A spectacular epigenetic silicification was encountered in the Oxfordian bedded limestones exposed in the Sokole Hills situated in the Krakow-Częstochowa Upland. The main epigenetic mineral is microcrystalline quartz accompanied by minor goethite, hematite, barite, galena and sphalerite. Locally, the mineralized limestones reveal Pb and Cu contents exceeding over 150 times the background values of these metals in unmineralized limestones.The epigenetic mineralization of the bedded limestones was probably a two-stage process. During the first, Early Cretaceous stage, silicified limestones formed at the erosional surface of a denuded carbonate complex. Such silicification greatly limited the progress of the first karstification phase of the Upper Jurassic carbonates initiated in the Hauterivian. The sources of silica accumulated in the limestones were descending solutions enriched in silica derived from the weathering zone. This silicification affected the topmost part of the Upper Jurassic massive limestones and the deeper portions of the bedded limestones along the fracture systems and stylolites.Early Cretaceous tectonic activity generated new dislocations and re-opened the existing faults, which were subsequently filled with permeable Albian quartz sands. These openings became the migration pathways for ascending, warm, relict, sulphide-carrying hydrothermal solutions at the second formation stage of the epigenetic mineralization. The newly supplied silica from the Albian sands precipitated on the silicified limestones and, as concentric rims, on brecciated, early diagenetic cherts. The second-stage mineralization proceeded under phreatic conditions, presumably close to a fluctuating mixing zone of ascending, warm hydrothermal solutions and descending cold groundwaters. The brecciated cherts acting as silica crystallization nuclei indicate that the last mineralization stage probably followed the final phase of Cenozoic faulting

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.