Search Results (15)

Archaeological evidence for prehistoric placer tin mining is rare due to the ephemeral nature of the workings and the associated tools in the dynamic setting of active river systems. Here, we report an additional line of evidence for metallurgical activities at stream tin mining in Serbia at Mt. Cer and Bukulja. Rivers at these locations contain Pb-rich-glass grains, many of which are also enriched in Cu and Sn. Compositionally, the detrital grains of glass are similar to the vitreous infillings on a bleached ceramic sherd found at Spasovine, an archaeological site situated on the bank of the tin-rich Milinska River. The high-Pb-bearing (average 42 wt%) and Sn-bearing (average 0.7 wt%) composition of the glass, along with the inclusions of secondary cassiterite, indicate that the slag was derived from the refinement of leaded bronze (i.e., lead removal). Although the detrital glass slag grains lack direct archaeological context, broader archaeological observations limit their production to either the Roman or Medieval Periods. The presence of Pb-Cu-Sn metallurgical glass grains in a river at Bukulja provides the first concrete evidence of prehistoric tin mining at this locality, which demonstrates that sluicing for crushed glassy residues is a viable means to prospect for as yet undiscovered sites of ancient metallurgical activities. Full article

This article deals with the experimental validation of an interpretation on the notable archaeological evidence patterns of early historical iron smelting in northern Central Europe. In this region, the inner Barbaricum, there was minimal evidence of iron smelting at the onset of the Roman Period. This shifts suddenly in the initial half of the first century AD: Numerous “centres of iron smelting” are identifiable in this region throughout this period. Numerous discoveries of iron smelting, known as “bloomery smelting furnaces”, are conspicuously clustered. It was formerly believed that the shafts of bloomery furnaces needed to be dismantled post-smelting to retrieve the produced iron. At the site “Sehnde 9” in Lower Saxony, Germany, it has been experimentally verified on several experimental furnace runs that the shafts can be reused, and these experimental results are consistent with the archaeological evidence from the site in question. The comparison with other Central European sites from the same period further substantiates that a reuse of bloomery furnace shafts was not an isolated phenomenon. This strategy markedly enhances the efficiency of iron production over time. Consequently, the designation of a novel furnace type “Sehnde” is suggested. Full article

Soil serves as a repository of human history, preserving artifacts within its horizons. However, the presence of chemically reactive remnants, such as ancient slags, can significantly impact the surrounding soil environment. This paper addresses this scarcely explored issue by focusing on soil contamination arising from pre-Roman slag deposits at the Monte Romero archaeological site in southwest Spain, dating back to the Tartessian period (c. 7th century BC). Through the high-resolution microscopy examination of slag wastes and the trace element analysis of soil samples by ICP-OES, this study evaluated current contamination status using a multi-index approach. The results revealed markedly high levels of Pb (>5000 mg kg⁻¹), Cu (up to 2730 mg kg⁻¹), and As (up to 445 mg kg⁻¹) in the soil compared to a control sample. The identification of secondary complex compounds like Cu arsenates and Pb arsenates/antimonates within slag cavities suggests post-depositional weathering processes, leading to the dispersion of potentially toxic elements into the surrounding soil. Assessments through indices of contamination and potential ecological risk highlighted severe contamination, particularly concerning Ag, Pb, Sb, Cu, and As. This study underscores the importance of addressing potential environmental hazards associated with archaeological sites hosting remnants of metal production. Full article

The scarcity of excavated early-stage smelting sites related to copper production presents significant challenges in gaining a comprehensive understanding of the copper production process. However, the archaeological site discovered in 2018 in Daeryang-ri, Jinan-gun, Jeollabuk-do, boasts a substantial number of copper smelting remains and related slags, marking it as the first copper manufacturing production site identified on the Korean Peninsula. Consequently, this study selected 10 slag samples, chosen based on surface color and characteristics indicative of a connection to copper smelting, for scientific analysis to accurately ascertain the site’s nature. The primary component analysis of the slags indicated that CuO content ranged from 0.30 to 3.29 wt%, which, although not high, reveals significant quantities of FeO and SiO₂. X-ray diffraction analysis revealed the presence of minerals such as cristobalite, along with fayalite and wüstite, commonly found in slags, varying by sample. Furthermore, microstructural observation revealed circular copper particles containing sulfur and iron, indicating the presence of copper particles in a matte state that have not been refined. This analysis suggests that the slags recovered from Jinan Daeryang-ri bear evidence of iron smelting at the site, with the slag being produced as an intermediate by-product during copper production. Full article

The production and trade of metals was the foundation of the economic wealth of many regions in the world, which makes the study of ancient metallurgical slags of primary importance. This type of study is relatively new for Bulgaria, where research in the field started in the late 1960s with chemical analysis of copper ore, slags, tools and finished goods from the ancient copper mine in the Ay-bunar area. Iron is one of the most commonly found elements in the earth’s crust and its deposits are widespread, including on Bulgaria’s territory. To this day, however, the study of iron slags from Bulgarian sites through chemical and phase analysis has almost never been explored. The application of these methods allows for the determination of the technology of the ancient metallurgical process. This study investigates iron slags from two Bulgarian archaeological sites, situated in close proximity to the Sarnevets hematite ore deposit, Sarnena Sredna Gora mountain. The ore bodies of the deposit outcrop on the earth’s surface and can be easily recognized due to the red coloring of the soil around them, which is a characteristic trait for finding iron deposits. In addition to the ancient mining activities in the region, proven by over 20 registered ancient mine workings, ancient metallurgical activities were established as well, as proven by the discovered slags. A sample from the hematite ore was studied along with the slags, so that the percentage of iron extracted during the metallurgical process can be determined. The samples were studied through X-ray fluorescence analysis, powder X-ray diffraction analysis, and Mössbauer spectroscopy. The obtained results show that the slags are of the “furnace bottom slags” type, which is a product of metallurgical activity achieved through bloomery technology. The temperature range of the furnaces was determined to be around 900–1100 °C. The reduction of iron was possible at such low temperatures due to the ore’s type—self-fluxing hematite ore. The percentage of iron extracted from the ore was calculated to be between 3.39% and 8.65%. Additionally, a relationship was established between the percentage of extracted iron, the Fe²⁺ content included in wüstite, and the viscosity index of the liquid slag. The acquired results are new to the archaeological studies conducted on Bulgaria’s territory and are a prerequisite for future interpretation and archaeological research. Full article

To explore the source of Pb in Bronze Age artefacts from the Central Plains (Zhongyuan) in China, we investigated non-ferrous minerals from the Qingyuan archaeological site in Yuanqu County near the Zhongtiao Mountains. Fragments of smelting slag from the Erlitou cultural layer were collected. The smelting slag was investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and lead isotope analysis. The SEM and EDS results confirmed that the slag contained Pb, Pb–As, and Cu–Pb–Sn inclusions and non-metal impurities such as low-Zn spinels. The XRD results signified that the bulk of the slag comprised Fe–Mn–Si phases. The chemical state of Pb was mainly Pb–O with some metallic Pb, as identified by XPS. The theoretical melting point was calculated using FactSage7.1 based on the composition and phase characterisation. The calculated temperature was 1100–1200 °C, which agreed well with the actual melting point of 1114–1354 °C. The slag composition and inclusion phases indicated that Pb–Zn–O ores with Mn and As were added during reduction smelting in Qingyuan. The raw materials of smelting included crude Pb with minor amounts of Cu, As, and Sn. Lead isotope analysis revealed that the lead materials produced in Qingyuan were likely transferred to Yanshi City in the Shang Dynasty. The findings of this study provide significant clues for exploring lead mineral production in the Central Plains during the Early Bronze Age. Full article

Findings of Iron Age metallurgical activities related to tin metal and mining are very rare. In the present work, we present a detailed study of the Outeiro de Baltar hillfort, dated to the Late Iron Age/Early Roman period, located in a place where 20th century tin mining work took place. Elemental and microstructural analysis by portable, micro and wavelength dispersive X-ray fluorescence spectrometry (pXRF, micro-XRF and WDXRF) and scanning electron microscopy with energy dispersion spectrometer (SEM-EDS) showed that metallurgical debris found at the archaeological site is related to tin smelting and binary and ternary bronze productions. Analysis of the artefacts of diverse typologies found at the site showed that a variety of metals and alloys were in circulation and use. Samples of tin ores (cassiterite) from the region were analyzed for comparison with an archaeological tin slag from the site. The analytical results point to the production of tin metal using local cassiterite and the production of bronze by directly adding cassiterite into a smelting process. Furthermore, data of remote sensing (airborne Light Detection and Ranging (LiDAR) and historical aerial imagery) and Geographical Information System (GIS) mapping were combined with archival mining documentation and maps to retrieve a landscape context for the site. The study showed that the place of the Outeiro de Baltar hillfort (NW Iberia) was mined periodically over time. Full article

The archaeological remains of a metallurgical workshop were excavated at Amboronala (northeast of Madagascar/1000–1200 CE). The bulk mineralogical (X-ray Diffraction) and chemical (X-ray Fluorescence) data on ores, building materials, and slag are used to carry out a mass balance calculation. The results show an important variability from one smelt to the other, reflecting a poorly controlled process. During each smelt, a given amount of building material contributes to the formation of the slag, and the conditions of reduction allow the extraction of a given amount of metal. These two main factors influence the composition of the slag independently and variably. This finding allows to make some inference on the origin of the technique and the organization of the production can be made. Full article

Archaeological investigations of the Colline Metallifere district (Southern Tuscany, Italy) have highlighted several Medieval sites located close to the main Cu-Pb-Fe (Ag) ore occurrences. This study is focused on the investigation of late-medieval slags from Cugnano and Montieri sites using both geochemical and mineralogical methods to understand slag heterogeneities as result of ore differences and technological processes. Matte-rich slags present in both sites (with abundant matte ± speiss and frequent relict phases) represent waste products related to primary sulphide ore smelting to obtain a raw lead bullion. The distribution of slags between the Ca-rich or Fe-rich dominant composition, and the consequent mineralogy, are tracers of the different ore–gangue association that occurred in the two sites. Silver is present only in very small matte-rich slags and ores enclosed within the mortar of the Montieri site; wastes derived from silver-rich mineral charges were probably crushed for the recovery of silver. Matte-poor slags found at Montieri represent a second smelting; raw lead bullion obtained from matte slags (both Fe- and Ca-rich) was probably re-smelted, adding silica and Al₂O₃-phase-rich fluxes, under more oxidizing conditions to reduce metal impurities. This second step was probably employed for Zn-rich lead ores; this process helped to segregate zinc within slags and improve the quality of the metal. Full article

This paper presents the provenance study of the iron reinforcements of Bourges Cathedral (13th c.): the links of a 100 m long iron chain, surrounding the eastern parts of the cathedral at the triforium level and 4.5 to 5 m long tie-rods consolidating the arches of the inner aisle at the same level. The analytical methodology is based on the determination of trace rare earth elements analyses by LA-ICP-MS in the slag inclusions of the artefacts and in the slag found on candidate production sites combined with statistical approaches. This chemical approach is crossed with archaeological and historical studies on the monument itself and on the production sites. Ninety-nine iron samples were analyzed on the bars and chains and 238 iron slags from 3 presumed areas of supply. For the first time, iron circulation and trade around a single building yard over a time of 30 to 40 years is studied with a precision never obtained before with historical sources. It shows that mainly four different metallurgical districts, local and more distant, supplied the building yard, mostly depending on the construction phases and also on the types of iron armatures needed. Full article

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. Full article

Iron slag samples unearthed from archaeological sites lying on the Eastern limes sector of Roman Dacia (the Brâncoveneşti and Călugăreni auxiliary forts and the Vătava watchtower) were studied in order to assess the probability of local iron working (smelting and smithing) during the 2nd–3rd centuries CE. Structural-mineralogic aspects revealed by PXRD analysis and FTIR spectroscopy indicate different slag types corresponding to different iron production and processing stages allowing the supposition that refining of the bloom and processing of the refined iron took place on the sites. The FTIR absorption bands obtained in the spectral domain 2000–400 cm⁻¹ show that mineralogically the samples are constituted mainly of silicates associated with minor quantities of aluminates and carbonates. The fayalite, haematite, and magnetite phases appearing on both the X-ray diffractograms and the FTIR spectra agree with the redox conditions of the slag formation process which result from the Fe³⁺/Fe²⁺ ratio determined using the EPR-method. The bulk macro-elemental PXRF and ICP-MS spectroscopy data support the slag typization proposed on the basis of the probable working conditions; trace-elemental bulk composition suggests that the provenance of the raw materials may be different. Full article

The Oiola archeological site, located in the mining complex of La Arboleda (Biscay, North Spain) was an important iron smelting center from the Roman Period to the Middle Ages and even in more current times (19th–20th centuries). Tap-slags and some plano-convex slags were identified as smelting slags. Samples were analyzed by optical microscopy, X-ray powder diffraction, scanning electron microscopy coupled with electron-dispersive spectroscopy and Raman microspectroscopy to perform a mineralogical and textural characterization. Additionally, thermogravimetric and thermodiffraction analyses were carried out to determine furnace operating temperatures. The mineral assemblage reflects furnace temperatures and cooling rates and the addition of quartz as the main flux to decrease the melting temperature of the iron ore. The comparison of slags from the Roman Period and the Middle Age reveals changes in the pyrometallurgical process through time. Full article

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 (PbCO₃, ZnCO₃, CaZn(CO₃)₂, FeOOH), sulfides (PbS and ZnS) and quartz (SiO₂). 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. Full article

In the paper, the results of an investigation into trace elements found in slag sulfides from 14 archaeological Bronze Age settlements of the Cis-Urals, Trans-Urals, and North and Central Kazakhstan are presented. The study used Cu-(Fe)-sulfides as indicator minerals. Cu-(Fe)-S minerals in slags are primarily represented by covellite and chalcocite, as well as by rarer bornite and single chalcopyrite grains. Slag sulfides formed relic clasts and neogenic droplets of different shapes and sizes. Supergenic ores in the Bronze Age in Urals and Kazakhstan played a significant role in the mineralogical raw material base. In sulfides, the main indicator elements, Fe, Co, Ni, As, Se, Te, Sb, Ag, Pb, and Bi, are important markers of copper deposit types. Sulfides from olivine Cr-rich spinel containing slags of Ustye, Turganik are characterized by As-Co-Ni high contents and confined to copper deposits in ultramafic rocks. Olivine sulfide-containing slags from Kamenny Ambar, Konoplyanka and Sarlybay 3 are characterized by Co-Se-Te assemblage and confined to mafic rocks. Glassy sulfide-containing slags from Katzbakh 6, Turganik, Ordynsky Ovrag, Ivanovskoe, Tokskoe, Bulanovskoe 2, Kuzminkovskoe 2, Pokrovskoe, Rodnikovoe, and Taldysay are characterized by Ag-Pb-(Ba)-(Bi) assemblage and confined to cupriferous sandstone deposits. High As, Sb, Sn, and Ba contents found in slags can be seen as indicators of alloying or flux components in primary copper smelting. These include samples from Ustye, Katzbakh 6, Rodnikovoe, and Taldysay sites, where high Ba and As slag contents are identified. The compilation of a database with a broad sample of sulfide compositions from Bronze Age slags and mines in the Urals and Kazakhstan will permit the further identification of ore types and raw materials associated with a particular deposit. Full article