Towards Zn-dominant tourmaline: A case of Zn-rich fluor-elbaite and elbaite from the julianna system at Piława Górna, Lower Silesia, SW Poland

Tourmalines are a group of minerals which may concentrate various accessory components, e.g., Cu, Ni, Zn, Bi, Ti, and Sn. The paper presents fluor-elbaite and elbaite from a dyke of the Julianna pegmatitic system at Piława Górna, at the NE margin of the Bohemian Massif, SW Poland, containing up to 6.32 and 7.37 wt % ZnO, respectively. Such high amounts of ZnO are almost two times higher than in the second most Zn-enriched tourmaline known to date. The compositions of the Zn-rich tourmalines from Piława Górna, studied by electron micropropy and Raman spectroscopy, correspond to the formulae:X(Na0.733Ca0.013□0.254)Y Σ1 (Al1.033Li0.792 Zn0.755Fe2+0.326Mn0.094)Z Σ3 Al6(TSi6O18)(BO3)V 3 (OH)W 3 (F0.654OH0.344), andX(Na0.779Ca0.015□0.206)Σ1 Y(Al1.061Li0.869Zn0.880Fe2+0.098Mn0.094)Z Σ3 Al6(TSi6O18)(BO3)V 3 (OH)W 3 (OH0.837F0.163), respectively, with Zn as one of the main octahedral occupants. A comparison with other tourmalines and associated Zn-rich fluor-elbaite and elbaite from the pegmatite indicates that atypically high Zn-enrichment is not a result of Zn-Fe fractionation, but dissolution and reprecipitation induced by a late (Na,Li,B,F)-bearing fluid within the assemblage of gahnite spinel and primary schorl-type tourmaline. This strongly suggests Na-Li-B-F metasomatism of gahnite-bearing mineral assemblages as that is the only environment that can promote crystallization of a hypothetical Zn-dominant tourmaline. The compositions of the Zn-rich fluor-elbaite and elbaite suggest three possible end-members for such a hypothetical tourmaline species: NaZn3Al6(Si6O18)(BO3)3(OH)3(OH), □(Zn2Al)Al6(Si6O18)(BO3)3(OH)3(OH) and Na(Zn2Al)Al6(Si6O18)(BO3)3(OH)3O by analogy with other tourmalines with divalent Y occupants, such as schorl/foitite/oxy-schorl and dravite/magnesio-foitite/oxy-dravite.National Centre for Atmospheric Scienc

Chemical composition of Mn-and Cl-rich apatites from the szklary pegmatite, central sudetes, SW Poland: Taxonomic and genetic implications

The research was founded by the National Science Centre (Poland) grant number 2015/17/B/ST10/03231 and the University of Wroclaw grant 0401/0156/18Although calcium phosphates of the apatite group (apatites) with elevated contents of Mn are common accessory minerals in geochemically evolved granitic pegmatites, their Mn-dominant analogues are poorly studied. Pieczkaite,M1 Mn2 M2 Mn3 (PO4)3 X Cl, is an exceptionally rare Mn analogue of chlorapatite known so far from only two occurrences in the world, i.e., granitic pegmatites at Cross Lake, Manitoba, Canada and Szklary, Sudetes, SW Poland. In this study, we present the data on the compositional variation and microtextural relationships of various apatites highly enriched in Mn and Cl from Szklary, with the main focus on compositions approaching or attaining the stoichiometry of pieczkaite (pieczkaite-like apatites). The main goal of this study is to analyze their taxonomical position as well as discuss a possible mode of origin. The results show that pieczkaite-like apatites represent the Mn-rich sector of the solid solutionM1 (Mn,Ca)2 M2 (Mn,Ca)3 (PO4)3 X (Cl,OH). In the case of cation-disordered structure, all these compositions represent extremely Mn-rich hydroxylapatite or pieczkaite. However, for cation-ordered structure, there are also intermediate compositions for which the existence of two hypothetical end-member species can be postulated:M1 Ca2 M2 Mn3 (PO4)3 X Cl andM1 Mn2 M2 Ca3 (PO4)3 X OH. In contrast to hydroxylapatite and pieczkaite, that are members of the apatite-group, the two hypothetical species would classify into the hedyphane group within the apatite supergroup. The pieczkaite-like apatites are followed by highly Mn-enriched fluor-and hydroxylapatites in the crystallization sequence. Mn-poor chlorapatites, on the other hand, document local contamination by the serpentinite wall rocks. We propose that pieczkaite-like apatites in the Szklary pegmatite formed from small-volume droplets of P-rich melt that unmixed from the LCT-type (Li–Cs–Ta) pegmatite-forming melt with high degree of Mn-Fe fractionation. The LCT melt became locally enriched in Cl through in situ contamination by wall rock serpentinites.National Science Centre (Poland), University of Wrocla

Żabińskiite, ideally Ca(Al_(0.5)Ta_(0.5))(SiO_4)O, a new mineral of the titanite group from the Piława Górna pegmatite, the Góry Sowie Block, southwestern Poland

Żabińskiite, ideally Ca(Al_(0.5)Ta_(0.5))(SiO_4)O, was found in a Variscan granitic pegmatite at Piława Górna, Lower Silesia, SW Poland. The mineral occurs along with (Al,Ta,Nb)- and (Al,F)-bearing titanites, a pyrochlore-supergroup mineral and a K-mica in compositionally inhomogeneous aggregates, ∼120 μm × 70 μm in size, in a fractured crystal of zircon intergrown with polycrase-(Y) and euxenite-(Y). Żabińskiite is transparent, brittle, brownish, with a white streak, vitreous lustre and a Mohs hardness of ∼5. The calculated density for the refined crystal is equal to 3.897 g cm^(–3), but depends strongly on composition. The mineral is non-pleochroic, biaxial (–), with mean refractive indices ≥1.89. The (Al,Ta,Nb)-richest żabińskiite crystal, (Ca_(0.980)Na_(0.015))Σ=0.995(Al_(0.340) Fe^(3+)_(0.029) Ti_(0.298)V_(0.001)Zr_(0.001)Sn_(0.005)Ta_(0.251)Nb_(0.081))Σ=1.005[(Si_(0.988)Al_0.012)O_(4.946)F_(0.047)(OH)_(0.007))Σ=5.000]; 60.7 mol.% Ca[Al_(0.5)(Ta,Nb)_(0.5)](SiO_4)O; is close in composition to previously described synthetic material. Żabińskiite is triclinic (space group symmetry Ai and has unit-cell parameters a = 7.031(2) Å, b = 8.692(2) Å, c = 6.561(2) Å, α = 89.712(11)°, β = 113.830(13)°, γ = 90.352(12)° and V = 366.77 (11) Å3. It is isostructural with triclinic titanite and bond-topologically identical with titanite and other minerals of the titanite group. Żabińskiite crystallized along with (Al,Ta,Nb)-bearing titanites at increasing Ti and Nb, and decreasing Ta activities, almost coevally with polycrase-(Y) and euxenite-(Y) from Ca-contaminated fluxed melts or early hydrothermal fluids

Limitations of Fe^(2+) and Mn^(2+) site occupancy in tourmaline: Evidence from Fe^(2+)- and Mn^(2+)-rich tourmaline

Fe^(2+)- and Mn^(2+)-rich tourmalines were used to test whether Fe^(2+) and Mn^(2+) substitute on the Z site of tourmaline to a detectable degree. Fe-rich tourmaline from a pegmatite from Lower Austria was characterized by crystal-structure refinement, chemical analyses, and Mössbauer and optical spectroscopy. The sample has large amounts of Fe^(2+) (~2.3 apfu), and substantial amounts of Fe^(3+) (~1.0 apfu). On basis of the collected data, the structural refinement and the spectroscopic data, an initial formula was determined by assigning the entire amount of Fe^(3+) (no delocalized electrons) and Ti^(4+) to the Z site and the amount of Fe^(2+) and Fe^(3+) from delocalized electrons to the Y-Z ED doublet (delocalized electrons between Y-Z and Y-Y): X(Na_(0.9)Ca_(0.1)) ^Y(Fe^(2+)_(2.0)Al_(0.4)Mn^(2+)_(0.3)Fe^(3+)_(0.2)) ^Z(Al_(4.8)Fe^(3+)_(0.8)Fe^(2+)_(0.2)Ti^(4+)_(0.1)) ^T(Si_(5.9)Al_(0.1))O_(18) (BO_3)_3^V(OH)_3 ^W[O_(0.5)F_(0.3)(OH)_(0.2)] with α = 16.039(1) and c = 7.254(1) Å. This formula is consistent with lack of Fe^(2+) at the Z site, apart from that occupancy connected with delocalization of a hopping electron. The formula was further modified by considering two ED doublets to yield: ^X(Na_(0.9)Ca_(0.1)) ^Y(Fe^(2+)_(1.8)Al_(0.5)Mn^(2+)_(0.3)Fe^(3+)_(0.3)) ^Z(Al_(4.8)Fe^(3+)_(0.7)Fe^(2+)_(0.4)Ti^(4+)_(0.1)) ^T(Si_(5.9_Al_(0.1))O_(18) (BO_3)_3 ^V(OH)_3 ^W[O_(0.5)F_(0.3)(OH)_(0.2)]. This formula requires some Fe^(2+) (~0.3 apfu) at the Z site, apart from that connected with delocalization of a hopping electron. Optical spectra were recorded from this sample as well as from two other Fe^(2+)-rich tourmalines to determine if there is any evidence for Fe^(2+) at Y and Z sites. If Fe^(2+) were to occupy two different 6-coordinated sites in significant amounts and if these polyhedra have different geometries or metal-oxygen distances, bands from each site should be observed. However, even in high-quality spectra we see no evidence for such a doubling of the bands. We conclude that there is no ultimate proof for Fe^(2+) at the Z site, apart from that occupancy connected with delocalization of hopping electrons involving Fe cations at the Y and Z sites. A very Mn-rich tourmaline from a pegmatite on Elba Island, Italy, was characterized by crystal-structure determination, chemical analyses, and optical spectroscopy. The optimized structural formula is ^X(Na_(0.6)□_(0.4)) ^Y(Mn^(2+)_(1.3)Al_(1.2)Li_(0.5)) ^ZAl_6 ^TSi_6O_(18) (BO_3)_3 ^V(OH)_3 ^W[F_(0.5)O_(0.5)], with α = 15.951(2) and c = 7.138(1) Å. Within a 3σ error there is no evidence for Mn occupancy at the Z site by refinement of Al ↔ Mn, and, thus, no final proof for Mn^(2+) at the Z site, either. Oxidation of these tourmalines at 700–750 °C and 1 bar for 10–72 h converted Fe^(2+) to Fe^(3+) and Mn^(2+) to Mn^(3+) with concomitant exchange with Al of the Z site. The refined ^ZFe content in the Fe-rich tourmaline increased by ~40% relative to its initial occupancy. The refined YFe content was smaller and the distance was significantly reduced relative to the unoxidized sample. A similar effect was observed for the oxidized Mn^(2+)-rich tourmaline. Simultaneously, H and F were expelled from both samples as indicated by structural refinements, and H expulsion was indicated by infrared spectroscopy. The final species after oxidizing the Fe^(2+)-rich tourmaline is buergerite. Its color had changed from blackish to brown-red. After oxidizing the Mn^(2+)-rich tourmaline, the previously dark yellow sample was very dark brown-red, as expected for the oxidation of Mn^(2+) to Mn^(3+). The unit-cell parameter α decreased during oxidation whereas the c parameter showed a slight increase