logo

Search published articles


Showing 2 results for Slag

Seyed Mohammad Amin Emami,
year 1, Issue 1 (12-2017)
Abstract

Abstract
The mineralogical and chemical investigation of ancient slag is of high importance for economic mineralogist and archaeometalurgist. These investigations reveal information, which is of general historical and mineralogical interest. Over than 95% of metallic reservoirs have proved antiquity evidences. By using mineralogical-petrographical studies on metallurgical slag as an object from the ancient world, it could be enhance to understanding about the major and trace elements via metal extraction.
The basin of Halil Rood (Halil River) is privileged to have a rich civilization. Many objects as well as metallurgical evidences belonging to the third millennium BC have been discovered in this district during the archeological excavations. Kerman – Rabor – Jiroft district is of great interest due to the archaeometallurgical signs in south-west Iranian desert and belong to the Halil Rood region. This district is important according to the enrichment of polymetallic hydrothermal ore reservoir such as Cu, Pb, Zn, Sn, Ag and Au in south and south-west of Zagros orogeny. Several scientists have been focused on this region, as one of the born place of metallurgy in the ancient World [1]. The primary aim of this study was the characterization of extracted metals and the methods of smelting. The objects to be discussed here are mostly copper slag as well as ores. 20 local mining- and metallurgical places have been found through recently archaeometallurgical expedition. These places are mainly consisted of slag-heap, fireplaces and ore deposition, which are remarked possibly as passage-metallurgy along south Iranian desert.
Keywords: Archaeometallurgy, Metallogeny, Petrology, Slag, Copper, Kerman.

Introduction
There are several slag accumulations in Halil region. The slag samples investigated during the present work were collected from thirty-seven different ones which were located in different parts of studied area. There are four Types of slags in these districts districts.
A) The slags are generally massive and in some cases the colour is black with some red spots (Copper). The sign of flow structures can be seen on some of them, but there is no glacial one. The porosity is high as well as their density. The structure such as furnace has been excavated from this area. This Furnace has ca. 1.5 m cross section dimension.
There was a deponie of slags materials upside this furnace. In the furnace there exist no slags by now. It could be the furnace with temporary employment in this region. Such furnaces with the same structures have been observed in the north of central desert in Iran, In sahroud and Khorasan region.
B) there are five small dumps located near each other which have been considered. These samples have flow structures. They are black and red in color and have more porosity than an accumulation’s samples.
C) several small dumps located at the main stream at the north of Rabor-Jiroft district, which considered as C accumulation. Only one slag was selected from it. This sample is black in colour and has massive structure. No flow or glacial structures can be seen between slag pieces in C accumulation.
D) A very small dump has been excavated. The physical properties of these slags are completely different from other ones. This sample has many porosity and low density. It is black in colour and no flow or glacial structures are seen. Mineralogical and petrological analyses were performed only on slag materials. The dating of all this samples to classify these dumps could not be possible in this project. The distribution of the dumps is not only statistically but also commonly on this field, and for this reason there is another factor to have no chance to get the better results in respect on the ageing of dumps on this region exactly. The topographic situation and the changing of the earth in each seasons, and the movement of the seasonal rivers disturb the structure of the surface topography permanently each year. This distribution during the overflows in the wet seasons could be the aspect of slag’s distribution either.

Halil region is located in south central of Iranian metallogenic zone. Rock types in this area are mainly divided into 6 sections as follow:
1. Upper Proterozoiec: the oldest and the most abundant rock type in studied area. This formation is composed of quartzitic shist, phyllic- like schist, green schist and marble. Quartz-chloric, quartz- seresic, chloritic schist are also existed with an admixture of carbonate with thick layers and lenses of dolomitize marble, dolomite and rare beds of chloritized calcareous-quartz.
2. Cretaceous: This rock type forms bands of sublatitudal. Lower Cretaceous deposits are spread in external parts. This rock type largely composed of carbonate rock, less abundant conglomerate, gravels and sand stone.
3. Eocene: This basal unit of tuff- conglomerate lies completely at the lower part of the complex. These are overlain by tuff and lavas of trachyandesitic and andesitic composition, with intercalation of trachyandesite- basalt and lime stone. The section is crowned by fine- fragment of tuff and tuff- mudstone.
4. Dykes: the oldest and the most abundant Dykes are porphyry granite, aplitic granite, microgranosyenite, syenite and lamprophyre. The younger ones are porphyry granodiorite and porphyry diorite.
5. Plutonic rocks: these rocks are very abundant and most of them are acidic. Linear ultra mafic structures are observed in this area. Plutonic units are divided into different parts: Diorite-Manzanite, Manzanite-Quartz Manzanite, Porphyry Alkaline, Graniteporphyry, Quartz Syenite.
6. Quaternary: these sediments are widespread in all over the studied area. Genetically, they are subdivided into alluvial- proluviall- and eolian sediments.
The probable ore types which is outcropped in this area are classified as the following table; The objects to be discussed here are the copper slag. The primary aim of this study was the characterization of materials and the methods of smelting. The objects which have been found here are mostly slag as well as ores. The slag shows the structure of casting slag and also remains from the smelting furnace. The materials are characterized by means of XRD-XRF and Pol-Microscopy methods.

Conclusion
The slag contains high amount of Copper oxide, hydroxide and carbonate and silicate and some amount of MgO or MnO complexes. The main silicate appeared here is Fayalite and pyroxene which has been existed in the matrix of slag. The main paragenesis is chalcocite-chalcopyrite-covellite. copper was smelted at the high oxygen fugacity; approximately about 10-7 atm. Indeed, the furnaces heated with charcoal and charcoal observed also in the macroscopic texture of slag.

References
- Alipour, K. Hushmandzadeh, A. (1997). History of Geology and Mining in Iran. Ministry of Mine and metals,  Geological Survey of Iran. Tehran.
- Eckert, H. E. (1974). Eisen Gewinnung bei den Senfo in Westafrika. Aus Eisen  Archäologie, Eisenerzbergbau und Verhüttung vor 2000 Jahren in der VR Polen. Deutsches Bergbau Museum, Bochum.
- Emami, M. (2006). Phase Transitions Induced by Solid Solution in the Pyroxene- Rich Ancient Copper Slags from Toroud, Iran. 36th international symposium on archaeometry (ISA 2006), Quebeck, Canada.
- Emami, M. (2014). “TOROUD”, The Late Motion for As-Sb Bearing Cu Production from 2nd Millennium B.C. in Iran: An Archaeometallurgical Approach, Mediterranean Archaeology and Archaeometry, Vol. 14, No 2, pp.185-204.
- Hauptmann, A. (1985). 5000 Jahre Kupfer in Oman.  die Entwicklung der Kupfermetallurgie vom 3.  Jahrtausend bis zur Neuzeit. Der Anschnitt, Beiheft 4. Bochum.
- Hezarkhani, Z. & Keesmann, I. (1995). Archäometallurgische Untersuchungen zur Buntmetallurgie in Zentraliran (Poscht-e-Badam – Sagand). Forschungsbericht des Deutschen Bergbau Museum, Bochum. S. 101.
- Keesmann, I., Kronz, A. & Meyer, K.E. (1998). “Archäometallurgische Untersuchungen auf der Iberische Halbinsel–Ergebnisse eine Geländebegehung in Umland des hispo-römischen Munizipiums Munigua (Castillo de Muelva, Prov. Sevilla)”. Hamburg S. 629-644.
- Keesmann, I. (1993). Montanarchäologie in Europa". Bericht zum Internationalen Kolloquium “Frühe Erzgewinnung und Verhüttung in Europa”. Veröff. Römisch -  Germanische Zentral Museum, Mainz.
- Keesmann, I., & Moreno Onorato, A. (1999). “Naturwissenschaftliche Untersuchungen zur früher Technologie von Kupfer und Kupfer-Arsen-Bronze”.  Der Anschnitt, Beiheft 9, S. 317-333.
- Loschiavo, F. (1989). “Early Metallurgy in Sardinien”.  Der Anschnitt, Beiheft 7. S. 211-227.
- Ribbe, P. H. (1976). Oxide Mineralogy. Mineralogical Society of America. Washington D.C.
- Ribbe, P. H. (1982). Sulfide Mineralogy. Fourth printing, Washington D.C.
- Stosgalle, S., Maliotis, G.,  & Gale, N. (1998). “Preliminary survey of the Cypriot slag heaps and their contribution to the reconstruction of copper production on Cyprus”. Der Anschnitt, Beiheft 8. S. 235-262.
- Schimada, I. & Merkel, J.F. (1991). “Copper-Alloy Metallurgy in Ancient Peru”. Journal of Scientific-American, vol 3, pp. 121-134.
 

Amin Allah Kamali, Mohammad Hossein Azizi Kharanaghi, Syed Iraj Beheshti, Ali Aarab,
year 9, Issue 32 (8-2025)
Abstract

Abstract
The slag sites under study are located in Khatam County, Yazd Province. In the archaeological surveys of Khatam County in 1400 AH, twelve metal smelting sites were identified through abundant metallic slag, and each of these sites was sampled. Petrographic analysis revealed that the predominant slag is iron, with only one instance of copper slag. The sites where metal smelting occurred, attributed to historical and Islamic periods based on pottery, exhibited evidence of iron smelting and its compounds in eleven samples. These samples contain metallic minerals such as wustite, marcasite, hematite, and magnetite. Marcasite and wustite minerals are related to smelting furnace processes and are products of mineral substances. It appears that in some mines in the region, magnetite and hematite are the predominant minerals, while in others, hematite is the predominant mineral, with a smaller amount of magnetite, which is evident in these primary minerals within the slag. Another sample related to copper slag exhibited small vesicular structures and limited copper ore minerals (chalcopyrite, digenite, and metallic copper) within the slag matrix. Alongside these primary minerals, there is a flow-like green glassy component indicating high furnace heat. The analytical results show that the MgO content in the samples is less than the amount of lime. Therefore, the limestone in this area is mainly ordinary limestone and not dolomite. Chemical analysis revealed that metal workers in this area were more successful at producing sponge iron.
Keywords: Archaeological Survey, Slag, Iron, Ancient Mining, Khatam.

Introduction
Iran has long been recognized as a center for mining and metal smelting. Archaeological evidence indicates that northern and central Iran are among the oldest centers of metallurgy in the world. The presence of rich mineral reserves in Iran, among other factors, has influenced the growth of mining and metalworking in this region (Momenzadeh, 2005). Due to the existence of various metal ores and advanced cultures in Iran, this area can be identified as one of the main hubs of technological innovation in the field of ancient mining and metalworking. Khatam County, located in the southern part of Yazd Province, holds particular significance in the realm of iron slag. One of the earliest efforts to produce steel worldwide took place in this region (Alipour et al., 2021). Considering the evidence of steel production in this area, it is essential (Alipour, 2017) to understand the role Khatam played in iron production during the Islamic and Sassanian periods. To investigate this matter, 12 sites in Khatam County were selected for studying iron slag. The main objective of this research includes petrographic and geochemical analysis of the slag to identify the type of extracted metal(s) and the extraction process and production of metal(s) at these sites. Additionally, the provision of necessary minerals for mining in this area is also under scrutiny. Historical and field research methods were employed for this study, involving the collection of data and archaeological investigations; field studies, such as topographic mapping, photography, identification of sites and metal smelting furnaces; and examination of samples using polarizing microscopes and XRF devices. This research has addressed primary inquiries related to the type of metals in slag, the mining process, and metal production at Khatam’s iron slag sites. Overall, Khatam County held significant importance in the production of metals during ancient and Islamic times. This region is recognized as one of the ancient mining and metalworking centers, and further research into the history and mining processes in this area could provide additional insights into the history of metalworking in Iran.

Discussion
Based on XRF chemical analyses of the slag, the results indicate that the majority of the mineral content in these slags consists of iron ore, with only one case showing the presence of copper. The CaO concentrations in these slags range from 3.59 to 28.41%, and an increase in CaO leads to the production of calcium-rich olivine. The type of slag (flow, permeable, massive, or furnace bottom) significantly impacts the results of chemical analysis and the ratio of oxides of the main elements (metallic oxides and silica). Additionally, the high amount of CaO facilitates the formation of a calcium-rich silicate phase. Petrographic microscopy studies confirm these findings, revealing observable olivine phases and primary silicate phases with metallic iron minerals such as magnetite and hematite. Due to the silica content, the addition of limestone to the smelting process increases the amount of duplex iron (Fe3O4). Consequently, silica stabilizes triplex iron oxide (hematite), while limestone stabilizes spinel iron oxide (magnetite). Moreover, microscopic examinations primarily reveal metallic minerals such as magnetite and metallic iron. Furthermore, sponge iron, like many other ancient civilizations in the region under study, was produced. The production of this type of iron requires less technical knowledge than other types of iron (Abbasnejad, 2009).
Surveying the region revealed that plants such as pistachios and wild almond produce high-quality charcoal. Since blacksmiths have no idea about using additional limestone in the furnace, the smelted slags were highly adhesive, leading to significant iron loss. The use of limestone in iron removal creates slags with fine properties that are easily separated from the iron (Abbasnejad, 2009). A good slag resulting from smelting should contain 30 to 40% limestone. Tests conducted on iron ore in this region show limestone percentages ranging from 3.59 to 28.41%. The slag analysis results also indicate a small amount of limestone, averaging approximately 11.38%. The deficiency of these two elements in slag, as they play crucial roles in reducing smelting heat and separating iron from slag, can indicate high iron levels and the inadequacy of slag (adhesiveness, viscosity, high density), resulting in low-quality sponge iron. The percentage of Fe2O3 ranges from 23.20 to 74.25%, and the percentage of Al2O3 ranges from 0.003 to 0.94%. The percentage of MgO in the tested slags is less than 0.003%. According to the mineral analysis, the most important iron minerals in this region include hematite (Fe2O3) and magnetite (Fe3O4). Due to technical flaws in these furnaces, sponge iron contains impurities such as silica, phosphorus, aluminum oxide, manganese oxide, and other metallic oxides, as confirmed by various tests conducted on ore and slag.

Conclusion
Eleven samples from the metal smelting site showed evidence of iron smelting and its compounds. In these samples, metallic ores such as wustite, marcasite, hematite, and magnetite are observed. Marcasite and wustite ores are related to smelting furnace processes and are mineral byproducts. It seems that in some mines in the region, magnetite and hematite are predominant, while in others, hematite is less prevalent, and magnetite dominates. Additionally, in the sample related to copper smelting slag, small and limited vesicles of copper ores (covellite, digenite, and metallic copper) are observed alongside a part of the green glassy matrix, indicating high furnace heat. This primary mineral evidence is observed in the slags. Considering the changes in the calcium oxide (CaO) concentration, it can be inferred that this substance was added during smelting operations to aid in smelting and reduce the temperature of the furnace materials. The microscopic results of some slags reveal primary minerals, mostly hematite and magnetite metallic ores, indicating a magmatic origin for the utilized minerals. The percentages of silica (SiO2), magnesium, and aluminum in these slags are relatively low. Analyses of these slags and iron stones from this region show that a deficiency of CaO and SiO2 leads to iron loss in the slag while increasing the iron content within it.
Based on this research, it is likely that iron ore was extracted from mines near the site and was subsequently transported to this location. Given the presence of iron mines at distances of 8, 10, and 15 kilometers from these sites, these mines are likely the source of these slags. Regarding the archaeology of the region, historical references indicate that the area held significance and prominence in various historical periods, particularly during historical and Islamic eras. However, due to insufficient information about the archaeology of the region and the lack of precise dating of these sites, accurate dating of these sites is unfeasible.


Page 1 from 1