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In natural corundum, a strong geochemical correlation is sometimes observed between Be and heavy high field strength elements (HHFSEs) such as Nb, Ta and W, and it has been hypothesized that trace elements are hosted in primary inclusions. However, no known mineral enriched in both Be and HHFSEs stable at these geological conditions can explain this correlation. To understand how Be and HHFSEs are distributed in natural corundum down to the atomic scale, two natural Be-bearing sapphire crystals from Afghanistan and Nigeria are studied using laser ablation inductively coupled plasma and time-of-flights secondary ion mass spectrometry, atom probe tomography and transmission electron microscopy. In addition to common trace elements such as Mg, Ti, and Fe, Be and W are detected in the metamorphic sapphire from Afghanistan, whereas Be, Nb and Ta are detected in the magmatic sapphire from Nigeria. Nanoclustering in both samples shows fractionation of Be and high field strength elements (including Ti) by atomic mass, suggesting a secondary process controlled by solid-state diffusion. The homogeneously distributed W and the secondary nano-precipitates bearing Nb and Ta indicates that HHFSEs can be incorporated into the corundum structure during crystallization, most likely through preferred adsorption on the growth surface. The strong correlation between Be and HHFSEs across the growth zones is probably due to Be being attracted by HHFSEs to partially balance the charge when incorporated into the corundum structure. The enrichment of high field strength elements by growth kinetics may result in supersaturated concentrations during crystallization, allowing them to precipitate out when the host corundum is heated above its formation temperature by basaltic magma. Comparison with previous transmission electron microscope studies suggests the same process for incorporating Be and HHFSEs also applies to other natural corundums from different localities. [ABSTRACT FROM AUTHOR]

Emeralds - the green colored variety of beryl - occur as gem-quality specimens in over fifty deposits globally. While digital traceability methods for emerald have limitations, sample-based approaches offer robust alternatives, particularly for determining the geographic origin of emerald. Three factors make emerald suitable for provenance studies and hence for developing models for origin determination. First, the diverse elemental chemistry of emerald at minor (<1 wt%) and trace levels (<1 to 100's ppmw) exhibits unique inter-element fractionations between global deposits. Second, minimally destructive techniques, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), enable measurement of these diagnostic elemental signatures. Third, when applied to extensive datasets, machine learning (ML) techniques enable the creation of predictive models and statistical discrimination with adequate characterization of the deposits. This study employs a carefully selected dataset comprising more than 1000 LA-ICP-MS analyses of gem-quality emeralds, enriched with new analyses. This dataset represents the largest available for global emerald deposits. We conducted unsupervised exploratory analysis using Principal Component Analysis (PCA). For machine learningbased classification, we employed Support Vector Machine Classification (SVM-C), achieving an initial accuracy rate of 79%. This was enhanced to 96.8% through the use of hierarchical SVM-C with PCA filters as our modeling approach. The ML models were trained using the concentrations of eight statistically significant elements (Li, V, Cr, Fe, Sc, Ga, Rb, Cs). By leveraging high-quality LA-ICP-MS data and ML techniques, accurate identification of the geographical origin of emerald becomes possible. These models are important for accurate provenance of emerald, and from a geochemical perspective, for understanding the formation environments of beryl-bearing pegmatites and shales. [ABSTRACT FROM AUTHOR]

Montana hosts the largest sapphire deposits in the US, but the genesis of and connection among the various secondary and primary sapphire occurrences remains cryptic. In situ SIMS measurements of oxygen isotopes in sapphires and zircon inclusions in sapphires provide an opportunity to study the isotope and trace element geochemistry in order to understand sapphire-forming protoliths (i.e. crustal setting and alteration). Sapphire from Montana was transported as xenocrysts in carrier (host) magmas that resorbed sapphire exteriors during transport. The timing and nature of sapphire genesis is elucidated by SIMS measurements of trace elements and U–Pb from discrete zones in zircon inclusions with rims that are interpreted to be syngenetic with host sapphire. Montana sapphires exhibit a large range of δ18O values, from −3‰ to +12‰ VSMOW. However, all but two anomalous crystals fall in the range of 0‰ to 8‰. There is significant crystal-to-crystal variability yet averages at most deposits are consistent with high-temperature equilibration with the mantle (δ18O(Crn) = 4.4‰ to 5.7‰), with the exception of the commercial sapphire deposits at Rock Creek that average 2.7‰. Ruby analyses are limited, but typically have lower δ18O values compared to sapphires from the same detrital localities. Homogeneity within individual crystals (avg. 2 s = ±0.2‰) indicates the absence of isotopically distinct fluid or melt during crystallization. But intercrystalline δ18O ranges by up to 7‰ at a single locality, suggesting sapphire variability at a deposit reflects heterogeneity in the original protolith. Oxygen isotope fractionations between zircon rims and surrounding sapphire suggest comagmatic zircon inclusions and corundum equilibrated at high temperature. No correlation is seen for the degree of radiation damage and alteration of δ18O(Zrc) when zircon inclusions are surrounded and armored by sapphire. U–Pb ages and trace elements were measured in a small subset of syngenetic zircon inclusions in Dry Cottonwood Creek sapphires, revealing a Proterozoic (1778 ± 9 Ma) age for the protolith of sapphires at this locality and a likely polygenetic history. Previous work has suggested formation of these sapphires through partial melting of anorthosites and several anorthosites occur locally and match the age of zircon inclusion cores—the Boehls Butte anorthosite (~180 km NW of Rock Creek) and the Bitterroot anorthosite (~55 km W of Rock Creek) could correlate with Al-rich protoliths at depth. Proterozoic U–Pb ages of zircon from the Boehls Butte anorthosite (1787 ± 2 Ma) match well with the age of zircon inclusion cores in Dry Cottonwood Creek sapphires and suggest genesis in these or similar protoliths. Zircon rims with Tera-Wasserburg lower intercept ages of 110 ± 9 Ma are consistent with previous observations of a xenocrystic relationship to the ~50 Ma Eocene volcanic rocks. Corundum that formed over 50 Ma prior to being scavenged by Eocene magmas likely originated by the anatexis of Precambrian anorthosites and possibly other aluminum-rich rocks at depth. [ABSTRACT FROM AUTHOR]

The beryl-group mineral johnkoivulaite, Cs(Be2B)Mg2Si6O18, was compressed hydrostatically in a diamond-anvil cell up to 10.2 GPa. In situ Raman spectroscopy and X-ray crystallography revealed a P6/mcc-to-P 3 c1 (second-order) phase transition on isothermal compression at the critical transition pressure Pc = 4.13 ± 0.07 GPa. The elastic parameters determined for the volume elasticity of the two polymorphs correspond to a Birch-Murnaghan equation of state with K0 = 148 ± 2 GPa and K ′ = 0 for P < Pc and K0 = 75.5 ± 0.9 GPa with K ′ = 4 for P > Pc. The low-P polymorph shows anomalously linear compression behavior, as reported for several other beryl-derived framework structures. The high-P polymorph, which was found to follow a a ′ = a ⋅ 3 , c ′ = c superstructure according to P 3 c1, is almost twice as compressible as its low-P form. This is unique for any beryl-derived structure and can be attributed to the high degree of freedom for atomic displacements in the superstructure. The reduced symmetry can also be understood as the effect of the driving mechanism of the transformation. The extra-framework Cs channel components counteract any lateral deformation of the channels parallel to [0001] within the microporous framework and, similar to pezzottaite, are responsible for maintaining the trigonal/hexagonal lattice metrics. [ABSTRACT FROM AUTHOR]

Research on photoluminescence spectroscopy on Cr-doped gem materials has demonstrated great success regarding the identification of gemstones in terms of building rapid test systems. In this study, 405 nm photoluminescence spectroscopy was used to measure the luminescence decay profiles of dozens of natural and lab-grown spinel (including heated spinel) and alexandrite. Spinel and alexandrite are both capable of producing photoluminescence with a long lifetime: spinel between 9 and 23 microseconds and alexandrite from 25 to 53 microseconds. The photoluminescence lifetime and exponential parameters of the half-life demonstrated notable differences in the ranges of decay times between natural, heated, and lab-grown versions of these materials. [ABSTRACT FROM AUTHOR]

The optical properties (scattering, absorption, and extinction) of spheroidal Cu particles embedded in intermediate plagioclase feldspar are computed for various sizes and shapes using the Mie theory and T-matrix method. The observed color for Cu-bearing plagioclase, as a function of particle size and shape, is also calculated from the computed extinction spectra. The colors and pleochroism observed in natural and treated Cu-bearing plagioclase can be explained from the computational results. The enigmatic green colors in some precious Oregon sunstones result from red light being scattered away by Cu nanoparticles of certain sizes. The UV-VIS spectra are collected on Cu-bearing plagioclase samples for comparison with the computational results, which are shown to match the optical observations. The results from this work may be used to quantify the concentration of colloidal Cu in plagioclase or glass with a similar refractive index. Particle sizes and shapes can also be characterized using extinction and scattering spectra, which can be collected with different optical configurations. New materials with special color effects and optical characteristics may be designed and engineered by applying the unusual properties of metal colloids. [ABSTRACT FROM AUTHOR]

The color of most garnets is derived from multiple color‐producing elements (chromophores). In this study we selectively isolate the ultraviolet–visible–near infrared (UV–Vis–NIR) spectra of four major chromophores (Fe2+, Mn2+, Cr3+ and V3+) by collecting and extrapolating the spectra of four representative pyrope‐almandine‐spessartine (pyralspite) garnets. In order to study the color strength of these isolated chromophores and their impact on color change in garnet, we have proposed a new quantitative definition of strength of a chromophore. With the isolated garnet chromophore spectra, hypothetical garnet spectra with various chemical compositions can be simulated. By using these hypothetical garnet spectra, the impact of each chromophore on the color change behavior in pyralspite garnet was also quantitatively studied. Most pyralspite garnets can be successfully modeled using these four chromophores, however, this model cannot adequately describe those garnets containing the Fe3+/Fe2+ intervalence charge‐transfer transitions. Finally, a comprehensive excel data processing template (Appendix 3) written with VBA macro code was generated to help other researchers calculate colorimetric parameters and color panels from UV–Vis–NIR spectrum. In the template, we provided multiple types of conversion matrices and power distribution curves of different illuminants, so that different colorimetric parameter conversion and color panel calculation from UV–Vis–NIR spectrum can be selected with different combinations based on people's preference. The user guide of the excel template can be found in Appendix 4. The detailed calculation procedures and formulae used for the excel template can be found in Appendix 5. [ABSTRACT FROM AUTHOR]

Iron oxide inclusions and exsolution lamellae in rainbow lattice sunstone (RLS) from Harts Range, Australia, are examined using optical and electron microscopy and single-crystal X-ray diffraction (SC-XRD). Laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) analyses show a bulk composition of An 1.4 Ab 14.8 Or 83.0 Cn 0.8 with < 200 ppmw (parts per million weight) of Fe. Two stages of exsolution can be identified in RLS from the bimodal distribution in the size and shape of the exsolution lamellae. Micron-scaled Albite-twinned oligoclase spindles (An 27 Ab 72 Or 1) first exsolved at ∼ 650 ∘ C were followed by nanoscaled Pericline-twinned albite films (∼ Ab 100) below 500 ∘ C that create adularescence. The albite films inherited and preserved the monoclinic tetrahedral framework of the orthoclase matrix (An 0.3 Ab 11.5 Or 87.3 Cn 0.9) as further ordering was completely inhibited by coherent-interface strain after exsolution. All the exsolution lamellae are pristine and strain-controlled with no signs of any deuteric or hydrothermal alteration, indicating the iron in the magnetite inclusions was not introduced by an external fluid. The magnetite inclusions nucleated around the same time as the exsolution of oligoclase spindles likely due to the reduction of Fe 3+ to Fe 2+ in the feldspar lattice. Magnetite films following the specific crystallographic orientation relationship (COR) of 111Mt∥100Or and 11‾0Mt∥001Or grew to extraordinarily large sizes due to the near perfect lattice match at the interface with the orthoclase host. Some thinner magnetite films were oxidized into hematite during weathering of the host rock. RLS reveals a new mechanism for the formation of the flaky hematite inclusions in feldspars, which may explain the enigmatic origin of aventurescence observed in many other sunstones and red-clouded feldspars. [ABSTRACT FROM AUTHOR]

A new mineral of the beryl group, johnkoivulaite, Cs(Be2B)Mg2Si6O18, was recovered from the gem gravels in the Pein Pyit area of the Mogok region in Myanmar. Thus far, only a single crystal has been identified. It has dimensions of about 5.8 x 5.7 x 5.5 mm. This specimen has an irregular shape but still has discernible crystal form with geometric growth patterns observed on the crystal faces. The crystal of johnkoivulaite is grayish-violet in color and strongly pleochroic, going from nearly colorless with E⊥c to dark bluish-violet with E||c. Johnkoivulaite has a Mohs hardness of about 7 1/2 and a measured density of 3.01(10) g/cm³. It is uniaxial (-) with ω = 1.607(1) and ε = 1.605(1) (white light). Electron microprobe analyses gave the empirical formula of (Cs0.85K0.10Na0.01) (Be1.88B1.12) (Mg1.66Fe0.27 Mn0.01Al0.05) (Si5.98)O18 with Be calculated by stoichiometry and confirmed by LA-ICP-MS measurements. Johnkoivulaite is hexagonal, P6/mmc (no. 192) with a = 9.469(2), c = 9.033(2) Å, V = 701.5(3) ų, and Z = 2. Johnkoivulaite is isostructural with beryl and exhibits partial substitution of B for Be at the distorted tetrahedral site, Mg for Al at the octahedral site, and Cs in the channel sites within the stacked Si6O18 rings. This substitution can be written as (CsMg2B)(□Al2Be)-1. Johnkoivulaite, the seventh member of the beryl group, is named in honor of gemologist John Koivula in recognition of his contributions to mineralogy and gemology. [ABSTRACT FROM AUTHOR]

The analysis of transparent conducting oxide nanostructures suffers from a lack of high throughput yet quantitatively sensitive set of analytical techniques that can properly assess their electrical properties and serve both as characterization and diagnosis tools. This is addressed by applying a comprehensive set of characterization techniques to study the electrical properties of solution-grown Al-doped ZnO nanowires as a function of composition from 0 to 4 at. % Al:Zn. Carrier mobility and charge density extracted from sensitive optical absorption measurements are in agreement with those extracted from single-wire field-effect transistor devices. The mobility in undoped nanowires is 28 cm2/V s and decreases to ∼14 cm2/V s at the highest doping density, though the carrier density remains approximately constant (1020 cm-3) due to limited dopant activation or the creation of charge-compensating defects. Additionally, the local geometry of the Al dopant is studied by nuclear magnetic resonance, showing the occupation of a variety of dopant sites. [ABSTRACT FROM AUTHOR]

In studies of the structures of silicate minerals and glasses, 29Si NMR spectroscopy has been applied almost exclusively to materials containing relatively low concentrations of ions with unpaired electrons spins, such as most transition metals and rare earths, because of sometimes severe broadening and shifting of resonances in such strongly paramagnetic systems. However, by adapting experimental methods to allow detection of very broad signals, and by examining a much expanded range of frequencies, we show here that accurate spectra can indeed be measured for a series of pure-phase transition metal silicates, including olivines (Fe2SiO4, Co2SiO4, Ni2SiO4), Co-akermanite (CoCa2Si2O7), and clinopyroxenes (CoCaSi2O6, NiCaSi2O6). For the latter two, we also present data for glasses of the same nominal compositions. For all of these phases, NMR peak broadening is large, in many cases to the point where magic angle spinning (MAS) does not enhance resolution; in all cases the observed paramagnetic shifts fall far outside the known range for diamagnetic silicates. There are clearly large effects of local structure on shift, suggesting great potential sensitivity to variations in chemical, electronic, and magnetic structure in both crystalline and amorphous phases. In particular, the spectra for the glasses are very different from those of crystals in both width and position. In most cases, measured spin-spin relaxation times are long enough to avoid major loss of signal during the NMR acquisition, but this may not always be the case in more magnetically dilute solid solutions, where small, broad paramagnetic resonances due to first cation neighbor interactions may in some systems be difficult to detect. To explore this issue, we present new data on a Ni-doped forsterite (Mg1.9Ni0.1SiO4) and on natural San Carlos olivine (Mg1.8Fe0.2SiO4), which improve upon the accuracy of our previous studies of these materials. It is clear that applications of NMR to paramagnetic silicates holds great promise not only for empirical studies of structure of a much wider range of compositions of minerals and glasses, but for future testing and application of advanced theoretical methods to more completely interpret such results. [ABSTRACT FROM AUTHOR]

A wide number of genetic models have been proposed for volcanically transported ruby and sapphire deposits around the world. In this contribution we compare the trace element chemistry, mineral and melt inclusions, and oxygen isotope ratios in blue to reddish-violet sapphires from Yogo Gulch, Montana, U.S.A., with rubies from the Chantaburi-Trat region of Thailand and the Pailin region of Cambodia. The similarities between Thai/Cambodian rubies and Yogo sapphires suggest a common origin for gem corundum from both deposits. Specifically, we advance a model whereby sapphires and rubies formed through a peritectic melting reaction when the lamprophyre or basalts that transported the gem corundum to the surface partially melted Al-rich lower crustal rocks. Furthermore, we suggest the protolith of the rubies and sapphires was an anorthosite or, in the case of Thai/Cambodian rubies, an anorthosite subjected to higher pressures and converted into a garnet-clinopyroxenite. In this model the rubies and sapphires are rightfully considered to be xenocrysts in their host basalts or lamprophyre; however, in this scenario they are not “accidental” xenocrysts but their formation is intimately and directly linked to the magmas that transported them to the surface. The similarities in these gem corundum deposits suggests that the partial melting, non-accidental xenocryst model may be more wide-reaching and globally important than previously realized. Importantly, in both cases the gem corundum has an ostensibly “metamorphic” trace element signature, whereas the presence of silicate melt (or magma) inclusions shows they ought to be considered to be “magmatic” rubies and sapphires. This discrepancy suggests that existing trace element discriminant diagrams intended to separate “metamorphic” from “magmatic” gem corundum ought to be used with caution. [ABSTRACT FROM AUTHOR]

Pleochroism plays an important role in determining the face-up visual color appearance of faceted, optically anisotropic (non-cubic) gemstones. One area that has received little attention is the interplay between pleochroism and the so-called alexandrite effect wherein the perceived color of a mineral changes with different lighting conditions (i.e., daylight vs. incandescent light). In this article we have collected ultraviolet/visible/near-infrared (UV-Vis-NIR) spectra of a gem-quality, synthetic Cr-bearing chrysoberyl crystal along its three crystallographic axes. We use these spectra to calculate the color and to quantify the color change that would be observed in a wafer or faceted gemstone in any orientation and for any prescribed path length of light between 1 and 25 mm. We describe the method used to perform these calculations and give an overview of color science and color space as it pertains to mineralogy and gemology. The data collected here are used to predict the optimum orientation for a wafer or a faceted alexandrite gemstone to produce the maximum color change sensation between daylight and an incandescent light source. We find that a wafer oriented with the unpolarized light-path-length perpendicular to the a-axis exhibits the strongest color change but that the color change is weaker parallel to the a-axis. Pleochroism in a faceted stone will mix light traveling in different directions. This relaxes requirements to orient a stone along the 'best' direction, but it is still found that stones cut with their table to culet direction oriented perpendicular to the a-axis show the best color-change while orientation parallel to the a-axis produces weaker color change. Nonetheless, there is a wide range of 'acceptable' orientations and no single 'best' direction for a faceted gemstone. The results of this study demonstrate the complex nature of color in minerals and shed light on the intricate interplay between several factors including pleochroism, lighting conditions, light path length through a transparent sample, and chromophore concentrations. The use of the techniques outlined here can lead to a better understanding of the color sciences in the mineral world in general. [ABSTRACT FROM AUTHOR]

Trace-element chemistry and microscopic observations of included gem corundum (a-Al[2]O[3]) suggests a new model of syngenetic growth of oriented rutile inclusions rather than the usual interpretation of their growth through exsolution. Laser ablation-inductively coupled plasma-mass spectrometry (LA- ICP-MS) is now a robust method for measuring trace elements in gem-quality corundum (ruby and sapphire). Nonetheless, the corundum structure is relatively unforgiving for substitutional components and typically only a small handful of minor to trace elements are measured by LA-ICP-MS (Mg, Ti, V, Cr, Fe, Ga). Less commonly, trace elements such as Be, Zr, Nb, Sn, La, Ce, Ta, and W are found in natural corundum. Their concentrations are typically correlated with high contents of Ti and silky or cloudy zones in the corundum that contain a high concentration of needle-like rutile or other oxide inclusions. Three metamorphic-type sapphires from Sri Lanka, Madagascar, and Tanzania were studied here using LA-ICP-MS, electronprobe microanalysis (EPMA), and nanoSIMS to document correlations between the various trace elements and their distribution between the corundum and included, oriented rutile TiO[2] needles. NanoSIMS and EPMA measurements show concentration of Be, Mg, Fe, V, Zr, Nb, Ce, Ta, and W in the rutile needles. The relative atomic concentrations of Mg and Ti from LA-ICP-MS measurements suggest the corundum-rutile intergrowth grew as a mechanical mixture of the two phases as opposed to rutile formation through exsolution from the corundum host. This scenario is also suggested for the three magmatic-type sapphires studied here based on the presence of glassy melt inclusions in close association with included, oriented oxide needles. The preservation of a glassy melt inclusion requires fast cooling, whereas exsolution of the oxide inclusions would require slow cooling and annealing at a temperature lower than sapphire formation. The studied sapphires suggest the likely origin of the oriented, needle-like rutile inclusions to be syngenetic epitaxial coprecipitation of both rutile and corundum. The interpretation of such oriented oxide inclusions has important implications for understanding the geological formation conditions based on trace element data or using such data to separate sapphires and rubies based on their geographic origin. [ABSTRACT FROM AUTHOR]

Most applications of high-resolution NMR to questions of short-range order/disorder in inorganic materials have been made in systems where ions with unpaired electron spins are of negligible concentration, with structural information extracted primarily from chemical shifts, quadrupolar coupling parameters, and nuclear dipolar couplings. In some cases, however, the often-large additional resonance shifts caused by interactions between unpaired electron and nuclear spins can provide unique new structural information in materials with contents of paramagnetic cations ranging from hundreds of ppm to several per cent and even higher. In this brief review we focus on recent work on silicate, phosphate, and oxide materials with relatively low concentrations of paramagnetic ions, where spectral resolution can remain high enough to distinguish interactions between NMR-observed nuclides and one or more magnetic neighbors in different bonding configurations in the first, second, and even farther cation shells. We illustrate the types of information available, some of the limitations of this approach, and the great prospects for future experimental and theoretical work in this field. We give examples for the effects of paramagnetic transition metal, lanthanide, and actinide cation substitutions in simple oxides, pyrochlore, zircon, monazite, olivine, garnet, pyrochlores, and olivine structures. [ABSTRACT FROM AUTHOR]

In marked contrast to the single, narrow 29Si MAS NMR resonance for pure forsterite (Mg2SiO4), the spectra for synthetic forsterite containing 0.05 to 5% of the Mg2+ replaced with Ni2+, Co2+, or Fe2+ display between 4 and 26 additional, small, paramagnetically shifted peaks that are caused by interactions of the unpaired electron spins on the transition metal cations and the nuclear spins. Analyses of these relative peak areas, their numbers, and comparison of their positions to those in spectra of synthetic monticellites (CaMgSiO4) containing similar levels of transition metals, allows at least partial assignment to the effects of cations in either the M1 octahedral site only or to both M1 and M2 sites. More detailed analyses indicate that in forsterite, Ni2+ occupies only M1, Fe2+ occupies M1 and M2 roughly equally, and Co2+ occupies both M1 and M2 in an approximately 3:1 ratio. These findings for low concentrations agree with expectations from previous studies by other methods (e.g., XRD) of olivines with much higher transition metal cation contents. However, even low concentrations of Mn2+ (e.g., 0.1%), as well as higher Fe2+ contents (e.g., in natural San Carlos olivine) can broaden NMR peaks sufficiently to greatly reduce this kind of information content in spectra. [ABSTRACT FROM AUTHOR]

A suite of Fe-bearing natural and synthetic grossular-rich [(Ca,Fe)3(Al,Fe)2Si3O12] and pyrope-rich [(Mg,Fe)3Al2Si3O12] garnets were investigated using 27Al and 29Si MAS NMR and 57Fe Mössbauer spectroscopy. This was done to study the state of cation order-disorder in garnet solid solutions by analyzing paramagnetically shifted resonances in high-resolution NMR spectra. The Mössbauer spectra, along with electron microprobe results, give the concentrations of Fe2+ and Fe3+ and their site occupancies, even in grossular samples with very low concentrations of Fe. MAS NMR spectra were collected on Fe2+-bearing grossular- and pyrope-rich garnets with up to 25 mol% almandine component and on other Fe3+-bearing grossular samples with up to 9 mol% andradite component. Despite peak broadening and signal loss, structural information was even obtained from garnet with relatively high Fe contents (25 mol% almandine component). Paramagnetically shifted NMR peaks, related to the presence of Fe2+, were observed in grossular samples and are similar in nature to those reported previously for natural, relatively low-Fe2+ pyrope garnets by Stebbins and Kelsey (2009). Additional NMR peaks appear as the concentration of Fe2+ increases, reflecting an increase in the average number of neighboring Fe2+ cations around AlO6 and SiO4 groups. These newly observed peaks hold potential to provide information concerning the presence or absence of short-range ordering in certain Fe-bearing silicate garnets. The effect of Fe3+ on the MAS NMR spectra of garnet appears to be less pronounced, because it does not produce any observable paramagnetically shifted resonances. [ABSTRACT FROM AUTHOR]

We present 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS-NMR) spectra of Al- and Fe-bearing, high-pressure pyroxene and perovskite samples, synthesized in a multi-anvil apparatus at 26 GPa and 1900 °C at targeted compositions of (Mg1--xFex)(Si1--xAlx)O3 (x = 0.01, 0.025, and 0.05). 27Al MAS-NMR spectra of the perovskite samples indicate that Al3+ replaces both Si4+ in the octahedral site and Mg2+ in the larger 12-coordinated site. NMR signal loss caused by paramagnetic interactions is often a severe complication when performing NMR on materials containing Fe2+,3+; however, careful measurement of signal loss and comparison to total Fe content in these samples sheds light on the nature of Al and Fe incorporation. NMR signal loss for the pyroxenes is linearly related to total Fe content as would be expected in the case of uncorrelated substitution of randomly distributed Al and Fe. However, 27Al signal loss for the perovskite samples increases only slightly between samples with x = 0.01 and 0.025 indicating similar coordination of Al by Fe and non-random distribution. Complete signal loss at Fe/(Fe + Mg) = 0.05 suggests the upper limit of Fe2+ and Fe3+ concentration at which useful NMR data can be obtained for this system. [ABSTRACT FROM AUTHOR]

We present the results of a variable-temperature (VT) 31P magic angle spinning NMR (MAS-NMR) study of a series of solid solutions between different synthetic rare earth (RE = Y, La, Ce, Pr, Nd, Eu, Dy) orthophosphates (REPO4) taking either the monoclinic monazite or tetragonal xenotime (zircon) crystal structure. Solid solutions were formed by mixing a small amount of a paramagnetic REPO4 material (RE = Ce, Pr, Nd, Eu, Dy) with either diamagnetic LaPO4 or YPO4, which take the monoclinic and tetragonal crystal structures, respectively. Mixtures were made with up to 10 mol% (nominal content) of the paramagnetic component. 31P spectra of these materials contained several paramagnetically shifted resonances indicating some dissolution of the paramagnetic rare earth into the host LaPO4 or YPO4 phase; however, it is clear that none of the samples studied here reached a state of complete solid solution. The use of multiple paramagnetic species in dilute solid solution with two diamagnetic materials taking different crystal structures enabled an investigation of the probable mechanisms of paramagnetic interactions in the 31P NMR experiments. A peak assignment model is introduced for the 31P spectra. Our analysis indicates that the paramagnetic interactions are dominated by the Fermi contact shift with a secondary contribution from the so-called "pseudocontact" shift. [ABSTRACT FROM AUTHOR]

We present variable-temperature (VT, 31 to 204 °C) 29Si magic angle spinning NMR (MAS-NMR) spectra of a synthetic forsterite containing dilute paramagnetic impurities and 27Al and 29Si spectra of two iron-bearing natural pyrope garnet specimens from the Dora Maira ultrahigh-pressure metamorphism locality. Previous NMR studies of these materials reported multiple "anomalous" resonances outside the range of expected frequencies. It has been hypothesized that these peaks were caused by interactions between paramagnetic centers and the resonating nuclei. Our VT MAS-NMR study shows a linear relationship between peak position and inverse temperature for the "anomalous" resonances, confirming their assignment as paramagnetic shifts. A detailed analysis of the peaks in the pyropes indicates that the "anomalous" resonances are caused by a combination of the Fermi contact and pseudocontact interactions. The paramagnetic shifts in the 29Si spectra are likely caused by Fe2+ in the first, second, and third nearest dodecahedral sites while those in the 27Al spectra are likely caused by one or two Fe2+ in the first shell dodecahedral site. [ABSTRACT FROM AUTHOR]

Raman and photoluminescence (PL) mapping is a non-destructive method which allows gemologists and scientists to evaluate the spatial distributions of defects within a gem; it can also provide a method to quickly distinguish different species within a composite gem. This article provides a summary of this relatively new technology and its instrumentation. Additionally, we provide a compilation of new data for various applications on several gemstones. Spatial differences within diamonds can be explored using PL mapping, such as radiation stains observed on the rough surface of natural green diamonds. Raman mapping has proven useful in distinguishing between omphacite and jadeite within a composite of these two minerals, identifying various tourmaline species within a heterogeneous mixture, and determining the calcium carbonate polymorphs in pearls. Additionally, it has potential to be useful for country-of-origin determination in blue sapphires and micro-inclusion analysis. As new avenues of research are explored, more applications for gem materials will inevitably be discovered. [ABSTRACT FROM AUTHOR]

The red variety of corundum owes its color and strong fluorescence to the presence of Cr, as well as traces of Fe. The latter can reduce the fluorescence and thus impact the appearance of the final gem. Gem quality rubies are rarely available for scientific study and even less common in their rough form. Opaque inclusions in rubies are often removed during faceting and remain unidentified. This study aims to identify opaque inclusions in rubies from the two most common origins seen in the high end market today: Mogok, Myanmar and Montepuez, Mozambique. Using electron probe microanalaysis (EPMA) the inclusions were identified as sphalerite and pyrrhotite in Mogok rubies. The paragenesis of Myanmar, marble-related rubies is fairly well understood and no Fe-rich minerals apart from sulfides have been identified. Opaque inclusions in Mozambican rubies are a complex mix of Fe-Cu-Ni sulfides with exsolution textures. These inclusions are interpreted to be small amounts of sulfide melt trapped during corundum formation. The different sulfide phases crystallized from this entrapped melt and some phases experienced later exsolution during cooling. The formation of amphibole-related, Mozambican rubies is not well understood, but it is obvious that very different processes are at work compared to the marble-related Myanmar ruby deposits. [ABSTRACT FROM AUTHOR]

Gem corundum deposits are typically divided into blue sapphire and ruby deposits. However, this classification often overlooks the fact that the precious stones produced are the same mineral with only an overall slight difference in their trace element profiles. It can take only a couple thousand ppm chromium to create the rich, red color expected of a ruby. This contribution deals specifically with economically important gem corundum mining regions that produce both blue sapphires and rubies either in comparable quantities (Mogok, Myanmar, and the basalt-related gem fields on the border between Thailand and Cambodia at Chanthaburi, Thailand, and Pailin, Cambodia) or predominantly blue sapphires with rare rubies (secondary Montana sapphire deposits and Yogo Gulch in Montana as well as the gem fields of Sri Lanka). Comparison of the trace element profiles and inclusions in the blue sapphire/ruby assemblages in these deposits shows that there are both monogenetic and polygenetic assemblages in which the blue sapphires and rubies have the same geological origin (monogenetic) or distinct geological origins (polygenetic). In the monogenetic assemblages, the rubies and blue sapphires have essentially indistinguishable inclusions and trace element chemistry profiles (with the exception of Cr contents). On the other hand, polygenetic assemblages are composed of rubies and blue sapphires with distinct inclusions and trace element chemistry profiles. Notably, in the monogenetic assemblages, chromium seems to vary independently from other trace elements. In these assemblages, Cr can vary by nearly four orders of magnitude with essentially no consistent relationship to other trace elements. The observations described herein are an attempt to address the question of what the geochemical and geological constraints are that turn gem corundum into a spectacular ruby. [ABSTRACT FROM AUTHOR]

In this article, the author presents his reply to Proyer on the origin of needle-like rutile inclusions in natural gem corundum using electron probe micro-analyzer data, laser ablation inductively coupled plasma mass spectrometry; and nano-secondary ion mass spectrometry image.

I American Mineralogist i greatly values the time and effort of the 2020 reviewers, especially in such an unprecedented year. [Extracted from the article]