Stanislava Milovská

Raman spectra of oriented and non-oriented Cu hydroxy-phosphate minerals: Libethenite, cornetite, pseudomalachite, reichenbachite and ludjibaite

Oriented cornetite [Cu3PO4(OH)3], libethenite [Cu2PO4(OH)] and pseudomalachite [Cu5(PO4)2(OH)4] and non-oriented reichenbachite [Cu5(PO4)2(OH)4] and ludjibaite [Cu5(PO4)2(OH)4] minerals from Ľubietová and Špania Dolina dump fields, Banská Bystrica, Slovakia were examined by polarized Raman spectroscopy. The examined minerals display the characteristic vibrational modes of PO4 and OH groups and further lattice modes. The PO4 stretching and bending vibrations of the investigated minerals occur between 1150 and 900 cm(-1) and between 700 and 350 cm(-1), respectively. On the other hand, the hydroxyl group stretching and bending modes appear above 3350 cm(-1) and between 900 and 700 cm(-1), respectively. The lattice vibrations occur below 350 cm(-1). The different bond distances of the PO4 groups readily explain the shift of the bands to higher or lower wavenumbers among the studied Cu hydroxy-phosphate minerals.

Raman spectroscopic and microthermometric studies of authigenic quartz (the Pepper Mts., Central Poland) as an indicator of fluids circulation

Differently colored authigenic quartz crystals were found as the druses compound within mudstone heteroliths from the Pepper Mts. Shale Formation (Cambrian unit of the Holy Cross Mts., Central Poland). The genesis of this mineral was established on the basis of fluid inclusion study. Raman microspectroscopy was the key instrumental technique to identify the nature of the compounds trapped in the fluid inclusions. Methane (2917cm-1) or water vapor (broad band ~2500-3000cm-1) occur within two-phased primary inclusion assemblages, while nitrogen (2329cm-1) associated with methane and trace amount of carbon dioxide (1285, 1388cm-1) occur within secondary fluid inclusion assemblage. Temperatures of homogenization of primary fluid inclusions was obtained on the basis of heating experiments and ranged from 171° to 266°C. These values are much higher than expected for the diagenetic system without metamorphic changes what may imply hydrothermal origin of quartz crystals. The source of fluids is uncertain as in the Holy Cross Mts. there was no volcanic activity to the end of Late Devonian. However, fluids originated in metamorphic basin could use deep faults as the migration paths.

Kerimasite, {Ca3}[Zr2]( )O12 garnet from the Vysoká-Zlatno skarn, Štiavnica stratovolcano, Slovakia

Abstract Kerimasite {Ca3}[Zr2](SiFe3+2 )O12, a rare member of the garnet supergroup, has been identified in association with andradite–grossular and their hydrated analogues, monticellite, perovskite, clintonite, anhydrite, hydroxylellestadite–fluorellestadite, spinel, magnetite, brucite, valeriite and other minerals from a Ca-Mg skarn in the exocontact of a granodiorite porphyry intrusion in Vysoká-Zlatno Cu-Au skarnporphyry deposit, the Štiavnica stratovolcano, Central Slovakia. Kerimasite forms euhedral-to-anhedral crystals, 2 to 100 μm across with 0.73-1.62 atoms per formula unit (a.p.f.u.) Zr (16.2-33.6 wt.% ZrO2), 0.34-0.66 a.p.f.u. Ti (4.6-9.3 wt.% TiO2), 0.01 to 0.05 a.p.f.u. Hf (0.4-1.7 wt.% HfO₂: the largest Hf content reported in kerimasite), and small amounts of Sn, Sc and Nb (≤ 0.02 a.p.f.u.). Tetrahedral Si (0.99-1.67 a.p.f.u.; 9.8-18.1 wt.% SiO2) is balanced by 0.85-1.26 a.p.f.u. Fe3+and by 0.46-0.76 a.p.f.u. Al. The crystals commonly show regular, oscillatory concentric zoning or irregular patchy internal textures due to Zr, Ti, Fe, Al and Si variations during growth or partial alteration and dissolutionreprecipitation. The main substitutions in kerimasite are Y(Fe,Sc)3+ + ZSi4+ = Y(Zr,Ti,Hf,Sn)4+ + Z(Fe,Al)3+ and Ti4+ = Zr4+. Associated andradite locally contains irregular Ti- and Zr-rich zones with ≤ 11 wt.% TiO2 and ≤ 4.4 wt.% ZrO2. In comparison with common Ca-rich garnets, the micro-Raman spectrum of kerimasite shows that many bands shift towards much lower wavenumbers, either due to Fe3+ substitution on the Z site or to the strong influence of neighbouring octahedrally-coordinated Zr4+ on internal vibrations of tetrahedra that share oxygens. The formation of kerimasite, monticellite, perovskite and other phases indicate a relatively Ca-rich and Si,Al-poor environment, analogous to other known occurrences of Ca-Zr garnets (Ca-rich skarns and xenoliths, carbonatites). Kerimasite and associated skarn minerals originated during contact-thermal metamorphism of Upper Triassic marl slates with limestone, dolomite, anhydrite and gypsum by Miocene granodiorite porphyry at T ≈ 700ºC and P ≈ 50-70 MPa.

Garavellite and associated sulphosalts from the Strieborná vein in the Rožňava ore field (Western Carpathians)

Abstract The article presents the first description of a complete and continuous series from berthierite to garavellite sulphosalts in the Western Carpathians. Berthierite is a common main or accessory phase of Sb mineralizations in the Western Carpathians, and occurs at many localities and ore deposits as well. On the other side, garavellite or Bi-rich berthierite is a relatively rare accessory phase. The highest Bi content in garavellite reaches up to 38.04 wt. % which represents 0.90 apfu, and its crystallochemical formula can be written as Fe0.97Sb1.07Bi0.90S3.98. Raman band shifts were observed in the isomorphic berthierite–garavellite series. Garavellite occurs in the younger stages of sulphidic mineralization, and associates with tetrahedrite, berthierite, Bi-chalcostibite, Sb-bismuthinite, Bi-stibnite, ullmanite and cinnabarite. It creates irregular grains and veinlets in pre-existing tetrahedrite, or forms myrmekite intergrowths with chalcopyrite in tetrahedrite. Bi content in chalcostibite is up to 0.20 apfu. Besides the tetrahedrite, pre-existing sulphosalts are the members of the tintinaite–kobellite series, Bi-jamesonite and bournonite. The Sb/(Sb+Bi) ratio of minerals of the tintinaite–kobellite series varies from 0.37 to 0.80. The maximum content of Bi in jamesonite is up to 1.22 apfu. A vertical zonation at the ore vein body (mining levels 6 / 180 a.s.l., 8 / 80 a.s.l., 10 / 20 b.s.l.) is represented by the Sb decrease along with the Bi increase with increasing depth. Bi content continuously decreases during the older ore mineralization stage and Sb increases at the younger mineralization stage. Both of the stages have been enriched by Sb as well.

The determination of the Sb/As content in natural tetrahedrite–tennantite and bournonite–seligmannite solid solution series by Raman spectroscopy

Abstract Natural samples containing tetrahedrite-tennantite, bournonite-seligmannite and geocronite-jordanite from the Coranda-Hondol ore deposit, Romania, were investigated by Raman spectroscopy to determine its capability to provide estimates of solid solutions in three common and widespread sulfosalt mineral series. Raman measurements were performed on extended solid solution series (Td1 to Td97, Bnn25 to Bnn93 and Gcn24 to Gcn67, apfu). The tetrahedrite-tennantite and bournonite-seligmannite solid solution series show strong correlations between spectroscopic parameters ( position, relative intensity and shape of the Raman bands) and the Sb/(Sb+As) content ratio, while Raman spectra of geocronite-jordanite shows no evolution of Raman bands. In order to simplify the method used to estimate the Sb/(Sb+As) content ratio in tetrahedrite-tennantite and bournonite-seligmannite series, several linear equations of the first-order polynomial fit were obtained. The results are in good agreement with electron microprobe data. Moreover, a computer program was developed as an analytical tool for a fast and accurate determination of Sb/(Sb+As) content ratio by at least one spectroscopic parameter. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of the tetrahedrite-tennantite and bournonite- seligmannite series.