Zn-Pb slag crystallization: evaluating temperature conditions on the basis of geothermometry

Warchulski, Rafał

doi:10.1127/ejm/2015/0027-2496

Cited by 17 publications

(20 citation statements)

References 19 publications

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“…The obtained results can be used to approximate the metallurgical process in the sampled location. On the basis of conducted furnace experiments, it has been confirmed that the temperature of smelting had been up to 1550 • C. Such high temperatures are not characteristic for more contemporary methods of Pb and Zn smelting, where they are in the 1000-1300 • C temperature range [34]. Studies show that such high temperatures could be obtained by using tuyeres in the furnace design [35].…”

Section: Discussionmentioning

confidence: 99%

Pb-Rich Slags, Minerals, and Pollution Resulted from a Medieval Ag-Pb Smelting and Mining Operation in the Silesian-Cracovian Region (Southern Poland)

Cabała

Warchulski

Rozmus³

et al. 2019

Minerals

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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...

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Section: Discussionmentioning

confidence: 99%

Pb-Rich Slags, Minerals, and Pollution Resulted from a Medieval Ag-Pb Smelting and Mining Operation in the Silesian-Cracovian Region (Southern Poland)

Cabała

Warchulski

Rozmus³

et al. 2019

Minerals

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“…The batch was loaded to heated muffles where it was melted at temperatures in the range ca. 1060-1350 • C (Warchulski 2015). During smelting, the batch underwent many physical and chemical transformations, among which the most important is reduction of ZnO by C as follows:…”

Section: Restoration Of the Smelting Process At The Katowice-szopienimentioning

confidence: 99%

“…In many cases, historical information about the smelting process is fully or partially lost and slags are the only remnants of the smelting plants. Thus, they are of interest as carriers of geochemical/mineralogical data that can be used for the restoration of ancient smelting processes at historical sites (Manasse and Mellini 2002a, b;Kierczak and Pietranik 2011;Warchulski 2015).…”

Section: Introductionmentioning

confidence: 99%

Geochemistry, petrology and evolutionary computations in the service of archaeology: restoration of the historical smelting process at the Katowice–Szopienice site

Warchulski

Juszczuk

Gawęda

2016

Archaeol Anthropol Sci

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Activity at the smelting plant at Katowice-Szopienice dates back to the nineteenth century. Currently, the Museum of Zinc has been funded at the site. Unfortunately, as a result of unrest during both World Wars, all technological descriptions were lost. Three historically described samples were provided by Museum of Zinc and additional slag and lining samples were collected directly from the furnace. "Enriched ore" is dominated by ZnS (89.5%) as sphalerite and wurtzite accompanied by gangue minerals. "Roasted ore" is composed mainly of zincite (74%) resulting from the oxidation of ZnS. Study has proved that "roasted ore with coke" sample description is inappropriate. It is zinc depleted and enriched in Si (22.93 wt.%), Al (9.16 wt.%), C (9.66 wt.%) and its phase composition suggest that it contains recycled lining material and coke. Such characteristics place sample as additions used for smelting process. Advanced mathematical tool, the differential evolution algorithm, was used for restoration of smelting process at the site. Algorithm proved great usefulness by providing low dispersed results for calculated compositions of loss on smelting (mainly yield) with the Rafał Warchulski

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“…The high concentration of Zn in silicates and oxides in slags resulted from the non-efficient metal extraction in smelters Warchulski 2015). All of major phases in the segregations (melilite, pyroxene, spinel) are enriched in Zn, relative to the bulk slag.…”

Section: The Origin Of Coarse-grained Segregations In Pyrometallurgicmentioning

confidence: 99%

“…This estimate is consistent with the temperature of the molten slag (1200-1300°C) that was transported to the slag bed. The temperature of the overlain vesicular slag calculated from the olivine-bulk chemical composition is in the range of 1200-1350°C, while calculations based on the clinopyroxene-bulk chemical composition give 1140-1260°C (Warchulski 2015.). Puziewicz et al (2007) by analogy to rapidly cooled, but holocrystalline silica-undersaturated lavas assumed that low viscosity is the key factor causing crystallization of slagforming phases.…”

Section: The Origin Of Coarse-grained Segregations In Pyrometallurgicmentioning

confidence: 99%

Mineralogy and origin of coarse-grained segregations in the pyrometallurgical Zn-Pb slags from Katowice-Wełnowiec (Poland)

et al. 2016

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The unique among pyrometallurgical slags, coarsegrained (up to 2.5 cm) segregations (up to 40 cm long) rimmed by Baplitic^border zones occur within holocrystalline historical Zn-smelting slag in Katowice, S Poland. Slag surrounding the segregations consists of olivine, spinel series, melilite, clinopyroxene, leucite, nepheline and sulphides. Ca-olivines, kalsilite and mica compositionally similar to oxykinoshitalite occur in border zones in addition to olivine, spinel series and melilite. Miarolitic and massive pegmatite-like segregations are built of subhedral crystals of melilite, leucite, spinel series, clinopyroxene and hematite. Melilite, clinopyroxenes and spinels in the segregations are enriched in Zn relatively to original slag and to fine-grained border zones. The segregations originated as a result of crystallization from residual melt rich in volatiles (presumably CO 2 ). The volatilerich melt was separated during fractional crystallization of molten slag under the cover of the overlying hot (ca. 1250°C) vesicular slag, preventing the escape of volatiles. That unique slag system is analogous to natural magmatic systems.

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Zn-Pb slag crystallization: evaluating temperature conditions on the basis of geothermometry

Cited by 17 publications

References 19 publications

Pb-Rich Slags, Minerals, and Pollution Resulted from a Medieval Ag-Pb Smelting and Mining Operation in the Silesian-Cracovian Region (Southern Poland)

Pb-Rich Slags, Minerals, and Pollution Resulted from a Medieval Ag-Pb Smelting and Mining Operation in the Silesian-Cracovian Region (Southern Poland)

Geochemistry, petrology and evolutionary computations in the service of archaeology: restoration of the historical smelting process at the Katowice–Szopienice site

Mineralogy and origin of coarse-grained segregations in the pyrometallurgical Zn-Pb slags from Katowice-Wełnowiec (Poland)

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