Since the 12th century in the Silesian-Cracovian area, lead, litharge, and silver have been produced by the pyrometallurgical processing of Pb-Ag-Zn ore. Slags and soils contaminated with heavy metals (Zn, Pb, Cd, Fe, Mn, As) were the subject of this research. Samples were collected during archaeological works in the area of early medieval metallurgical settlement. The main goals of the analyses (Scanning Electron Miscroscopy-Energy Dispersive Spectroscopy (SEM-EDS), Electron Probe Microanalyzer (EPMA), X-ray diffraction (XRD), Atomic Absorption Spectroscopy (AAS)) were the determination of the mineralogical composition of furnace batches and smelting temperatures and conditions. In soils, the anthropogenic phases enriched in Pb, Zn, Fe, Mn, P, and primary minerals like goethite, ferrihydrite, sphalerite, galena, smithsonite, minrecordite, cerussite, gypsum, anglesite, jarosite, and hemimorphite were identified. The soil from former metallurgical settlements contained up to 1106 mg·kg −1 Pb, 782 mg·kg −1 Zn, 4.7 mg·kg −1 Cd in the fine fraction. Much higher heavy metal concentrations were observed in the waste products of ore rinsing, up to 49,282 mg·kg −1 Pb, 64,408 mg·kg −1 Zn, and 287 mg·kg −1 Cd. The medieval smelting industry and Pb-Ag-Zn ore processing are marked by highly anomalous geochemical pollution (Pb, Zn, Cd, Fe, Mn, Ba) in the topsoil. The methods of mineralogical investigation, such as SEM-EDS or EMPA, can be used to identify mineralogical phases formed during metallurgical processes or ore processing. Based on these methods, the characteristic primary assemblage and synthetic phases were identified in the area polluted by medieval metallurgy and mining of Pb-Ag-Zn ores, including MVT (Mississippi Valley Type) deposits. The minerals distinguished in slags and the structural features of metal-bearing aggregates allow us to conclude that batches have included mostly oxidised minerals (PbCO 3 , ZnCO 3 , CaZn(CO 3 ) 2 , FeOOH), sulfides (PbS and ZnS) and quartz (SiO 2 ). The laboratory experiment of high-temperature heating of the examined slags showed that smelting temperatures used in the second half of 13th century were very high and could have reached up to 1550 • C. The results indicate, that geochemical and mineralogical methods can be used to obtain important information from archaeological sites, even after archaeological work has long ceased.Minerals 2020, 10, 28 2 of 16 mining and metallurgy centres since Roman times. In the period between the 10th and 12th centuries, iron, lead, tin, silver, and gold had become more important for the development of civilization in Central and Eastern European countries. Since the beginning of the 10th century in medieval Europe, in areas where ores of Ag-Pb, Au, As-Au, Cu, Sn and Fe occurr, mining centres have appeared, such as at the Ore Mountains (Erzgebirge), Harz Mountains, and Sudetes.One of Europe's largest Zn-Pb, MVT (Mississippi Valley) type ore deposits can be found in the Silesian-Cracow area (southern Poland) [1]. Shallow deposits are represented...

Textural relationships and compositional variations of (Fe,Mn)-(Ti,Sn)-(Nb,Ta) oxides and associated minerals from low-to moderately fractionated, mixed (NYF + LCT) anatectic pegmatites, which belong to the Julianna pegmatitic system, exposed at Piława Górna, Lower Silesia, Poland, were studied to elucidate the geochemical evolution of the pegmatite-forming melt. The primary Nb-Ta oxides crystallized in the following sequence: (1) columbite-(Fe) evolving to columbite-(Mn), associated with Nb-and Ta-bearing ilmenite-pyrophanite + almandine-spessartine garnet + Ti-poor schorl, (2) columbite-(Fe), (3) tantalite-(Fe), (4) Ti-and Sn-bearing ixiolite ± ferrowodginite ± Nb-and Ta-bearing cassiterite ± columbite-(Fe), all crystallizing along with Ti-enriched schorl evolving to dravite. The most characteristic features of the mineral assemblages are the reversed Mn-Fe fractionation trends and increasing Ca concentrations at the final stage of crystallization. These compositional variations are explained by a possible pre-emplacement contamination of the pegmatite-forming melt and re-equilibration of biotite and plagioclase from the early-crystallized outer zones of the pegmatites with rapidly cooling pegmatitic melt. Local changes in melt composition were of minor importance. Late alterations, such as chloritization and muscovitization of biotite or albitization of Ca-rich plagioclase were significant only at the hydrothermal stage.

The newly dis cov ered Julianna peg ma titic sys tem from the Pi³awa Górna Quarry (the Góry Sowie Block, Sudetes, NE mar gin of the Bo he mian Mas sif) is de scribed in terms of geo log i cal set ting, pe trog ra phy and de scrip tive min er al ogy. The sys tem repre sents the larg est peg ma titic oc cur rence in the Pol ish Sudetes and con sists of a com plex net work of cogenetic rare-el e ment gra nitic pegmatites that in truded into tectonized am phi bo lite as dis cor dant dikes. The pegmatites range from bar ren and weakly zoned to tex tur ally well-dif fer en ti ated ones that are com posed of a fine-grained bor der zone, coarse-grained wall zone, graphic and blocky feld spar in ter me di ate zones and a quartz core. Uni di rec tional and skel e tal so lid i fi ca tion tex tures are well-de vel oped. The Julianna pegmatites con sist of rock-form ing plagioclase (£An 39 ), microcline, quartz and bi o tite accom pa nied mostly by ac ces sory to mi nor mus co vite, tour ma line, gar net and beryl. They crys tal lised from anatectic melt of hy brid NYF (ni o bium-yt trium-flu o rine) + LCT (lith ium-ce sium-tan ta lum) geo chem i cal char ac ter is tics. Pegmatites with a low to mod er ate de gree of frac tion ation, that dom i nate in the Julianna sys tem, bear NYF-sig na ture ac ces sory min er als, such as al la nite-(Ce), colum bite-, euxenite-and samarskite-group min er als, fergusonite-(Y) and gadolinite-(Y). How ever, rare dikes that at tained a very high de gree of frac tion ation con tain typ i cal min er als of LCT-sig na ture in clud ing tour ma lines of the elbaite-olenite-rossmanite se ries, le pido lite, lithiophilite, spodumene, Cs-rich beryl and pollucite.

Yellowish dravitic tourmaline (dominated by the oxy-dravite component) associated with secondary fluor-dravite/fluor-schorl and dravite/schorl tourmalines was found in a quartz vein cropping out in the eastern part of the Karkonosze Mountains range, SW Poland. The crystal structure of this tourmaline was refined to an R1 value of 1.85% based on single-crystal data, and the chemical composition was determined by electron-microprobe analysis. The tourmaline, a representative of the alkali-tourmaline group, has the structural formula: (Na0.75Ca0.12□0.13)Σ1(Mg1.93Al0.95Ti0.06${\rm Fe}_{{\rm 0}{\rm. 04}}^{{\rm 2 +}} $ V0.01)Σ3(Al5.38Mg0.62)Σ6B3Si6O27(OH)3(O0.46OH0.33F0.21)Σ1, and is characterized by an extremely high Mg/(Mg + Fe) ratio of 0.97–0.99, the WO2– content that reaches 0.59 apfu resulting in a local predominance of the oxy-dravitic component and Mg–Al disorder on the octahedral Y and Z sites of the order of 0.64 apfu. This disordering results in an increasing <Z–O> distance with ~1.925 Å, and unit-cell parameters a = 15.916(1) Å and c = 7.180(1) Å. The tourmaline formed during Variscan prograde metamorphism under the influence of a released (H2O,B,F)-bearing fluid. The fluid mobilized the most soluble components of partly altered silicic volcaniclastic material of the Late Cambrian to Early Ordovician bimodal volcanism to become the protolith for adjacent quartzo-feldspathic schists and amphibolites, and propagated them into the surrounding granitic gneisses of the Kowary unit in the eastern metamorphic cover of the Karkonosze granite.

This paper presents the results of the study on chemical and the physical properties of waste phosphogypsum (PG) of apatite origin from the former chemical plant Wizow, Poland which are important for further processing and economic use. The research was carried out to verify whether the waste might be useful as a raw material for rare earth elements (REE) recovery and the manufacture of building materials. The following methods were chosen: X-ray diffraction, scanning electron microscopy with an energy-dispersive X-ray detector, atomic absorption spectrometry, inductively coupled plasma spectrometry, differential thermal analysis, thermogravimetry, and gamma spectrometry with natural radioactive contamination analyzer. It has been proven that the chemical physical properties of phosphogypsum provide an opportunity to utilize this waste material as a source of REE and raw material for building purposes. PG contains an overall amount of REE in the interval of 0.343-0.637% by mass and does not show radioactivity level which would exclude it from construction purposes. The presented results serve as the basis for currently available technological directions in the management of apatite PG for useful trade products, which creates a chance for the elimination of its storage necessity by further processing.