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.     

Microstructural and elemental analyses of slags excavated from Xuxiebian iron‐smelting site,Sichuan, China

Xuxiebian is an iron‐smelting site located in Pujiang county of Sichuan province, China. Two excavations were carried out in 2007 and 2011, and four bowl‐shaped furnaces were excavated. Ten slag samples from the site were prepared and analysed. The present paper reports the results of metallographic and elemental examination of the specimens. It is concluded that both pig‐iron‐smelting and refining process were applied at the Xuxiebian site, and the bowl‐shaped furnaces are possibly refining furnaces. The function of the site was probably to produce pig iron and refine the pig iron into wrought iron.     

The Mechanism and Kinetics of In Situ Conservation of Iron Cannon on Shipwreck Sites

Analysis of the pre‐disturbance values of the in situ corrosion parameters on historic iron shipwrecks and artefacts has established that the arithmetic product of the pH and corrosion potential is dependent on the burial environment and provides a unique insight into the objects' state of decay. The value of the product changes during in situ conservation treatment with sacrificial anodes, and reaches a minimum at which point the treatment is completed. Treatment times vary with water‐depth, being faster on shallower sites and shorter for more extensively corroded artefacts. The model was developed using data from the Duart Point wreck (1653), the Monitor‐styled warship HMVS Cerberus (1926) and a series of wrecks in Australia and the USA.     

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.     

THE ANCIENT MINE OF SERVETTE (SAINT‐MARCEL,VAL D’AOSTA,WESTERN ITALIAN ALPS): A MINERALOGICAL,METALLURGICAL AND CHARCOAL ANALYSIS OF FURNACE SLAGS*

The Cu–Fe mining district of Servette is located in the valley of Saint‐Marcel (Val d’Aosta) at about 1800 m a.s.l. in the western Italian Alps. A large furnace slag deposit occurs near the Servette mine. Slags are mainly constituted by silicate and oxide in a glassy matrix, with disseminated sulphides and iron–copper alloys, and they record temperatures of 1380–1100°C. Radiocarbon dating of slag charcoals has shown that metallurgy in this site took place around ad 890–980. The charcoal analysis has shown that coniferous wood was mainly utilized, and intensive exploitation over the centuries led to a change in the composition of the local woods.     

Slag as evidence for early iron production in arctic Norway

Physical, structural and chemical analyses were made on slag remains obtained from three sites in Iron Age arctic Norway. Scanning electron microscopy and x‐ray microanalysis were employed to confirm that the slag can only be a result of iron production. Although a distinction between slag produced by smithing and smelting proved difficult, consideration of the processes and the resources available support the assumption that both were practiced at the sites. The results provide firm evidence of iron production in the region of Norway north of the 69th parallel, by at least the sixth century AD.     

At the Transition from Late Medieval to Early Modern: the Archaeology of Three Wrecks from Turkey

During surveys in the Rhodian Straits in 2005–06, the staff of the RPM Nautical Foundation discovered three deepwater wrecks which reflect elements of the transition from late medieval to early modern seafaring. The assemblages, and their plotting on site‐plans generated from photographic evidence, point to the finding of a small oared warship equipped with wrought‐iron carriage‐ and swivel‐guns, a small coasting vessel armed with wrought‐iron swivel‐guns, and a larger merchantman equipped with cast‐iron carriage‐guns. While the features of the smaller vessels do not identify their country of origin, those of the larger merchantman have good parallels with known English wrecks. © 2009 The Authors     

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.     

The Construction of the Blists Hill Ironworks

Abstract

The manufacture of wrought iron by the puddling process has a long history in the UK and in Shropshire. Commercial production ended in 1976 when the firm of Thomas Walmsley and Sons Limited ceased its manufacture at their Atlas Forge in Bolton. The Ironbridge Gorge Museum is to reconstruct and operate a wrought iron manufactory at its Blists Hill Museum. This paper presents the nature of the intended reconstruction and discusses, the manning and material requirements for its operation.     

PHOSPHATES IN ARCHAEOLOGICAL FINDS: IMPLICATIONS FOR ENVIRONMENTAL CONDITIONS OF BURIAL*

The occurrence of coarse‐grained vivianite and mitridatite aggregates in a potsherd, a grand ring and a timber imprint from the Second Iron Age site of Adria (Rovigo, northeastern Italy) suggest contrasting environmental conditions of burial. In particular, bone fragments were replaced by vivianite at relatively low pH and Eh, due to the presence of deteriorating organic matter, together with slag and iron flakes. Subsequent interactions with Ca‐rich groundwater characterized by higher pH and Eh determined the growth of mitridatite after vivianite. Although phosphates crystallized after burial, the examined samples were not involved in pervasive chemical contamination.     

Mineralogical And Chemical Investigations Of Bloomery Slags From Prehistoric (8th Century Bc To 4th Century Ad) Iron Production Sites In Upper And Lower Lusatia,Germany

More than 400 fayalitic bloomery slags from prehistoric iron production sites in Upper and Lower Lusatia, eastern Germany, as well as bog iron ore samples and intermediary samples of the smelting process, were analysed by chemical and mineralogical techniques. While the precursor bog iron ores exploited in the two regions under investigation were very similar in composition, consisting of low‐manganese/low‐barium as well as high‐manganese/high‐barium types of ore, pronounced differences in slag composition were detected. Slags from 17 investigated sites in Upper Lusatia showed average P₂O₅ contents between 1 and 3 mass%, whereas slags from 15 investigated sites in Lower Lusatia were generally much richer in phosphorus, reaching values as high as 7 mass% P₂O₅. Since a reasonable correlation exists between calcium and phosphorus contents in the slags of the latter sites, it is conjectured that deliberate addition of CaO to the ore/charcoal charge of the bloomery furnace may have taken place in order to fix the phosphorus in the slags effectively. In many samples, this conjecture is being supported by the detection of a slag mineral Ca–Fe phosphate Ca_9?xFe_1+x(PO₄)₇ that presumably crystallized from a residual phosphorus‐rich melt and shows a cotectic relationship to both Ca‐rich fayalite and wustite, as well as to members of the solid solution series magnetite–hercynite.     

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.     

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.     

A Box Containing Carpenter's Accessories from The Akko 1 Shipwreck,Israel: Archaeometallurgical Analysis of Surviving Ironwork

The Akko 1 shipwreck was an Egyptian armed vessel, built at the beginning of the 19th century. A wooden saw handle and a box containing iron nails and two split pins were discovered towards the stern. Given their function, location and context, these were part of the ship's carpenter's tools and accessories. A methodology was developed for conducting systematic metallurgical analysis in order to understand the manufacturing process of the surviving ironwork items, as well as to enlarge our knowledge regarding ironworking technologies during the early 19th century. Such methodology may assist in the future understanding of the technological evolution of similar wrought‐iron objects. The results demonstrated that the artefacts have a wrought‐iron heterogeneous microstructure and were manufactured by hot‐working prior to surface hardening by pack carburization.     

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.     

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.     

Site Charting and Environmental Studies of the Monitor Wreck

Abstract

Marine geological and geophysical techniques have been applied to studies of the Monitor wreck to chart the fragments of the wreck and to determine the corrosion state of the remaining iron and the state of the geological and oceanographic environment in the immediate area of the wreck. Methods included magnetic surveying of the wreck site, computer calculations of the magnetization of the Monitor iron, and comparisons with magnetic measurements on iron artifacts from the wreck. Piston coring of the strata immediately beneath the wreck and near-bottom current measurements revealed evidence on the sedimentation rates and sediment transport at the site; these data confirmed interpretations made from high-resolution subbottom reflection profiles across the site.     

THE AMBER OF EL DORADO: CLASS IB ARCHAEOLOGICAL AMBERS ASSOCIATED WITH LAGUNA GUATAVITA*

Laguna Guatavita, a crater‐like lake located in central Colombia, was used by pre‐Columbian Muisca people for a variety of socio‐religious ceremonies, many of which involved casting offerings into the lake. Of these, the installation of a new ‘king’ became the basis of the El Dorado myth that was carried back to Europe by 16th century conquistadores. In the present study, beads collected from Laguna Guatavita during a late 19th/early 20th century attempt to recover valuables from the lake bed, have been subjected to geochemical analysis. Results establish that these artefacts have been fabricated from Class Ib amber. Class Ib ambers have not previously been reported in either the geological or archaeological records of Central or South America, and their existence in this context implies that the Muisca people had access to a unique local or regional source of amber, knowledge of which has subsequently been lost.     

An Empirical Comparison of Edge Effect Correction Methods Applied to K‐function Analysis

This paper explores various edge correction methods for K‐function analysis via Monte Carlo simulation. The correction methods discussed here are Ripley's circumference correction, a toroidal correction, and a guard area correction. First, simulation envelopes for a random point pattern are constructed for each edge correction method. Then statistical powers of these envelopes are analyzed in terms of the probability of detecting clustering and regularity in simulated clustering/regularity patterns. In addition to the K‐function, K(h), determined for individual distances, h, an overall statistic k is also examined. A major finding of this paper is that the K‐function method adjusted by either the Ripley or toroidal edge correction method is more powerful than what is not adjusted or adjusted by the guard area method. Another is that the overall statistic k outperforms the individual K(h) across almost the entire range of potential distances h.     

CUERDA SECA CERAMICS FROM AL‐ANDALUS,ISLAMIC SPAIN AND PORTUGAL (10TH−12TH CENTURIES AD): INVESTIGATION WITH SEM–EDX AND CATHODOLUMINESCENCE*

Since little is known about the cuerda seca technique, our aim has been to complete an initial analysis of 11th‐century cuerda seca by studying fragments from the 10th century (Pechina, Almería) and the 12th century (Mértola and Almería), so as to establish the diachronic evolution of this technique. Characteristics specific to cuerda seca ceramic glazes were investigated using scanning electron microscopy (SEM) and quantitative chemical analysis with energy‐dispersive X‐ray spectrometry (EDX). The chemical compositions of the different‐coloured glazes (green, black, yellow and white) have given us valuable indications about the evolution of the technique. The opacification mode and the firing process were also investigated. With the help of cathodoluminescence (CL) and the study of modern ‘cuerda seca’ glazed ceramics, new hypotheses regarding the number of firing stages, taking into account glaze and paste transformations and their interactions, are put forward.