared to the relatively bright and cloudier Equatorial Region, consistent with traditional theories of belts being regions of relative downwelling. Additional Saturn results include (1) the mapping of enhanced trace gas absorptions at the south pole, and (2) the first high phase-angle, high-spatial-resolution imagery of CH4 fluorescence. An additional fundamental new result is the first nighttime near-infrared mapping of Saturn, clearly showing discrete meteorological features relatively deep in the atmosphere beneath the planet's sunlit haze and cloud layers, thus revealing a new dynamical regime at depth where vertical dynamics is relatively more important than zonal dynamics in determining cloud morphology. Zonal wind measurements at deeper levels than previously available are achieved by tracking these features over multiple days, thereby providing measurements of zonal wind shears within Saturn's troposphere when compared to cloudtop movements measured in reflected sunlight. For Titan, initial results include (1) the first detection and mapping of thermal emission spectra of CO, CO2, and CH3D on Titan's nightside limb, (2) the mapping of CH4 fluorescence over the dayside bright limb, extending to approximately 750 km altitude, (3) wind measurements of approximately 0.5 ms(exp -1), favoring prograde, from the movement of a persistent (multiple months) south polar cloud near 88 deg S latitude, and (4) the imaging of two transient mid-southern-latitude cloud features.

Cassini Mission↗

Results from a controlled depleted uranium metal casting experiment designed to investigate nuclear Forensic Radiochronometry Signatures

The accurate interpretation of uranium metal 230 Th/ 234 U and 231 Pa/ 235 U radiochronometry model ages requires an understanding of how uranium parent nuclides and decay progeny ( 230 Th and 231 Pa) behave during uranium metal casting. In order to directly measure the spatial distribution of 230 Th and 231 Pa in uranium metal before and after vacuum induction melting (VIM), Los Alamos National Laboratory identified uranium metal feedstock, characterized the metal feedstock, conducted a controlled casting experiment of an approximately 120 kg uranium metal rod, and characterized the cast metal. Herein this study presents radiochronometry results and quantified 230 Th and 231 Pa VIM separation factors from bulk uranium.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Polymeric ionic liquids containing copper(I) and copper(II) ions as gas chromatographic stationary phases for olefin separations

Copper(I) ions (Cu + ) are used in olefin separations due to their olefin complexing ability and low cost, but their instability in the presence of water and gases limits their widespread use. Ionic liquids (ILs) have emerged as stabilizers of Cu + ions and prevent their degradation, providing high olefin separation efficiency. There is limited understanding into the role that polymeric ionic liquids (PILs), which possess similar structural characteristics to ILs, have on Cu + ion-olefin interactions. Moreover, copper ions with diverse oxidation states, including Cu + and Cu 2+ ions, have been rarely employed for olefin separations. In this study, gas chromatography (GC) is used to investigate the interaction strength of olefins to stationary phases composed of the 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 6 MIM + ][NTf 2 – ]) IL and the poly(1-hexyl-3-vinylimidazolium [NTf 2 – ]) (poly([C 6 VIM + ][NTf 2 – ])) PIL containing monovalent and divalent copper salts (i.e., [Cu + ][NTf 2 – ] and [Cu 2+ ]2[NTf 2 – ]). The chromatographic retention of alkenes, alkynes, dienes, and aromatic compounds was examined. Incorporation of the [Cu 2+ ]2[NTf 2 – ] salt into a stationary phase comprised of poly(dimethylsiloxane) resulted in strong retention of olefins, while its addition to the [C 6 MIM + ][NTf 2 – ] IL and poly([C 6 VIM + ][NTf 2 – ]) PIL allowed for the interaction strength to be modulated. Olefins exhibited greater affinities toward IL and PIL stationary phases containing the [Cu 2+ ]2[NTf 2 – ] salt compared to those with the [Cu + ][NTf 2 – ] salt. Elimination of water from both copper salts was observed to be an important factor in promoting olefin interactions, as evidenced by increased olefin retention upon exposure of the stationary phases to high temperatures. Furthermore, to evaluate the long-term thermal stability of the stationary phase, chromatographic retention of probes was measured on the [Cu 2+ ]2[NTf 2 – ]/[C 6 MIM + ][NTf 2 – ] IL stationary phase after its exposure to helium at a temperature of 110°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermomechanical Processing of Uranium Alloys with 10 and 50 Weight Percent Zirconium

This work focuses on casting and thermomechanical processing for moderate sized (500-1000g) 10% by weight and 50% by weight uranium-zirconium alloys. Three castings of uranium – 10wt% zirconium and a fourth casting of uranium – 50wt% zirconium were completed using different castings processes. The first casting process relied on only induction mixing within the VIM system thereby eliminating the need for an arc-melting feedstock preparation step. The second casting process used the arc-melting process prior for feedstock to the same VIM system. In this study, the induction mixing process alone with a graphite crucible appears insufficient for the fabrication of UZr alloys. Graphite is suitable with the use of master alloy UZr feedstock produced by arc-melting. There was a moderate increase of approximately 100 ppm of carbon within the U10Zr alloys. However, there was a near 1000 ppm increase of carbon in the U50Zr alloy. This carbon content is considered too high for forming processes, and therefore, warrants the use of a ceramic crucible for UZr castings near 50wt% zirconium. Zirconia does not appear suitable for UZr castings near 50wt% zirconium. The use of Beryllia or Thoria may be a more suitable option. However, due to the significantly lower liquidus and lower zirconium content, Zirconia crucibles do appear viable for carbon reduction in the U10Zr system. Two thermomechanical processes are also studied in this work - hot extrusion of the U50Zr system and heat treatment in an argon atmosphere. This work demonstrated that extrusion of the U50Zr alloy near 680°C is a viable choice even with +1000 ppm carbon. Extrusion of the U50Zr system near 630°C was unsuccessful and does not appear viable unless significant force and tooling strength is available. There appears to be a moderate increase in extrudate hardness when compared to as-cast. Heat-treatment reduced the hardness of as-cast alloys in the U10Zr castings as well as resolve some variance in the microstructures. However, for the U50Zr billet that did not successfully extrude at 630°C, heat treatment at 900°C for 96 hours did not have a significant impact on hardness or microstructure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Casting and Characterization of U-50Zr

Uranium alloyed with 50 wt% zirconium (U-50Zr) is a proposed light water reactor (LWR) nuclear fuel by Lightbridge Corporation (LTBR). The proposed method for making the U-50Zr alloy is to arc-melt master alloys and then remelt in a vacuum induction melter (VIM) to consolidate the material and cast into an intermediate shape. After casting, the material will eventually need to be formed into a desired fuel shape. The work discussed in this report resulted from a joint effort between Ltbr and Pacific Northwest National Laboratory (PNN) to investigate a 500g – 1kg scale casting process to produce the U-50Zr alloy in the desired δ-UZr 2 phase and characterize the impurities and microstructure that result from the casting process. Master alloys were fabricated in an arc melter, then five castings were carried out in a VIM with multiple inert coating and crucible materials to find an appropriate combination. Both ZrO 2 and graphite crucibles were used and different combinations of Y 2 O 3 , CaZrO 3 , and TiC to identify which would contain the molten metal with the least reaction. On each casting, the C, O, N, H impurities were analyzed as well as the phase by x-ray diffraction and microstructure. Of the five castings, two resulted in majority of δ-UZr 2 phase-pure material and had impurity levels within acceptable ranges. The two most successful castings utilized a graphite crucible with a TiC undercoating and a Y 2 O 3 overcoat. The O and N levels were below 1000 ppm and the C content was variable but did not result in measurable carbide formation. The highest success casting resulted in an average of 282 ppm C, 567 ppm O, 217 ppm N and 79 ppm H. This casting's crucible and inert coating material was repeated with slightly different casting parameters and resulted in higher C numbers but similar phase identification. The differences between each casting are discussed and recommendations are made for future experiments to better decide on a casting process to go forward with.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluation of the Mechanical Properties of Electroslag Refined Fe-12Ni Alloys

Three Fe-12Ni alloys, individually alloyed with small amounts of V, Ti, and Al, were manufactured through different melting techniques, with special emphasis on electroslag remelting, in order to achieve different levels of metal purity and associated costs. The relative effectiveness of these melting techniques was evaluated from tensile and slow bend fracture toughness behavior at 25 C and -196 C after tempering the test specimens at various temperatures. The best melting procedure was vacuum induction melting (VIM) with or without electroslag remelting (ESR). VIM+ESR is the recommended procedure since ESR provides increased yield of plate product, a reduction of overall manufacturing costs and, depending on the alloy composition, improved tensile and fracture toughness properties.

Bhat, G. K.↗

Nature of gamma-prime precipitates in rheocast IN-100 alloy

The microstructures of commercial VIM-cast and rheocast (Apelian and Cheng, 1983) IN-100 superalloy are investigated optically and by two-stage replica TEM, with an emphasis on the nature of the gamma-prime (GP) precipitates. Photomicrographs at magnifications of 39, 390, 2145, and 6630 are presented and discussed. VIM-cast IN-100 has dendritic structure, 10-20-micron primary GP particles, and uniformly distributed cuboid GP precipitates of a uniform size (about 0.5 micron). Rheocast IN-100 (stirred 20 min at 350 rpm, 1291 C, and 0.0006 torr) has a nondendritic structure, 20-100-micron primary GP particles, and a smaller volume fraction of cuboid GP precipitates with a bimodal (either 1-1.5 microns or less than 0.5 micron) size distribution. Such distribution should increase fatigue-crack-nucleation resistance.

Surappa, M. K.↗

Responsivity of silicon photodiodes from 0.5 to 1.1 micron at 77 K

The responsivities of Si, Ge, and InSb photodiodes at 77 K are measured and compared. The results are used to determine the wavelength at which a change should occur in the detector materials used in the focal plan of the Mars Observer Visual and IR Mapping Spectrometer (VIMS). Quantitative responsivity data for Si photodiodes in the band from 0.5 to 1.1 were needed for the VIMS system analysis. The results show that the Si array for the focal plane should have two different antireflection coatings. It is found that the Si and InSb materials have equivalent quantum efficiencies at about 0.9 microns. Because of unknown signal chain complications that could be caused by a multiplexer accessing two different capacitances, the focal plane was designed with a change from Si to InSb at 1 micron.

Staller, C.↗

VIMS/Cassini mission at Titan: Scientific objectives and observational scenarios

The scientific objectives and observational scenarios of the Cassini/Visual Infrared Mapping Spectrometer (VIMS) Mission at Titan are addressed. The VIMS represents a powerful and effective means to both investigate, in four dimensions (latitude, longitude, altitude, and time), Titan's atmospheric structure and to map the near infrared spectral character of Titan's surface. Its broad spectral coverage from 0.35 to 5.1 micrometers together with its significant spectral resolution allows it to determine minor constituent distributions and cloud optical/microphysical properties from the surface to several hundred km. A promising means of obtaining high vertical resolution stratospheric profiles of hydrocarbons, oxides, and hazes via stellar occultation observations is discussed.

Baines, Kevin H.↗

Visible and infrared mapping spectrometer for exploration of comets, asteroids, and the Saturnian system of rings and moons

Consideration is given to a visible and infrared mapping spectrometer (VIMS) developed by American, Italian, and French scientists and engineers as a facility instrument for the Comet Rendezvous Asteroid Flyby (CRAF) mission and as a candidate facility instrument for the Cassini mission to explore Saturn and its rings and moons. VIMS is characterized by 0.35-5.2 micron spectral range with a nominal spatial resolution of 0.5 mrad and spectral resolutions of 7 nm at 0.35-1.0 micron wavelength and 16 nm at 1.0-5.2 micron wavelength.

Juergens, David W.↗

A radiation-hard, low-background multiplexer design for spacecraft imager applications

A possible multiplexer design for the focal plane for the Cassini Visible and Infrared Mapping Spectrometer (VIMS) is reviewed. The instrument's requirements for the multiplexed array are summarized. The VIMS instrument has a modest radiation-hardness requirement due to the trajectory and planetary environments in which the instrument will be required to operate. The total ionizing dose hardness requirement is a few tens of kilorads. A thin-gate oxide of a few hundred angstroms thickness is to be used. Field hardness is to be achieved by guard bands or hardened dielectric isolation. The design is argued to meet the low-noise and radiation-hardness required for imaging at Saturn. The design is versatile enough to provide double-correlated and double-uncorrelated sampling, which is accomplished in the signal processing electronics outside the focal plane.

Staller, Craig↗

Surface Fatigue Tests Of M50NiL Gears And Bars

Report presents results of tests of steels for use in gears and bearings of advanced aircraft. Spur-gear endurance tests and rolling-element surface fatigue tests performed on gear and bar specimens of M50NiL steel processed by vacuum induction melting and vacuum arc remelting (VIM-VAR). Compares results of tests with similar tests of specimens of VIM-VAR AISI 9310 steel and of AISI 9310 steel subjected to VAR only.

Townsend, Dennis P.↗

Grant Proposal for the Continuation of the Voyager Interstellar Mission: LECP Investigation

This proposal documents the plans of the Low Energy Charged Particle (LECP) investigation team for participation in NASA's Voyager Interstellar Mission (VIM) as the Voyager 1 and 2 spacecraft explore the outer reaches of the heliosphere and search for the termination shock and the heliopause. The proposal covers the four year period from 1 January 1997 to 31 December 2000. The LECP instruments on Voyager 1 and 2 measure in situ intensities of charged particles with energies from about 30 keV to 100 MeV for ions, and about 20 keV to greater than 10 MeV for electrons. The instruments provide detailed spectral, angular, and compositional information about the particles. Composition is available for greater than 200 keV/nuc using multi-parameter measurements. Angular information is obtained by a mechanically scanned platform that rotates at various commanded rates. Measurements of low energy ion and electron intensities versus time and spatial location within the heliosphere contain an abundance of information regarding various transport and acceleration processes on both local (approx. 1 hr, approx. 0.01 AU) and global (approx. 11 yrs, approx. 100 AU) scales. The LECP instruments provide unique observations of such dynamical processes, and we anticipate that it will return critical information regarding the boundaries of the heliosphere. Several recent and exciting discoveries based on LECP measurements emphasize the important role that low energy charged particle distributions play in physical processes in the interplanetary medium. Yet, at the same time, these discoveries also underscore the fact that our understanding of processes in the outer heliosphere is, in most cases, incomplete, and in others, only rudimentary at best. Among the discoveries referred to above are the following: (1) Shocks: Examination of greater than 30 keV ion intensities have revealed: (a) a total absence of acceleration beyond only -100-200 keV at a strong transient shock in May 1991 at 35 AU, despite an enhanced level of seed particles; (b) a large transient shock in September 1991 of global scale, with intensities of shock-accelerated ions greater than or equal to 30 keV to approx. 30 MeV showing complex, highly energy-dependent spatial evolution, and small-scale (approx. few gyroradii), often anisotropic, micro-structures; (c) recurrent intensity increases in greater than or equal to 30 keV to -few MeV ions, with structures that, in some cases, show no correlation with the associated corotating shock. (2) Superthermal ion pressure: A global merged interaction region with a leading shock, downstream of which the superthermal ion (greater than or equal to 30 keV to approx. 4 MeV) pressure is comparable to that of the thermal plasma, and the total particle pressure yields a plasma beta of order unity. (3) Pickup ions: Measurements of the C/O ratio within transient structures at 35-45 AU showing the first clear evidence that transient shocks can pre-accelerate interstellar pickup ions from approx. 1 keV/nuc to at least 1 MeV/nuc. (4) Seed particles: Injection of ions for acceleration to high energies at the termination shock is unlikely to be a problem, since interplanetary transient and recurrent shocks are continually accelerating ions, of solar wind or interstellar origin, to highly superthermal energies. (5) Precursor electrons: Ambient solar electrons (greater than or equal to few tens of keV) that exist in the outer heliosphere ca form a broad precursor, several days wide, that is upstream of the termination shock and potentially observable a few months prior to the shock crossing. (6) Solar wind velocity at Voyager 1: We can use LECP ion data to obtain the solar wind velocity at Voyager 1, enabling us to provide critical measurement of the plasma flow as we approach and encounter the termination shock and other regions (necessary due to the partial failure of the Voyager 1 PLS experiment). The work of the LECP investigator team during the VIM will include: (1) Continuing operations with regard to the receipt, processing, verification, cataloging, display, and distribution of the data from the LECP instruments on Voyager 1 and 2, (2) Monitoring the health and performance of the LECP instruments, and evaluating and characterizing the response of the LECP instruments to various energetic particle and plasma environments, (3) Participating in, and supporting Voyager Project planning exercises and other coordinated activities relevant to exploration of the outer heliosphere, (4) Developing analysis techniques and operational procedures suitable for searching for and characterizing the boundaries and unique regions of the outher heliosphere, (5) Continuing the preparation of data sets appropriate for submission to the National Space Sciences Data Center (NSSDC) and, where appropriate, the Planetary Data System (PDS), (6) Maintaining direct Web access to online LECP data through the JHU/APL Voyager LECP home page, (7) Performing scientific evaluations of the Voyager 1 and 2 LECP data sets in conjunction with other data sets and other investigators, with particular focus on the outer regions of the heliosphere, and (8) Publishing the results of these evaluations in the scientific literature and presenting the results in scientific conferences.

Krimigis, Stamatios M.↗

Processing ISS Images of Titan's Surface

One of the primary goals of the Cassini-Huygens mission, in orbit around Saturn since July 2004, is to understand the surface and atmosphere of Titan. Surface investigations are primarily accomplished with RADAR, the Visual and Infrared Mapping Spectrometer (VIMS), and the Imaging Science Subsystem (ISS) [1]. The latter two use methane "windows", regions in Titan's reflectance spectrum where its atmosphere is most transparent, to observe the surface. For VIMS, this produces clear views of the surface near 2 and 5 microns [2]. ISS uses a narrow continuum band filter (CB3) at 938 nanometers. While these methane windows provide our best views of the surface, the images produced are not as crisp as ISS images of satellites like Dione and Iapetus [3] due to the atmosphere. Given a reasonable estimate of contrast (approx.30%), the apparent resolution of features is approximately 5 pixels due to the effects of the atmosphere and the Modulation Transfer Function of the camera [1,4]. The atmospheric haze also reduces contrast, especially with increasing emission angles [5].

Perry, Jason↗

Photometric and Spectral Study of the Saturnian Satellites

Photometric and spectra analysis of data from the Cassini Visual and Infrared Mapping Spectrometer (VIMS) has yielded intriguing findings regarding the surface properties of several of the icy Saturnian satellites. Spectral cubes were obtained of these satellites with a wavelength distribution in the IR far more extensive than from any previous observations. Disk-integrated solar phase curves were constructed in several key IR wavelengths that are indicative of key properties of the surface of the body, such as macroscopic roughness, fluffiness (or the porosity of the surface), global albedo and scattering properties of surface particles. Polynomial fits to these phase curves indicate a linear albedo trend of the curvature of the phase functions. Rotational phase functions from Enceladus were found to exhibit a double-peaked sinusoidal curve, which shows larger amplitudes for bands corresponding to water ice and a linear amplitude-albedo trend. These functions indicate regions on the surface of the satellite of more recent geologic activity. In addition, recent images of Enceladus show tectonic features and an absence of impact craters on Southern latitudes which could be indicative of a younger surface. Investigations into the properties of these features using VIMS are underway.

Newman, Sarah F.↗

Hydrocarbons on Saturns Satellites: Relationship to Interstellar Dust and the Solar Nebula

To understand the origin and evolution of our Solar System, and the basic components that led to life on Earth, we study interstellar and planetary spectroscopic signatures. The possible relationship of organic material detected in carbonaceous meteorites, interplanetary dust particles (IDPs), comets and the interstellar medium have been the source of speculation over the years as the composition and processes that governed the early solar nebula have been explored to understand the extent to which primitive material survived or became processed. The Cassini VIMS has provided new data relevant to this problem. Three of Saturn's satellites, Phoebe, Iapetus, and Hyperion, are found to have aromatic and aliphatic hydrocarbons on their surfaces. The aromatic hydrocarbon signature (C-H stretching mode at 3.28 micrometers) is proportionally significantly stronger (relative to the aliphatic bands) than that seen in other Solar System bodies (e.g., comets) and materials (Stardust samples, IDPs, meteorites) and the distinctive sub-features of the 3.4 micrometer aliphatic band (CH2 and CH3 groups) are reminiscent of those widely detected throughout the diffuse ISM. Phoebe may be a captured object that originated in the region beyond the present orbit of Neptune, where the solar nebula contained a large fraction of original interstellar ice and dust that was less processed than material closer to the Sun. Debris from Phoebe now resident on Iapetus and Hyperion, as well as o Phoebe itself, thus presents a unique blend of hydrocarbons, amenable to comparisons with interstellar hydrocarbons and other Solar System materials. The dust ring surrounding Saturn, in which Phoebe is embedded, probably originated from a collision with Phoebe. Dust ring particles are the likely source of the organic-bearing materials, and perhaps the recently identified small particles of Fe detected on Saturn's satellites. Lab measurements of the absolute band strengths of representative aliphatic and aromatic molecules, together with measurements from the VIMS data, allow us to calculate the number of C atoms to find the relative abundances of C atoms in the two kinds of organic molecules. The strength of the prominent aromatic C-H stretch band relative to the aliphatic band complex in Phoebe and Iapetus indicates that the relative abundance of aromatic to aliphatic carbon is very large (greater than 200). In contract, the aromatic band is nearly imperceptible in spectra of interplanetary dust particles (IDP), returned samples from comet 91P/Wild 2, insoluable carbonaceous material in most meteorites, and the diffuse interstellar dust (DISM) (although aromatics are known in all these materials-here we consider only the spectroscopic signature)

Cruikshank, D. P.↗