REGIONAL VARIATIONS IN BLOOMERY SMELTING SLAG OF THE IRON AGE AND ROMANO‐BRITISH PERIODS*

This study highlights regional variation in the composition of iron‐smelting slag produced in England prior to the medieval period and attempts to link slag composition to the type of ore smelted. For many sites, the slag compositions were consistent with the use of limonite ore, but there is evidence that siderite ore was smelted at sites in Sussex in the late Iron Age/Romano‐British periods. A compositional comparison of smelting slags and slag inclusions in Iron Age currency bars, using data from Hedges and Salter (1979 ), illustrates the potential of smelting slag compositional data in provenance studies of early iron objects.     

METALLOGRAPHIC STUDY OF IRON ARTEFACTS FROM THE EASTERN TRANSVAAL,SOUTH AFRICA

The microstructures of two adzes, two hoes and a spear point from Iron Age settlement sites in the Kruger National Park have been examined. Electron microprobe analyses of the slag inclusions were also made. Some of the objects are made of high carbon steel while others have a highly variable carbon content. All appear to have been forged at relatively low temperature and then annealed at a low temperature near 700°C. None have been hardened by quenching and tempering. Some of the objects contain only traces of included slag while others have large slag inclusions. The slag compositions are quite different from those of medieval bloomery slags and are representative of African iron smelting practice in their high content of CaO, K₂ O and Na₂O. On the basis of the titanium content of the included slag, two of the objects are identified as made of the ore from Rooiwater and one from Phalaborwa ore.     

Does it come from the Pays de Bray? Examination of an origin hypothesis for the ferrous reinforcements used in French medieval churches using major and trace element analyses

A new methodology based on major and trace element analyses of slag inclusions is proposed to determine (or exclude) the provenance of iron artefacts. It is applied to verify if the Pays de Bray, a French area between Rouen and Beauvais, could have been an important supplier for the ferrous reinforcements used in the Middle Ages for the building of churches and cathedrals in these two towns. To this purpose, the behaviour of trace elements during both direct and indirect operating chains is studied combining experimental smelting and different analytical methods, such as SEM–EDS, ICP–MS, LA–ICP–MS and INAA, performed on archaeological samples. The chemical signature of the Pays de Bray iron ore and slag is determined considering MnO and P₂O₅ contents as a first rough filter and seven couples of trace elements. Then, the major and trace elements are analysed using the same methods in the slag inclusions of 32 artefacts from the Beauvais and Rouen churches, made by the bloomery process. The trace element signature of the inclusions from each artefact is compared with the ore from the Pays de Bray area. The iron used in the Rouen and Beauvais churches seems not to come mainly from the Pays de Bray.     

THE USE OF TRACE ELEMENT ANALYSIS OF ENTRAPPED SLAG INCLUSIONS TO ESTABLISH ORE – BAR IRON LINKS: EXAMPLES FROM TWO GALLO‐ROMAN IRON‐MAKING SITES IN FRANCE (LES MARTYS,MONTAGNE NOIRE,AND LES FERRYS,LOIRET)*

Knowledge of the iron trade in ancient times rests on determining the source of the objects recovered during archaeological excavations. Unfortunately, attributing the origin is not always possible using archaeological tools alone. Trace element data of the ore and the archaeological material (reduction and reheating slags, entrapped slag inclusions from the bloom, bar iron and iron blades) from two Gallo‐Roman iron‐making centres, Les Martys (Montagne Noire) and Les Ferrys (Loiret), were determined using ICP–AES/MS and LA–ICP–MS. The results highlight a continuity of composition that makes it possible to establish a link between the initial ore and the semi‐finished iron products.     

First Finding of Early Medieval Iron Slags in Sardinia (Italy): A Geochemical–Mineralogical Approach to Insights into Ore Provenance and Work Activity

At Santa Filitica, a Roman settlement in north‐western Sardinia occupied until the ninth century ad , archaeological excavations have found the remnants of a furnace consisting of a semi‐circular base made of stony slabs and tiles bound with clay. The furnace is attached to a wall of Roman age. Layers of the sixth century ad , bearing several variously oxidized slags, were found close to the furnace. These findings first testify to an ironworks in Sardinia, within a well‐defined context. XRPD and SEM–EDS mineralogical and textural analyses suggest that the slags derive from a bloomery and smithing work that was the first evidence of this type documented in Sardinia during the Early Middle Ages. Chemical analyses (performed with ICP and INAA) of rare earth elements and trace elements in two slags and in two Sardinian iron deposits allow some conclusions to be drawn on the local provenance of the ore. Our comparison of the Sardinian findings and some slags representative of archaeological smelting sites at the front of Elba island—the largest and longest lived iron‐working sites in the Mediterranean—also improves the methodology with which iron slags derived from different ores are compared.     

The technology of tin smelting in the Rooiberg Valley,Limpopo Province,South Africa,ca. 1650–1850 CE

A substantial indigenous tin-smelting industry arose in the Rooiberg valley of northern South Africa in the second millennium CE. This study concentrates upon tin-smelting slags and refractory ceramics from two archaeological sites that date between ca. 1650 CE and ca. 1850 CE. These were studied by optical and electron microscopy, wavelength-dispersive x-ray fluorescence (WD-XRF), inductively-coupled plasma mass spectrometry (ICP-MS), and electron microprobe (EMPA). The slags are predominantly glassy; high SnO and relatively low SiO₂ contents indicate that tin is a major glass-forming element. Comparison of slag chemistries with the mineralogy of ore deposits and host rocks shows that alluvial cassiterite was used at one of the sites, while cassiterite from hard-rock mining was smelted at the other site. Since few preindustrial tin slags have been studied, we compare our findings to other published examples, mostly from southwest England.     

Using mineral magnetism to characterise ironworking and to detect its evidence in peat bogs

An experimental approach has been used to establish whether medieval ironworking activity could be identified in peat bogs using mineral magnetic measurements. The research project comprised three elements. First, magnetic susceptibility and remanence properties were obtained for materials from an experimental iron smelt, in a furnace of medieval design, and from material collected during the excavation of the medieval bloomery at Llwyn Du in Coed y Brenin, Snowdonia. Materials sampled and measured included charcoal, aerial dust, roasted bog ore and furnace dust. A second experiment determined whether small amounts of aerial dust released from the furnace could be detected in accumulating peat samples. This was achieved by sprinkling small quantities of dust on to a constructed ’peat core’ that had no detectable magnetic signature prior to the addition of the dust. The application rates used were within the range expected to fall on a peat bog located close to a medieval furnace. Thirdly, mineral magnetic measurements were made on a peat core collected close to the Llwyn Du bloomery. The results confirm that roasted bog ore, aerial dust released from and dust accumulating in the furnace after a smelt, are magnetically detectable. The aerial dust and roasted bog ore produced enhanced susceptibility and remanence signatures in the constructed ’peat core’ experiments. Peaks in IRM_(0.88T) and HIRM were measured in the Llwyn Du peat monolith and appear to correlate with a time when the medieval bloomery was operational. The results presented here suggest that it is possible to identify evidence of past ironworking in peat bogs using mineral magnetic measurements and that the signatures remain well preserved in the peat record even after burial for several hundred years.     

Indigenous African Furnace Types and Slag Composition—Is there a Correlation?

Within variation, three major iron smelting furnaces were used in the Iron Age of sub‐Saharan Africa, ranging from the natural draught driven tall shaft to the forced draught powered low shaft and bowl furnaces. These furnace types are, however, mostly known from the ethnographic context. Often, archaeologists are confronted with remnants from the smelting process, forcing them to speculate on the anatomy of the extant furnaces. The presence of multiple fused tuyeres has been used to identify natural draught furnaces in the archaeological record. However, working back from smelting remains such as slag to the furnace type using physical and chemical evidence has generally proved to be ‘undoable’. Thus, when randomly selected, the chances are high that one cannot separate bowl furnace slags from those that formed in their tall or low shaft counterparts. This observation is hardly unexpected; analogous thermodynamics and thermo‐chemical reactions governed bloomery smelting irrespective of furnace type. Rehren et al. (2007) have labelled this phenomenon the ‘tyranny of system driven constraints’. In this study, we argue that the hierarchical use of statistical methods may add another layer of evidence which, when coupled to archaeological indicators, may be useful in correlating slag chemistry to furnace types used in antiquity.     

MINERALOGICAL AND PETROLOGICAL INVESTIGATIONS OF EARLY BRONZE AGE COPPER‐SMELTING REMAINS FROM THE KIECHLBERG (TYROL,AUSTRIA)

The prehistoric settlement on the Kiechlberg hilltop is located a few kilometres to the north‐east of Innsbruck, in the Tyrolean Inn Valley. Despite its rather isolated location, a multiphase settlement between the fifth and the second millennium bc was confirmed by archaeological investigations in 2007 and 2008. Metallurgical artefacts, such as copper ore fragments, copper slag and raw copper, as well as finished copper and bronze artefacts, are concentrated mainly in Late Copper Age to Middle Bronze Age layers. The chemical compositions of the slag and raw metals confirm Fe—Zn tetrahedrite–tennantite (fahlore) smelting. The ore was most probably imported from the 30–50 km distant copper ore deposits (mainly fahlore) of Schwaz–Brixlegg, in the Lower Inn Valley. The small amount of slag and the presence of slagged and thermally altered ceramic fragments suggest copper production in small‐scale workshops. Most probably, sulphide‐rich ores were smelted in crucibles in a hearth fire. The process was relatively reducing below the 2Sb + 1.5O₂ → Sb₂O₃ reaction (?8.5 log fO₂ at 1100°C), producing Sb‐rich (>10 wt% Sb in metal) raw copper. Inhomogeneous slag remains containing high amounts of sulphide and metal inclusions suggest a poor separation of the metal, matte (copper sulphide) and silicate/oxide melt during the smelting process.     

THE PROVENANCE OF IRON ARTEFACTS FROM MANCHING: A MULTI‐TECHNIQUE APPROACH*

Iron finds from the Celtic oppidum of Manching in southern Bavaria (Germany) are analysed in view of their possible provenance. The exceptional size and the location of Manching are usually attributed to the presence of abundant iron ores in its vicinity. After a review of previous approaches for source determination of iron artefacts, we introduce lead isotope analysis as a new approach. However, only by combining the trace element patterns of slag inclusions and iron metal with lead isotope ratios in the metal is it possible to distinguish various iron ore formations near Manching. As a result, it turns out that, indeed, the most obvious ones—namely, bog ores near the Danube—constituted the main resources for iron production at Manching. It was even possible to select one occurrence as the most likely ore source.     

Slag inclusions in iron objects and the quest for provenance: an experiment and a case study

Slag inclusions are found within most archaeological bloomery iron artefacts and are remainders of slag created during the smelting and smithing processes. Although they are widely believed to provide data with the potential for provenancing iron artefacts, previous slag inclusion studies have mostly proven inconclusive. The main aim of the work reported here is to analyse experimental smelting and smithing assemblages (including ore, furnace lining, fuel and slag), to compare these to slag inclusions in the resulting bloom and worked objects, and then explore the relationships between ore, slag and slag inclusions. This study has revealed that the composition of slag inclusions most closely relates to the smelting slag produced, whereas provenance to a specific ore would be difficult due to the chemical variability derived from furnace lining, fuel and any fluxes used. Some compounds in the slag inclusions are particularly affected during smithing of the artefact, i.e. those present in the sand flux and fuel used. However, trends are observed in the K₂O/MgO, MnO/SiO₂, Al₂O₃/SiO₂, Al₂O₃/MgO, Al₂O₃/K₂O and Al₂O₃/CaO ratios that allow comparison between slag inclusions and smelting slag in these experiments, and may therefore be used during other provenancing attempts. The knowledge gained from the experimental assemblages was subsequently applied to an archaeological case study, examining objects from the 900 Cal BC smithing site of Tel Beth-Shemesh, Israel and the 930 Cal BC smelting site of Tell Hammeh, Jordan. The analyses suggest that none of the artefacts examined derived from the Hammeh smelting system.     

Vietnamese (15th Century) Blue‐And‐White,Tam Thai and Lustre Porcelains/Stonewares: Glaze Composition and Decoration Techniques*

EDS, X‐ray fluorescence, Raman spectroscopy, thermal expansion–shrinkage measurement and scanning electron microscopy were applied to determine the elemental components, structural phases and glazing temperatures of the transparent glazes, blue underglaze and overglaze tam thai (including gold‐like lustre) decorations from the 15th‐century Vietnamese porcelains/stonewares found at the Chu Ðâu–My Xa kiln site and in the Cù Lao Chàm (Hôi An) cargo. The ancient technology for colouring the glazes is discussed. The various blue tones in the underglazed décor result from cobalt‐containing manganese ore, with the intentional addition of iron oxide. The overglaze copper‐green and the gold‐like lustre were obtained by dispersing copper in lead‐based glass. The red colour was made using hematite dispersed in lead‐rich flux.     

An assessment of the magnetic response of an iron‐smelting site*

The magnetic response derived from an iron‐smelting site was investigated by comparing magnetometry and magnetic susceptibility geophysical survey data and laboratory analyses of the magnetic characteristics of the furnace and slags. Magnetic analysis and microscopy (optical and SEM) of samples from the furnace lining and the slag deposits demonstrated the heterogeneity in the magnetic, morphological and mineral compositions of both materials. The comparison of the magnetic characteristics of the material with the geophysical survey data illustrated the importance of using both magnetometry and magnetic susceptibility survey techniques to maximize the information from an iron‐smelting site. The furnace was dated archaeomagnetically to the 14th century ad . The results demonstrate that the magnetic analysis of iron‐smelting sites is highly valuable, both to characterize sites and to improve the understanding of early iron‐working technology.     

THE TUNGSTEN AND TIN SIGNATURE OF IRON ORES FROM ELBA ISLAND (ITALY): A TOOL FOR PROVENANCE STUDIES OF IRON PRODUCTION IN THE MEDITERRANEAN REGION

The mineralogy, petrography and major‐ and trace‐element composition of iron ores from Elba Island (Tuscany, Italy), one of the most important iron sources in the Mediterranean area since the first millennium bc , revealed that hematite‐rich ores display prominent enrichments in W and Sn (up to 4950 μg g^?1 and 8400 μg g^?1, respectively). These two elements are hosted by tiny grains of W–Sn mineral phases (ferberite, scheelite and cassiterite) that are disseminated throughout the hematite matrix. A comparison with iron ores from many Italian and European localities (most of which were exploited in ancient times) suggests the uniqueness of the geochemical pattern of Elba Island hematite‐rich ores (i.e., high W and Sn, low Mo and low Cu, Pb and Zn). We suggest that this geochemical signature may represent a new provenance marker not only for discarded ore at smelting/smithing sites, but, possibly, also for metallurgical slag and smelted metal produced in the chaîne opératoire of the iron process.     

MINERALOGY OF MEDIEVAL SLAGS FROM LEAD AND SILVER SMELTING (BOHUTÍN,PŘÍBRAM DISTRICT,CZECH REPUBLIC): TOWARDS ESTIMATION OF HISTORICAL SMELTING CONDITIONS*

Slags from the Pb/Ag medieval (14th century) smelting plant located at Bohutín, P?íbram district, Czech Republic, were studied from the mineralogical and geochemical points of view. Two types of slags were distinguished: (i) quenched slags formed mainly by Pb‐rich glass and unmelted residual grains of SiO₂ and feldspars, and (ii) crystallized slags mainly composed of Fe‐rich olivine (fayalite) and glass. The mean log viscosity value of the slags calculated for 1200°C was 2.119 Pa s. The morphology of olivine crystals was used to estimate the cooling rates of the melt, for some slags indicating rates > 1450°C/h. The projection of the bulk composition of slags onto the SiO₂–PbO–FeO ternary system was used for rough temperature estimates of slag formation, lying probably between 800 and 1200°C.     

Excavations at Rockley Smithies,a water-powered bloomery of the 16th and 17th Centuries

Abstract

Between about 1500 and 1640 iron was smelted by the direct, bloomery, process on the lands of the Rockley family at (N.G.R.) SE/340023, to the south-west of Barnsley, Yorkshire, using charcoal and ore from the well-wooded outcrops of the Tankersley ironstone, adjacent to the site. Evidence for operation early in the 16th century was limited to accumulations of hearth-cinder and of debris from ore-roasting, minor structures and traces of a dam. About 1600 a major rebuilding involved the construction of a bloom-hearth and probably two stringhearths, with bellows powered by waterwheels, and an unpowered hammer. Minor rebuilding took place early in the 17th century, and archaeological and documentary evidence combine to place abandonment at about 1640. Demolition and stone-robbing could well have provided material for the blast-furnace built a short distance away in 1652. The bloomery site was abandoned to pasture and perhaps a cottage, and at some time early in the 19th century was occupied by two houses and a workshop for an adjacent colliery tramway. It was covered by a road embankment in 1966.

Evidence was found of techniques at a comparatively advanced bloomery, in operation at a time when English ironmasters were, however, increasingly favouring the use of the blast furnace.     

The Source of Iron‐Oxide Pigments Used in Pecos River Style Rock Paints

The likely sources of iron‐oxide pigments used in prehistoric rock paintings in the Lower Pecos Archaeological Region were identified on the basis of chemical fingerprinting using LA–ICP–MS. The chemical signatures of 13 red rock paint samples collected from two south‐west Texas sites were compared with three potential source materials (ochre, siltstone and rhyolite), and two pigment cakes (crayons) that were excavated near the sampling sites. The significant chemical similarities between the paint and siltstones suggest that siltstone was used as the source of the colour. The overlapping chemical signatures for one of the pigment cakes and siltstone further suggests that some of the prehistoric people inhabiting the area 3000–4000 years ago had acquired the skills to extract iron oxide from siltstone and process it into paint pigments.     

The Glaze Technology of Hispano‐Moresque Ceramic Tiles: A Comparison Between Portuguese and Spanish Collections

For the first time, Hispano‐Moresque glazed tiles from Portuguese and Spanish collections were studied together and compared. This work is included in a wider study tackling the technology of Hispano‐Moresque tile production from several collections in the Iberian Peninsula. While showing many similarities, differences were identified between collections, regarding both chemical and morphological characteristics. The collection from the Mosteiro de Santa Clara‐a‐Velha (Coimbra) stands out from the other collections, with higher SnO₂ content (up to 14 wt%), the highest Fe₂O₃ contents in amber glazes and a Ca‐rich interface layer (mostly comprised of wollastonite, CaSiO₃). Samples from Palácio Nacional de Sintra (near Lisbon) and Seville‐attributed samples (from the Instituto Valencia de Don Juan) are chemically similar, except that most Sintra's samples display a K‐rich glaze/ceramic interface, whereas the ones from Seville exhibit both K‐rich and Ca‐rich inclusions. The samples attributed to Toledo show glazes with many inclusions, contrasting with the homogeneous glazes in most Hispano‐Moresque tiles. From these results, we identify differences that can be used as markers in future studies on Hispano‐Moresque tiles.     

IDENTIFICATION OF POST‐DEPOSITIONAL CHEMICAL ALTERATION OF CERAMICS FROM THE NORTH COAST OF PAPUA NEW GUINEA (SANDUAN PROVINCE) BY TIME‐OF‐FLIGHT–LASER ABLATION–INDUCTIVELY COUPLED PLASMA–MASS SPECTROMETRY (TOF–LA–ICP–MS)*

The measured chemical composition of archaeological ceramics can result from a variety of geological, cultural and taphonomic factors. In the present study, we evaluate the likelihood that elevated barium concentrations in ceramics from the archaeological site of Wom/Aiser, located on the northern coast of Papua New Guinea, result from post‐depositional enrichment. Using time‐of‐flight–laser ablation–inductively coupled plasma–mass spectrometry, we mapped chemical compositional profiles across cut sections of ceramic sherds from four archaeological sites, all previously chemically characterized. We identify the formation of pronounced concentration gradients in samples from Wom/Aiser relative to sherds with low barium concentrations, consistent with post‐burial uptake.     

The Origin and Archaeometallurgy of a Mixed Sulphide Ore for Copper Production on the Island of Kea,Aegean Sea,Greece

At the hill of Agios Symeon, on the island of Kea, Aegean Sea, Greece, ancient metallurgical slags with a high Pb–Zn–Cu content have been found. Thermodynamic simulations have been carried out, using the FactSage? thermodynamic database computing system, with a view to understanding the ancient metallurgical processes that produced the observed slag compositions and morphologies. The simulations demonstrate that the slag samples resulted from Cu‐making processes. It would thus appear that mixed ores were used, containing Cu₂S–FeS–PbS with significant amounts of sphalerite (ZnS) as impurity. The roasted ores were reduced at relatively high oxygen potentials at ～1125°C to form Cu containing low levels of Pb, Fe and Zn.