Zinc-rich fluor-elbaite from Piława Górna, Poland, was studied by electron microprobe (EPMA), single-crystal X-ray diffraction (SREF), and Raman spectroscopy (RS) to check the possibility of the application of RS to draw crystal-chemical conclusions for Al-rich and Li-bearing tourmalines on basis of the O–H stretching vibrations in the spectral range 3400–3800 cm–1. This tourmaline, forming a thin metasomatic zone around gahnite, features varying compositions with a ZnO content reaching in the studied fragment of 5.70(12) wt%. The crystal structure of this Zn-rich fluor-elbaite [a = 15.921(1), c = 7.127(1) Å] was refined with a R1 value of 1.67%. Its formula was determined on the basis of electron-microprobe and structure refinement as (Na0.84☐0.14Ca0.01)XΣ1.00(Al1.06Li0.84Zn0.69Fe0.322+Mn0.09)YΣ3.00AlZ6(BO3)3(Si6TO18)(OH)3V(F0.65OH0.26O0.09)W. The deconvolution of the O–H stretching vibration bands, performed by fitting of an input model of component bands with Gaussian function shapes for the empirical spectrum, indicates that each of the three maxima assigned for VOH bonded to YAl3+, Y2+, and YLi+ and with the total integral intensity of at least 75% of the total OH content could be resolved into 1 to 3 bands, depending on the X-site occupation (vacancies, Na+, and Ca2+). The deconvolution indicates further that several low intense bands of WO–H modes above a Raman shift of 3600 cm–1, totally reaching ≤25%, are dependent on the occupation of triplets of YYY cations bonded to the hydroxyl. These WO–H modes are also influenced by the X-site occupation. Due to ordering of all octahedral cations (except Al) at the Y site and a complete occupation of the Z site by Al and the V site by OH, it seems possible to evaluate the Li and OH contents in a Al-rich and Li-bearing tourmaline directly from the Raman spectrum. By using the ratio VOHIYAlZAlZAl/(VOHIYZZ + WOHIYYY) as evaluated from RS, corresponding to the ratio YAl/V+WOH in the crystal, the formula of the Zn-rich fluor-elbaite can be calculated as (Na0.85☐0.14Ca0.01)XΣ1.00(Al1.11Y1.112+Li0.78)YΣ3.00AlZ6(BO3)3(Si6O18)(OH)3(F0.65OH0.13O0.22), where Y 2+ = Zn + Fe + Mn. The formula, determined only on basis of EPMA and deconvolution of RS in the O–H stretching bands, corresponds very well (≤1 SD range of EPMA) to the formula determined on basis of EPMA and SREF. This result implicates that the O–H stretching vibrations, measured by Raman spectroscopy, could be applied for Al-rich and Li-bearing tourmalines as a useful tool for providing additional information for determining the crystal-chemical formula. It is also very helpful when crystal structural data are not available.

A geochemically primitive, moderately fractionated, LCT pegmatite from Lutomia (Góry Sowie Block, SW Poland) has been characterized in respect of the primary and secondary phosphate assemblages. The pegmatite crystallized from anatectic granitic magmas mobilized by M 2-3 metamorphism at ~370-380 Ma. Three phosphate assemblages had a different origin: (1) the primary, magmatic one [graftonite-(I)-beusite-(I) + triphylite ± sarcopside], (2) a secondary, metasomatic one [Ca-rich graftonite-(II)-Ca-rich beusite-(II) + wolfeite/triploidite/stanĕkite + hagendorfite/alluaudite + kryzhanovskite ± a Ca-bearing phosphate close to ferromerrillite + fluorapatite], and (3) a secondary, hydrothermal and weathering one [ferrisicklerite ± heterosite + phosphoferrite-kryzhanovskite + ludlamite + vivianite ± hureaulite + earlshannonite-whitmoreite + strunzite-ferrostrunzite + beraunite + dufrénite + jahnsite-(CaMnFe),-(CaMnMn) and-(MnMnMn) + landesite + fairfieldite + Mn 2+-bearing hydroxyapatite]. The magmatic assemblage resulted from the breakdown of a primary, high-T, Ca-and Li-enriched graftonite-like phase. It was induced by cooling and elevated incompatible Ca, Na, Li and F concentrations. The metasomatic assemblage reflects the destabilization of the magmatic phosphates and their Ca-and Na-metasomatism by a high-T fluid connected with a PO 4-bearing melt, which previously had evolved along with graftonite-(I)-beusite-(I). The assemblage of secondary, hydrothermal and weathering, phosphates was a result of lower T alteration by hydrothermal fluids and meteoric water by both topotactic Fe and Mn oxidation as well gradual hydration and Fe oxidation. Taken together, the Lutomia pegmatite has been compared to the phosphate-bearing pegmatite at Michałkowa and the mixed NYF + LCT, PO 4-poor pegmatitic system of Piława Górna.

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(Na_0.733Ca_0.013☐_0.254)_Σ1^Y(Al_1.033Li_0.792Zn_0.755Fe²⁺_0.326Mn_0.094)_Σ3^ZAl₆(^TSi₆O₁₈)(BO₃)₃^V(OH)₃^W(F_0.654OH_0.344), and ^X(Na_0.779Ca_0.015☐_0.206)_Σ1^Y(Al_1.061Li_0.869Zn_0.880Fe²⁺_0.098Mn_0.094)_Σ3^ZAl₆(^TSi₆O₁₈)(BO₃)₃^V(OH)₃^W(OH_0.837F_0.163), 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.

Ishikawaite and samarskite-(Y) are indicators of an NYF signature in the mildly to moderately fractionated parts of the hybrid NYF + LCT Julianna pegmatitic system at Piława Górna, the Góry Sowie Block, SW Poland. The minerals were metasomatically altered by a Ca-bearing and Ta-enriched highly fluxed residual silicate melt. The intensity of the metasomatism and the chemical composition of its products strongly depended on the efficiency of the transport of ions to and from the replacement front. Restricted access of the fluid promoted the formation of calciosamarskite and oxycalciopyrochlore. Where the fluid could migrate more easily, with decreasing pH and temperature the alteration products became deficient in A-site cations (mainly Ca²⁺ and Mn²⁺). Consequently, earlier-crystallized pyrochlores transformed to zero-valent-dominant pyrochlores and microlites enriched in U+Th, Y+REE, or Ca. Low-temperature hydrothermal fluids were responsible for the final enrichment in Pb and Bi.