Browsing by Author "Karfunkel, Joachim"

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    57Fe-Mössbauer spectroscopy on natural eosphorite-childrenite-ernstite samples.
    (2005) Costa, Geraldo Magela da; Cipriano, Ricardo Augusto Scholz; Karfunkel, Joachim; Bermanec, Vladimir; Chaves, Mario Luiz de Sá Carneiro
    Samples of the eosphorite-childrenite [(Mn2+, Fe2+)AlPO4(OH)2H2O] series from Divino das Laranjeiras and Araçuaí (Minas Gerais State) and Parelhas (Rio Grande do Norte State) pegmatites have been investigated by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy at 295 and 77 K. The Mössbauer spectra of ernstite [(Mn2+, Fe3+)Al- PO4(OH)2-xOx] showed the existence of ferric ions in both A and B sites, whereas ferrous ions seem to be located exclusively in the A site. Nonoxidised samples show ferrous ions located in both sites, and no Fe3+ could be detected. The interpretation of the Mössbauer spectra of both, oxidised and nonoxidised samples, is difficult because the hyperfine parameters of these minerals are rather similar, rendering it difficult to make proper site assignments.
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    On the yellow color of gamma‐irradiated brazilianite from Minas Gerais (Brazil).
    (2021) Pinheiro, Mauricio Veloso Brant; Cipriano, Ricardo Augusto Scholz; Karfunkel, Joachim; Chaves, Mario Luiz de Sá Carneiro; Krambrock, Klaus Wilhelm Heinrich
    The origin of gamma irradiation-induced strong yellow color in brazilianite from Brazil is investigated. The irradiation- induced optical absorption band responsible for the color shows an onset in the blue spectral region at about 2.5 eV and maximum centered in the UV at ~ 4.24 eV. From the ratio between the squared value of the line width (W2 ) and the peak energy (M), a value of about 0.09 eV is estimated, which is consistent with an absorption band caused by a Schirmer ́s-type O− bound small polaron. By electron paramagnetic resonance (EPR), we are able to confrm its microscopic structure. This O− hole center is in fact the Al3+–O−X2+–P5+ hole center already identifed by EPR earlier in the literature (where X2+ stands for a nearby divalent cation with negligible abundance of magnetic isotopes). The EPR spectrum of the Al3+–O−X2+–P5+ hole center, along with the O− bound small polaron absorption band responsible for the yellow color, appears simultane- ously at high concentrations after gamma irradiation, and vanishes together for thermal annealing above 300 °C, returning after re-irradiation in a reversible way. Their appearance is concomitant with the H0 centers and Ti3+ electron centers, and possible charge-compensating centers.
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    Palaeoecological implications of an Upper Cretaceous tetrapod burrow (Bauru Basin; Peirópolis, Minas Gerais, Brazil).
    (2019) Martinelli, Agustin Guillermo; Basilici, Giorgio; Fiorelli, Lucas Ernesto; Klock, Carolina; Karfunkel, Joachim; Diniz, Ariela Costa; Soares, Marcus Vinícius Theodoro; Marconato, André; Silva, João Ismael da; Ribeiro, Luiz Carlos Borges; Marinho, Thiago da Silva
    We describe a globally rare example of a tetrapod burrow from the Upper Cretaceous Bauru Group (Bauru Basin) from Peirópolis, Minas Gerais State, Brazil. The sedimentary succession containing the burrow includes a rich vertebrate assemblage comprising fish, podocnemid turtles, mesoeucrocodylians, saurischian dinosaurs, among others. The burrow is composed of an oblique tunnel (~30°), oval in cross-section, with a horizontal and suboval terminal chamber; it is 1.3 m long from the midpoint of its inferred entrance to the midpoint of the bottom of the chamber. It occurs in the upper portion of a sandstone succession, interpreted as a braided channel deposit, and the burrow-fill comprises medium-grained sandstone with mudstone intraclasts derived from fluvial floodplain facies. it is overlain by other fluvial channel deposits. Analyses suggest that the burrow was dug after the filling of the braided channel and during the pedogenesis of its exposed upper surface. Based on burrow morphology and size, the most plausible producer of this burrow is a notosuchian mesoeucrocodylian, such as small to mid-sized notosuchians (e.g., sphagesaurids). The Bauru Group has an extensive fossil record of notosuchians with disparate morphologies, and it is noteworthy that the small-sized notosuchian Labidiosuchus amicum comes from the same unit as the burrow. Moreover, arid to semi-arid conditions have been inferred for fossil-bearing rocks of this unit, and as such the data here presented add to our palaeoecological knowledge of Cretaceous mesoeucrocodylians in Gondwana. Moreover, it constitutes a new Cretaceous record of a tetrapod burrow during a period when such ichnofossils are globally rare.
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    Radiation-induced defects in montebrasite : an electron paramagnetic resonance study of O – hole and Ti3+ electron centers.
    (2020) Toledo, José Roberto de; Gonçalves, Raphaela de Oliveira; Dias, Lorena N.; Chaves, Mario Luiz de Sá Carneiro; Karfunkel, Joachim; Cipriano, Ricardo Augusto Scholz; Pinheiro, Mauricio Veloso Brant; Krambrock, Klaus Wilhelm Heinrich
    Montebrasite is a lithium aluminum phosphate mineral with the chemical formula LiAlPO4(Fx,OH1–x) and considered a rare gemstone material when exhibiting good crystallinity. In general, montebrasite is colorless, sometimes pale yellow or pale blue. Many minerals that do not have colors contain hydroxyl ions in their crystal structures and can develop color centers after ionization or particle irradiation, examples of which are topaz, quartz, and tourmaline. The color centers in these minerals are often related to O– hole centers, where the color is produced by bound small polarons inducing absorption bands in the near UV to the visible spectral range. In this work, colorless montebrasite specimens from Minas Gerais state, Brazil, were investigated by electron paramagnetic resonance (EPR) for radiation-induced defects and color centers. Although γ irradiation (up to a total dose of 1 MGy) did not visibly modify color, a 10 MeV electron irradiation (80 MGy) induced a pale greenish-blue color. Using EPR, O– hole centers were identified in both γ- or electron-irradiated montebrasite samples showing superhyperfine interactions with two nearly equivalent 27Al nuclei. In addition, two different Ti3+ electron centers were also observed. From the γ irradiation dose dependency and thermal stability experiments, it is concluded that production of O– hole centers is limited by simultaneous creation of Ti3+ electron centers located between two equivalent hydroxyl groups. In contrast, the concentration of O– hole centers can be strongly increased by high-dose electron irradiation independent of the type of Ti3+ electron centers. From detailed analysis of the EPR angular rotation patterns, microscopic models for the O– hole and Ti3+ electron centers are presented, as well as their role in the formation of color centers discussed and compared to other minerals.
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    Spectroscopic characterization of transition metal impurities in natural montebrasite/amblygonite.
    (2010) Dias, Lorena Nunes; Pinheiro, Mauricio Veloso Brant; Moreira, Roberto Luiz; Krambrock, Klaus Wilhelm Heinrich; Guedes, Kassílio José; Menezes Filho, Luiz Alberto Dias; Karfunkel, Joachim; Schnellrath, Jurgen; Cipriano, Ricardo Augusto Scholz
    Natural single-crystal specimens of the montebrasite/amblygonite series from Brazil, with general formula LiAlPO4(F,OH), were investigated by electron microprobe, Raman spectroscopy, X-ray diffraction, and infrared absorption. Since little is known about impurities and their local symmetries, electron paramagnetic resonance (EPR) was applied. Six different paramagnetic impurities and radiation defects were detected by EPR. Three of them, all substituting for Al3+ ions, namely, iron (Fe3+), vanadium (V4+), and niobium (Nb4+) impurities were characterized in this work. The Fe3+ (3d5)-related EPR spectra and angular dependencies show occupation of low-symmetry sites that are revealed in the high asymmetry parameter of the electronic fine structure, E/D = 0.27. Vanadium and niobium impurities are identified through their typical strong hyperfine interactions. Both form interesting examples for which the properties of 3d1 ion (V4+) and 4d1 ion (Nb4+) in the same host matrix can be compared. It is shown that both ions form complex defects of type VO2+ (vanadyl) and NbO2+ (niobyl), showing superhyperfine interaction with two equivalent hydrogen ions and not to fluorine. The EPR rotation patterns are analyzed in detail for three mutually perpendicular crystal planes. Spin Hamiltonian parameters are calculated and discussed.