Ancient Metallurgical Iron Slags—Chemical, Powder X-ray Diffraction and Mössbauer Spectroscopic Study

Abstract

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.