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    Polytypism in micas from Black Hill and apparent polytypism in micas from Alto Paranaibo

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    Micas are commonly found minerals of igneous and metamorphic rocks which form in a wide range of chemical and physical conditions. This particular feature can be understood on the ground of the compositional variation and different cation arrangement connected with the intensive parameters change during the crystallization process. Recent studies of cation site partitioning in Tirich 1M polytype from Black Hill (Australia) using a multi-technical approach [1] showed the occurrence of Fe, as Fe2+ and Fe3+, and Ti, as Ti3+ and Ti4+. While Titanium populates both octahedral and tetrahedral site, Fe is located only at the octahedral position. In addition Mg and Fe distribution was shown to be shared out in approximately equal amounts across M1 and M2 site. The present study investigates the 2M1 polytype, coexisting with 1M form, from Black Hill. Structural analysis showed similar M1 and M2 cation distribution in both polytypes with some noteworthy differences regarding occupancy of the octahedral cations. More specifically, while Mg and Fe randomly populate both M1 and M2 site in the 1M polytype, these cations are distributed in orderly manner in the 2M1 polytype, resulting in symmetry change from C2/m (1M) to C2/c (2M1) as well as c parameter doubling. This work also investigates an apparent polytype, observed in the trioctahedral micas from Alto Paranaibo igneous province (Southeastern Brazil). Crystal chemistry of 1M polytype from this locality was investigated by [2]. By making use of the multitechnical approach, [3] recently reanalysed one of the sample quoted in [2] and labelled Ma1. A number of interesting new results were found: Na is lodged at octahedral site, Ti at both octahedral and tetrahedral sites and all Fe3+ at tetrahedral site and Fe2+ populating the same octahedral site. Further investigations showed that the Ma1 can also form apparent polytypes, i.e. twinnings of 1M polytype which simulate diffraction of polytype patterns with long periodicity (c ≈ 30 Å). Structure refinement of the twinned crystal (R = 3.9%, carried out on the family reflections) indicated that the twin law is [310], the twin index is 3 and the volume element ratio is roughly 0.85 : 0.09 : 0.06. The same conclusions were reached by [4] when studying ferric phlogopites from Ruiz Peak (Northern Chile)

    A new application of SIMS to the analysis of nitrogen in mica minerals: tobelite.

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    Muscovite, KAl2[AlSi3O10](OH)2, is a common rock-forming mineral in igneous and metamorphic-rocks, sediments, hydrothermal alteration and ore deposits. The site between two adjacent T-O-T (tetrahedral-octahedral-tetrahedral) layers is shared between K and NH4 in any proportion leading to the building of the “ammonium micas”. Mica with: (i) NH4>K, □ (vacancy); (ii) Si ≥ 3 apfu (atoms per formula unit); (iii) layer charge (T-O-T) less than one, is named tobelite [Brigatti M F and Guggenheim S 2002 Rev. Mineral. Geochem. 46 1-97]. The NH4-analog of muscovite, i.e., tobelite, has been predominantly associated to two distinct geological settings: a) diagenetic to low grade metamorphic shales from meta- anthracite and anthracite coal fields; b) hydrothermal areas alteration [Ruiz Cruz M D and Sanz de Galdeano C 2010 Clays Clay Miner. 58 558-572]. In this work three crystals labelled Tob_M2, Tob_M3, Tob_3 were investigated by electron probe microanalysis (EPMA) in terms of major constituents, and in terms of nitrogen by secondary ion mass spectrometry (SIMS) in order to gain information on the presence and amount of NH4. Nitrogen was detected as secondary positive ions by means of a Cameca IMS 4f ion microprobe installed at CNR-IGG, Pavia. SIMS analysis on 14N+ was performed with 16O- primary beam at a mass resolution (M/ΔM) of ~ 1250 required to discriminate the 28Si2+ and 12CH2 + interferences at the nominal mass number 14 (a.m.u.). In spite of the severe inhomogeneity of nitrogen in each crystal, the SIMS data put Tob_M2 as the N-richest crystal of the set. The crystal, analyzed at different spots, is characterized by an ion signal in the range 399 - 560 (c/s). For Tob_M3 the 14N+ average ion signal is 91 (c/s). In Tob_3 the N content is likely the lowest in the sample set with an average count rate of 61 (c/s). The lack of calibration standards did not allow so far to obtain quantitative results for N at the ion microprobe. Nevertheless, our SIMS data agree qualitatively with constraints derived from EPMA and charge-balance crystal chemical considerations, and point out that the ion probe is a valuable tool for the investigation of N in mica minerals

    SIMS investigation of nitrogen in tobelite. Constraints from EMPA and crystal chemical charge-balance

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    Possibility to develope reference materials (standards) for quantitative SIMS analysis of nitrogen in mica
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