Paint It Black: The Rise of Metallurgy in the Balkans

This paper integrates archaeological, material, microstructural and compositional data of c. 7,000 years old metallurgical production evidence with the aim to address the knowledge of the world’s earliest metalworkers. The main focus is placed on copper minerals, ores, slags, slagged sherds and metal droplets coming from four Vin?a culture settlements in Serbia and Bosnia and Herzegovina: Belovode, Plo?nik, Vin?a and Gornja Tuzla, all dated between c. 5400 and 4400 BC. Chemical study of copper minerals throughout all sites points at striking uniformity in selecting black and green minerals from the early days of the settlements’ occupation, some of which predate the metal smelting events. Microstructural examination of metal production debris showed convincing technological similarity throughout c. six centuries of copper making in the studied sites, as well as a consistent choice of black and green ores for metal extraction. We argue that black and green ores were intentionally selected as ingredients for the metal smelting ‘recipe’ in the early stages of Balkan metallurgy based on the knowledge related to their characteristic visual aspects. This finding demonstrates how important the adequate combination of colours was for the early copper metalworkers and suggests a unique technological trajectory for the evolution of metallurgy in this part of the world. It also illustrates the capacity that micro-research carries in addressing the how and why of the emergence of metallurgy, and outlines a methodology for future studies of early metallurgies worldwide.     

The production of speiss (iron arsenide) during the Early Bronze Age in Iran

In this paper, analyses of some unusual slag samples from the prehistoric site of Tepe Hissar in northeastern Iran are presented. These slags are the remains of a five-thousand-year-old pyrotechnological process that produced speiss, a quasi-metallic material usually formed as an accidental by-product of copper or lead smelting. We argue that the “speiss slags” from Tepe Hissar suggest the intentional production of iron–arsenic alloy (“speiss”) in prehistory. Why the Tepe Hissar metalworkers produced speiss is a question that requires further investigation, but our preliminary assessment suggests that it was to provide arsenic as an alloying component for arsenical copper, the preferred copper alloy during much of the Early Bronze Age in Iran, and widely used across the ancient world. This recognition significantly advances our understanding of the early stages of metallurgy in the Old World.     

Reassessment and new data on the diachronic relationship of Thassos Island with its indigenous metal resources: a review

The extraction of mineral ores and its associated metal production has been a persistent element of the economy on Thassos Island since prehistoric times. As early as the Upper Palaeolithic, around 20,000 years ago, ochre had been mined and used for painting, while early silver extraction is attested during the Final Neolithic (early fourth millennium BC). Copper production and alloying becomes an important activity in the coastal settlements of the island during the third and second millennia. The inception of iron metallurgy has been seen in association with copper smelting as confirmed by analyses on slag found in Early Iron Age upland cemeteries. With the arrival of the Greek colonists around 650 BC, intensification in silver and gold extraction became paramount for further economic expansion. This deep history in the use of Thassian metals is being reviewed based on archaeological findings and archaeometallurgical research of the last three decades, while new analytical data on Early Bronze Age copper smelting at Aghios Antonios are being presented.     

Copper production at Baratti (Populonia,southern Tuscany) in the early Etruscan period (9th–8th centuries BC)

Populonia is commonly regarded as one of the most important iron working centres in Europe in the 1st millennium BC. However, multiple layers of copper slags have been recently discovered at the bottom of the slag deposit occurring along the shoreline of the underlying Baratti Gulf. Copper slag layers have been radiocarbon dated to the 9th–8th centuries BC, i.e. to an early metallurgical stage predating the later large-scale iron production. The overall features of copper slags indicate a single-step smelting process of copper-rich ores containing variable amounts of Zn and Pb. Chemical and textural features of copper slags indicate an optimised, high-efficiency metallurgical process.     

Transitions in cast iron technology of the nomads in Mongolia

Metallurgical study of seven cast iron artifacts recovered from sites of the former Xiongnu (BC 3rd to AD 1st), Turk (AD 6th to 8th), Khitan (AD 10th to 12th), and Mongolian empires (AD 12th to 15th) shows that the earlier Xiongnu and Turk artifacts were made of cast iron alloys of near eutectic composition. The later Khitan and Mongol objects had greatly reduced carbon content in the range of ultrahigh carbon steel rather than cast iron, and contained more than 0.5 mass % silicon as an alloying element. Inclusions high in sulfur, phosphorus or silicon are also present. These differences suggest that Mongolia experienced a technical transition a few centuries before the establishment of the Mongolian empire, which is in agreement with some written accounts. The microstructures of the cast iron artifacts are compared with the related archaeological and documentary evidence. The results suggest that the use of fossil coal in smelting and the state policy of controlling iron production were the major factors responsible for the transition.     

EARLY BRONZE AGE TIN PROCESSING AT KESTEL/GÖLTEPE,ANATOLIA

Chemical analysis of statistically significant numbers of samples including minerals, sediments, soil, host rock as well as powdered materials, crucible accretions and metal artefacts revealed information about the distribution of cassiterite at Kestel and the tin smelting processes that took place at Göltepe c. 2600 BC. Using the ancient technique of vanning for the isolation of tin ore (cassiterite), followed by assaying by blowpipe/charcoal block, as well as crucible smelting with a blowpipe, good tin metal suitable for alloying with copper to make bronze was obtained. There is every indication that tin was mined and smelted in the Early Bronze Age at the Kestel/Göltepe sites.     

古代钢铁制品中的浮凸组织初步研究

为研究钢铁制品中浮凸组织产生的原因,对14件取自不同地方、属于不同时期的具有浮凸组织的样品利用金相组织鉴定、扫描电镜能谱分析、化学分析和显微硬度测定等方法进行了研究。结果表明：金相组织观察发现浮凸组织与夹杂物和铁素体晶粒间界有一定的关系,并存在有不同的形貌,其显微硬度均比附近基体高;成分分析表明有浮凸组织的样品磷含量要比没有浮凸组织的样品磷含量高一个数量级。有浮凸组织样品内部磷含量的分布也不均匀。这些结果说明,浮凸组织的产生主要原因是矿石中的磷在冶炼过程中进入铁中,而在随后的脱碳退火、炒炼和冷、热加工过程中均不能有效地脱去;同时,固溶在铁中的磷与铁形成薄膜阻止晶粒间界长大、或在埋葬条件下长期时效引起的晶界移动而产生了浮凸组织。     

SERIPHOS SURFACES: A STUDY OF COPPER SLAG HEAPS AND COPPER SOURCES IN THE CONTEXT OF EARLY BRONZE AGE AEGEAN METAL PRODUCTION

Kephala and Phournoi, on the island of Seriphos, add to a growing number of EBA metal production sites identified in the south‐central Aegean. Analytical examination of samples from the two sites addressed the technological parameters of the copper smelting process, indicating the use of mixed oxidic and sulphidic copper–iron ores to produce unalloyed copper with minute copper sulphide inclusions. A preliminary geological reconnaissance of the island identified several small copper mineralizations, one of them close to the site of Kephala. Nevertheless, the ore sources used remain unclear. Comparisons are made with other contemporaneous neighbouring smelting sites.     

A discussion of magic and medicines in East African iron working: actors and artefacts in technology

Through an inquiry into locally constructed, pre‐industrial Tanzanian iron smelting practices this article looks beyond social representation of technologies and suggests a more nuanced perspective than the more familiar rituals of transformation and gendered procreative paradigm. It is demonstrated that among the Pangwa and Fipa peoples iron smelting symbolism was not merely a social representation of “something” else and of something of greater significance such as religion, economy and politics, rather there were no real distinctions between technology and other spheres of life; there was no (ontological) difference between humans and non humans. Drawing on inspiration from phenomenology and semantics, as well as Actor Network Theory, I will argue that among Fipa and Pangwa iron workers the use of magic and medicines, as well as an overall thermodynamic conception of the body, was transferred from personal and collective lived experience by metaphorical imagination to the iron smelting furnaces.     

Partitioning of trace elements between the ores, fluxes, slags and metal during the smelting of copper

This paper gives the results of smelting seven parcels of copper ores from well-known mining areas. The behaviour of the trace elements introduced from the ore, the fuel, and the fluxes has been investigated by analysis of the main products, metallic copper and the slags. Most of the ores were capable of giving copper of relatively high purity and therefore, in order to represent conditions believed to have existed in the Early Bronze Age, two artificial ores were made up and copper high in arsenic and nickel was obtained.The results show that it is relatively easy to smelt a wide range of copper minerals to give copper of high purity apart from iron. This latter element can be removed by careful refining. The remaining elements are present at the parts/10³ level. Wood fuel is thought to contribute little to the trace element pattern. Even if it did, it would merely reinforce the elements already contributed by the ore and flux as the timber is likely to have been grown in the immediate vicinity of the ore and will probably contain the same trace elements.Useful comparison is made between the trace element pattern resulting from these smelting runs and material from archaeological sites in the vicinity of the mining areas.     

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.     

‘DE CAERIMONIAE’ TECHNOLOGICAL CHOICES IN COPPER‐SMELTING FURNACE DESIGN AT EARLY BRONZE AGE CHRYSOKAMINO,CRETE*

The excavation of a number of Early Bronze Age sites in the Aegean has recovered perforated ceramic fragments. Archaeometallurgical analysis of slag adhering to these fragments indicates that they are the remains of copper‐smelting furnaces. Despite compelling analytical data supporting this identification, no attempt has been made, thus far, to establish how these unusual furnaces may have operated. The use of perforations is poorly understood and can be considered a counter‐intuitive solution for the reduction of oxidic copper ores. The experiments reported here explore the possible technological choices made by the ancient metalworkers of Chrysokamino to ensure the effective reduction of copper minerals. Temperature data and slag samples were obtained to ascertain the technical performance of the furnace structure with, and without, perforations. Possible reasons are given for the use of a perforated design, and the implications of such technological choices are considered.     

GIS在北京延庆大庄科辽代冶铁遗址群景观考古研究中的初步应用

以北京延庆县大庄科乡冶铁遗址群为例,对空间结构及其与资源、环境间的关系通过GIS工具进行分析。根据对冶炼活动有显著关系的影响因子,建立遗址分布之间的定量关系,进而模拟小区域范围内的遗址预测。研究发现,该区冶铁遗址群对地理位置中的坡度和高程因素展现出较强的依赖性,主要表现为遗址的坡度(7°以下)和高程(650m以下)数值均相对较小;遗址与水系间联系明显,冶铁遗址主要集中在河流交汇处,方便冶炼过程及相关活动水源的供应;而随着冶炉容积(即冶铁产量)的增加,小范围内的冶铁遗址选择,并未以铁矿资源距离就近为最佳选取原则,表明了人类生产活动中对资源的依赖程度有所减低。     

Investigating the production provenance of iron artifacts with multivariate methods

The quest for suitable data, data treatments and statistical methods for identifying the provenance of iron artifacts has led to a variety of analytical strategies. Researchers working on the problem have been slow to develop or adopt the use of multivariate statistical techniques, despite their successful implementation in other archaeomaterials sourcing frameworks. This paper explores the analytical potential of a comprehensive multivariate statistical strategy for identifying the primary production origins of bloomery iron artifacts using bulk chemical analyses of bloomery smelting slag and slag inclusions in iron artifacts. This strategy includes a multivariate model for identifying distinct slag inclusion types introduced during smelting and refining. Principal component analysis and linear discriminant analysis are then applied to smelting slag training sets to create multivariate provenance fields, the chemical distributions of which are defined by kernel density estimation. Single and multi-group evaluation methods are examined. Appropriate data transformations are discussed to facilitate the projection of the chemistry of “unknown” slag inclusions into the multidimensional space generated by the smelting slag groups of known provenance. The efficacy of this strategy is demonstrated through its application to a previously examined data set derived from three iron production experiments and a published archaeological example. Results indicate that an appropriately designed multivariate strategy can be an effective tool for evaluating provenance hypotheses for bloomery iron artifacts.     

IRON IN ANCIENT COPPER

Analysis of early copper-base artifacts invariably reveals traces of iron. Iron enters the copper during the smelting process and the level of iron in the metalwork is an indication of the smelting technology. In areas such as Western Europe where prehistoric slag heaps are absent even in the proximity of undoubted ancient mines, the iron content is low reinforcing the link between smelting technology and iron content. Very occasionally the iron content was deliberately encouraged and alloys containing between 30% and 50% of iron in copper were made, mainly for use in currency. These alloys are without modern parallel and their metallography and method of production are considered in some detail here.     

济南运署街汉代铁工场遗址的相关问题探讨

为探讨济南运署街汉代铁工场遗址的性质和冶炼技术,应用X-射线荧光、X-射线衍射、热膨胀测温等方法,对遗址出土的部分遗物进行了相关分析。结合出土实物和测试结果,可以推断运署街遗址是汉代一处兼有冶炼和铸造的铁作坊。陶范、耐火砖、铁渣及矿石原料等冶铸遗物的分析指出,当时的矿石分选、加工、冶炼、铸造技术已经十分成熟,在一定程度上反映了汉代冶铁业的工艺水平。     

DID THE GREEKS GO TO COLCHIS FOR METALS?

A too simple understanding of the process of Greek colonisation, especially the reasons for it, sometimes leads modern scholars to unrealistic conclusions. This paper examines the view commonly found in the literature that the main reason for the arrival of the lonians in Colchis in the middle of the 6th century BC was the area's richness in metals. Archaeological material discussed here shows that Eastern Pontus was far from being so well endowed, and that the local tribes were less advanced in metallurgy than is often believed. The Scythian 'incursion'into Colchis at the end of the 7th century BC both introduced Colchians to iron metallurgy and gave rise to a lacuna in the material culture of the area. New tribes in the Eastern Black Sea in the middle of the 6th century BC revived the iron industry, but it never again reached the scale of production achieved in the 7th century BC. The involvement of the Greeks in iron metallurgy is a matter of which, so far, we know nothing. Nevertheless, the Greeks, trying to adapt their art to the tastes of the local rulers, established in Colchis in the 5th century BC schools of gold- and silver-smiths, as well as the production of metal seals and engraved gems.     

Malkata and Lisht Glassmaking Technologies: Towards a Specific Link between Second Millennium BC

Elemental analyses have been conducted on 61 coloured opaque glasses from the Malkata and Lisht New Kingdom glass factories. The presence of tin in several of the blue glasses suggests that a bronze casting byproduct or corrosion product was the source of the copper colorant for these glasses. A positive correlation between the lead and antimony concentrations of the yellow and green opaque glasses, plus a consistent excess of lead oxide in these glasses, suggests the use of antimony‐rich cupellation litharge as the source for the Pb₂Sb₂O₇ , colorant in these glasses. The metallurgical byproducts used to colour the Malkata and Lisht glasses provide an explicit mechanism for Peltenburg's theory of interaction between second millennium BC glassmakers and contemporary metalworkers.     

A STATISTICAL STUDY OF THE IMPURITY OCCURRENCES IN COPPER ORES AND THEIR RELATIONSHIP TO ORE TYPES

A study of the impurity distributions in copper obtained from various ores shows no significant correlations between the impurity distributions. A test of 390 samples of copper obtained from various ores shows that more than 75% of copper samples can be correctly identified as coming from either simple copper metal ores, oxidized ores or more complex reduced ores thereby yielding information on the metallurgical capabilities of the society smelting the ores.     

Comparative microstructural and elemental analysis of iron artefacts from Kaveri valley archaeological sites

Iron has been one of the most critical technotraditions that had lasting impact on social formation throughout the Iron Age and historical period. Iron was used in warfare and subsistence economy. Our knowledge on ancient iron smelting and working have generally been derived from ethnography and ethnohistory, which is by all means, time, region, and raw material specific. Scientific analyses of ancient iron have contributed in understanding this heritage to a respectable extent, yet a comprehensive knowledge about the evolution of iron making through time and space in India eludes us. In this work, a comparative study of iron artefacts from two Iron Age/Megalithic-Early Historic sites of Tamil Nadu, south India, that is, Mangadu (burial site) and Ambal (habitation-cum-burial site) is carried out to understand the iron thermal-processing capabilities. The retrieved artefacts were examined using X-ray fluorescence (XRF) for elemental composition. The imaging of the artefacts was done using Scanning Electron Microscopy (SEM), Electron Backscatter Diffraction (EBSD), and Optical Microscopy (OM). In addition, phase identification was performed using X-ray diffraction (XRD) and Energy Dispersive X-ray Spectroscopy (EDS). Combination of these analyses illustrates that inhabitants of Mangadu and Ambal were aware of the iron alloy manufacturing/processing techniques such as forging and hammering.