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...

Wastes accumulated at Piekary Śląskie, Poland, are the result of 150 years of continuous working of the Orzeł Biały smelting plant. Slags are composed of: oxides (spinel, hematite, zincite); silicates and aluminosilicates (olivine, monticellite–kirschteinite, titanite, merwinite, pyroxene, melilite, feldspars: plagioclases and plumbean K-feldspar, nepheline, kalsilite, leucite); sulfides (pyrrhotite, rudashevskyite, galena), metallic phases (pure iron and iron–arsenic mixture) and secondary phases (gypsum, rapidcreekite, apatite). Interstices between the crystalline phases are filled by glass, concentrating toxic and potentially harmful elements, e.g. up to 53.22 wt.% PbO. The sequence of crystallization of primary phases depended on the local variability of oxygen fugacity and degree of calcination, while the texture type resulted from the cooling time and partial pressure of volatiles. Suggested crystallization temperatures are in the range of 1200–1500°C. Bulk chemical analyses show that the slags are composed mainly of SiO2, Al2O3,Fe2O3, MgO and CaO. Among the potentially harmful elements, Zn is the most common, reaching up to 5.93 wt.%, Pb is present in concentrations up to 3.9 wt.% and As in weathered samples exceeds 1 wt.%. Leaching tests of these elements confirms As mobility as Zn and Pb are preferably leached from fresh slags, while As is present in greater amounts in leachate from weathered slag samples. The documented amounts of As, Zn, Pb and their mobility in slags produce an environmental risk, as this material is currently used widely for commercial purposes.

The study focuses on the reconstruction of the technological process in the 16th–17th century lead smelter in Sławków based on chemical and petrographic analyzes of slags. There are three main types of material at the landfill: glassy, crystalline, and weathered. Glassy slags are made of amorphous phase in which crystals of pyroxene, willemite, olivine, wüstite, and lead oxide appear. Crystalline slags are composed of wollastonite, rankinite, melilite, anorthite, quartz, and Fe oxides. Weathered slags have a composition similar to glassy slags, but they also contain secondary phases: anglesite and cerussite. Chemical analyzes confirmed that the smelter used sulphide ores, which were roasted, and the main addition to the charge was quartz sand. The smelting process took place in a brick-built furnace, under reducing conditions, with varied oxygen fugacity ranging from WM to MH buffer. The slag characteristics show a knowledge of the workers in the field of smelting methods. The addition of SiO2 allowed for the binding of elements that could contaminate the obtained lead, and at the same time, the low melting point of the material (1150 °C) and the melt viscosity (logη = 1.34 for 1150 °C) was maintained, enabling the effective separation of liquid lead.

No abstract

No abstract