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A complex crystal-chemical investigation based on spectroscopic methods, Electron MicroProbe Analysis (EMPA), and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) was made on sphalerite samples from the Terézia and Rozália veins in the Banská Štiavnica ore district. The yellow (sample A) and olive-green sphalerite (C) are in association only with quartz; orange sphalerite (B) is associated with quartz and chalcopyrite; and black sphalerite (D) is associated with galena, chalcopyrite, quartz, and baryte. EMPA revealed that Cd and Fe are substituting for Zn with variable proportions; the Cd/Fe ratio decreases from 2.82–2.85 in the A sample to 0.42 in the D sample. LA-ICP-MS showed that, except Cd and Fe, only Mn has content above 20; Co and Cu vary between 2 and 17 ppm. The optical absorption spectra exhibit absorption between 644 and 740 nm with three smaller humps at 669–671, 698–702, and 732–743 nm, and weaker absorption bands at 858–894 nm in the NIR region, which can be all assigned to crystal-field transitions of Fe2+. The absorption edge starts at about 600 nm to the UV region. Minimal absorption is in the yellow-red part of the visible spectrum giving rise to yellowish-orange and orange-red colors. Absorption in the red region for olive-green sphalerite is more pronounced, explaining the shift to greenish hues. In black sphalerite, the absorption pattern is similar to the olive-green sphalerite, but the bands in the 644 to 740 nm region are less defined. The black color could be caused by slightly higher concentrations of Fe, the smaller size of individual crystals in the aggregate reducing macroscopic transparency, and/or the presence of submicroscopic inclusions. [ABSTRACT FROM AUTHOR]

A heat treatment was performed on selected epidote and clinozoisite crystals to establish the nature of any changes in the optical and crystal-chemical properties and to identify a breakdown product using a wide spectrum of analytical methods. Natural samples were heated from 900 to 1200 °C under atmospheric pressure in ambient oxidation conditions for 12 h. Epidote and clinozoisite were stable at 900 °C; those heated at 1000 °C, 1100 °C, and 1200 °C exhibited signs of breakdown, with the development of cracks and fissures. The average chemical composition of epidote is Ca2.000Al2.211Fe0.742Si2.994O12(OH), while that of clinozoisite is Ca2.017A12.626Fe0.319Si3.002O12(OH). The breakdown products identified by electron microanalysis, powder X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy were anorthite, pyroxene compositionally close to esseneite, and wollastonite. The decomposition of the epidote-clinozoisite solid solution is controlled by the following reaction: 4 epidote/clinozoisite → 2 pyroxene + 2 wollastonite + 4 anorthite + 2 H2O. Pyroxene likely contains a significant proportion of tetrahedral Fe3+ as documented by the Mössbauer spectroscopy. Moreover, the presence of hematite in the Mössbauer spectrum of the clinozoisite sample heated at 1200 °C can result from the following reaction: 4 epidote → pyroxene + 3 wollastonite + 4 anorthite + hematite + 2 H2O. [ABSTRACT FROM AUTHOR]

We studied 12 crystal fragments of natural spinel from Mogok, Myanmar and Lục Yên, Vietnam. All samples were crystal fragments of various shapes and sizes and several of them had gemological quality. Studied samples are enriched in Cr, V, Fe2+, Fe3+, Zn, which are responsible for its resulting color. They could be divided into groups of V-Cr spinels with Cr 0.001–0.006 apfu, V 0.001–0.004 apfu, and Fe spinels containing increased Fe2+ (0.001–0.017 apfu) and Fe3+ (0.004–0.012 apfu). Some samples show luminescence bands at 677, 685, 697, 710, and 718 nm assigned to Cr3+. The optical absorption spectra of spinels were divided into two groups of V-Cr and Fe spinels based on the dominant element acting on optical spectra. The optical spectrum of V-Cr spinels can be divided into two zones (1) 420–550 nm (V3+ and Cr3+ absorption); (2) 640–1000 nm (Fe2+-Fe3+ charge transfer). The optical absorption spectra of Fe spinels can also be divided into two zones (1) 410–650 nm (Fe2+-Fe3+ charge transfer) and (2) 770–1000 nm (Fe2+). This variation in chromophores results in the differences in color: V-Cr spinels are pink to red, Fe spinels are in shades of blue as well as yellow and pink. [ABSTRACT FROM AUTHOR]

Metamorphic evolution of an accretionary wedge can be constrained by a reconstructed P–T conditions of the oceanic and continental margin fragments. This paper deals with the metamorphic overprinting of the Inner Western Carpathians (IWC) Meliatic Triassic–Jurassic paleotectonic units after the closure of the Neotethyan Meliata Basin. Medium to high-pressure and lower temperature conditions were estimated by Perple_X pseudosection modelling, combined with garnet–phengite, calcite–dolomite and chlorite thermometers and chlorite–phengite and phengite barometers. The Late Jurassic subductional burial to a maximum 50 km depth was estimated from the Bôrka Unit continental margin fragments at 520 °C and 1.55 GPa. This is compatible with the metamorphic peak garnet–glaucophane–phengite assemblage of blueschist facies in metabasites. The Jaklovce Unit oceanic fragments were subducted to maximum 35–40 km at 390–420 °C and 1.1–1.3 GPa. Metabasalts and metadolerites contain winchite, riebeckite, actinolite, chlorite, albite, epidote and phengite. A glaucophane-bearing metabasalt recorded an intra-oceanic subduction in blueschist-facies conditions. Rare amphibolite-facies metabasalts of this unit indicate the base of an inferred oceanic crust sliver obducted onto the continental margin wedge. The Meliata Unit oceanic/continental margin flysch calciclastic and siliciclastic metasediments suggest the burial to approximately 15–20 km at 250–350 °C and 0.4–0.6 GPa. This is indicated by a newly formed albite, K-feldspar, illite–phengite and chlorite associated with quartz and/or calcite and dolomite in these rocks. Magnesio-hastingsite to magnesio-hornblende bearing metagabbro with newly formed metamorphic magnesio-riebeckite and actinolite is an inferred detached Meliatic block tectonically emplaced in a Permian salinar mélange in the Silica Nappe hanging wall. Reconstructed P–T paths indicate variable metamorphic conditions from the medium-pressure to high-pressure subduction of the Bôrka and Jaklovce units to the Meliata Unit shallow burial in an accretionary wedge during Late Jurassic to Early Cretaceous Meliaticum evolution. Mélange blocks of Meliaticum incorporate different juxtaposed Meliatic paleotectonic units exposed in nappe outliers overlying the IWC Gemeric and Veporic superunits. [ABSTRACT FROM AUTHOR]

In talc-magnesite veins in serpentinite near Muránska Dlhá Lúka (MDL), Slovakia, yellow euhedral to subhedral crystals apatite of a gem quality occur. It has a composition of hydroxylapatite with F− varying between 0.29 and 0.34 apfu, Cl− in range of 0.02–0.05 apfu and calculated OH− content between 0.62–0.68 apfu. Moreover, [CO3]2− molecules were identified by FTIR and Raman spectroscopy. MDL apatite contains only up to 0.003 apfu As5+ and Si4+ substituting for P5+; Ca is substituted by small amount of Na, Fe2+, Mn2+ (all up to 0.006 apfu), and Rare Earth Elements (REE—in total up to 0.017 apfu). Compared to trace-element composition of similar apatites from Durango, Mexico, the REE content in MDL apatite is around ten times lower with Nd > Ce >> La, its chondrite-normalized REE pattern has almost a horizontal slope and larger negative Eu anomaly. The MDL apatite is richer in Mn, Pb and Li, but poorer in As, V, Th and U. The concentrations of Sr and Y are similar. In the optical absorption spectra, the most prominent bands are at 585–590 nm (Nd3+) and between 600 and 800 nm (Mn2+, Ce3+-SiO3− photochromic center and Nd3+). The photoluminescence spectrum of MDL apatite shows bands between 550 and 620 nm (Dy3+, Sm3+, Pr3+ and also Mn2+) which likely enhance its yellow color. MDL hydroxylapatite likely formed from fluids derived from granitic rocks as evidenced by the chondrite-normalized REE patterns, Li, Mn and Y concentrations. The Sr content reflects the host-rock serpentinite composition. Fluids for its crystallization were likely derived from Muráň complex orthogneisses by the Alpine deformation and recrystallization in greenschist to lower amphibolite facies. [ABSTRACT FROM AUTHOR]

Copper- and Mn-bearing elbaitic tourmaline ("Paraíba tourmaline") sometimes contains significant amounts of Pb and Bi. Their position in the tourmaline crystal structure was studied with correlation analysis and bond valence calculations. Correlations between the F content and the X-site charge allow predicting the X-site occupancy. Three sets of tourmaline analyses were studied: (1) Pb-rich tourmalines from the Minh Tien pegmatite, Vietnam; (2) Cu-, Pb- and Bi-bearing tourmalines from the Mulungu mine, Brazil; (3) Cu- and Bi-bearing tourmalines from the Alto dos Quintos mine, Brazil. Two correlations were plotted: (1) the charge by considering only Na1+, Ca2+ and K1+; (2) the charge by adding Pb2+ and Bi3+ to the X-site charge. When plotting correlations for the Minh Tien tourmalines, the correlation significantly improves by adding Pb2+ to the X site. For the Alto dos Quintos tourmalines, only a slight increase of the correlation coefficient is observed, while such a correlation for tourmalines from Mulungu interestingly shows a slight decrease of the correlation coefficient. Bond valence calculations revealed that Bi3+ and Pb2+ can indeed occupy the X site via BiLi(NaAl)−1, PbLi(NaCu)−1 and possibly PbCu(NaAl)−1 substitutions as seen in the investigated tourmaline samples. At the Y site, Pb4+ can be substituted via PbLi(AlCu)−1, and PbVO(AlVOH)−1, while Bi5+ does not have any stable arrangement in Cu-bearing fluor-elbaite. The occurrence of Pb4+ at the Y site could be one explanation for the results of the correlations of the Mulungu tourmalines. Another explanation could be that during the tourmaline crystallization some additional Bi and Pb came into the pegmatitic system and hence disturbed the correlation between the average X-site charge and the F content. Further plots of such correlations in "Paraíba tourmaline" samples might also help to distinguish between the worldwide localities of these rare and sought-after tourmalines. [ABSTRACT FROM AUTHOR]

The site preference for each cation and site in beryl based on bond-length calculations was determined and compared with analytical data. Tetrahedral SiO4 six-membered rings normally have no substitutions which results from very compact Si4+–O bonds in tetrahedra. Any substitution except Be would require significant tetrahedral ring distortion. The Be tetrahedron should also be negligibly substituted based on the bond-valence calculation; the tetrahedral Li–O bond length is almost 20% larger than Be2+–O. Similar or smaller bond lengths were calculated for Cr3+, V3+, Fe3+, Fe2+, Mn3+, Mg2+, and Al3+, which can substitute for Be but also can occupy a neighboring tetrahedrally coordinated site which is completely vacant in the full Be occupancy. The octahedral site is also very compressed due to dominant Al with short bond lengths; any substitution results in octahedron expansion. There are two channel sites in beryl: the smaller 2b site can be occupied by Na+, Ca2+, Li+, and REE3+ (Rare Earth Elements); Fe2+ and Fe3+ are too small; K+, Cs+, Rb+, and Ba2+ are too large. The channel 2a-site average bond length is 3.38 Å which allows the presence of simple molecules such as H2O, CO2, or NH4 and the large-sized cations-preferring Cs+. [ABSTRACT FROM AUTHOR]

Andradite, variety demantoid, is a rare gem mineral. We describe gem-quality garnet crystals from serpentinized harzburgites from Dobšiná, Slovakia which were faceted. Both the andradite samples were transparent, with a vitreous luster and a vivid green color. They were isotropic with refractive indices >1.81. The measured density ranged from 3.82 to 3.84 g·cm−3. Andradite var. demantoid appeared red under Chelsea filter observation. Both samples contained fibrous crystalline inclusions with the typical "horsetail" arrangement. The studied garnet had a strong Fe3+ dominant andradite composition with 1.72–1.85 apfu Fe3+, Cr3+ up to 0.15 apfu, Al3+ 0.03 to 0.04 apfu, V3+ up to 0.006 apfu substituted for Fe3+, Mn2+ up to 0.002 apfu, and Mg up to 0.04 apfu substituted for Ca. Raman spectrum of garnet showed three spectral regions containing relatively strong bands: I—352–371 cm−1, II—816–874 cm−1, and III—493–516 cm−1. The optical absorption spectrum as characterized by an intense band at 438 nm and two broad bands at 587 and 623 nm and last one at 861 nm, which were assigned to Fe3+ and Cr3+. Transmission was observed in the ultraviolet spectral region (<390 nm), near the infrared region (700–800 nm), and around 530 nm in the green region of visible light, resulting in the garnet's green color. [ABSTRACT FROM AUTHOR]