Copper sulphosalts in early metallurgy (2600–1900 BC) – chemical-mineralogical investigation of artefacts from southern Poland

Abstract

1 Pol ish Acad emy of Sci ences, In sti tute of Ar chae ol ogy and Eth nol ogy, al. Solidarnooeci 105, 00-140 Warszawa, Po land 2 Uni ver sity of War saw, Fac ulty of Ge ol ogy, ¯wirki i Wigury 93, 02-089 Warszawa, Po land 3 War saw Uni ver sity of Tech nol ogy, Fac ulty of Chem is try, Noakowskiego 3, 00-664 Warszawa, Poland 4 War saw Uni ver sity of Tech nol ogy, Fac ulty of Ma te rial Sci ence and En gi neer ing, Wo³oska 141, 02-507 Warszawa, Po land 5 Pol ish Acad emy of Sci ences, In sti tute of Ar chae ol ogy and Eth nol ogy, S³awkowska 17, 31-016 Kraków, Po land Bugaj, U., Nejbert, K., Ilnicki, S., Wieciñski, P., Onyszczuk, T., Garbacz, H., W³odarczak, P., 2019. Cop per sulphosalts in early met al lurgy (2600-1900 BC) -chem i cal-min er al og i cal in ves ti ga tion of artefacts from south ern Po land. Geo log i cal Quar terly, 63 (2): 302-318, doi: 10.7306/gq.1473We de scribe a meth od ol ogy of in ves ti ga tion of both Cu metal ma trix and its min eral in clu sions that aims at in creas ing the effec tive ness of iden ti fy ing the type of ore used in metal pro duc tion. We point to sulphosalt ores as the main source of metal for the Fi nal Neo lithic/Early Bronze Age cop per artefacts from south ern Po land. The in clu sions, rich in Ag, As, Sb and Sn, doc ument the type of ore, re gard less of the met al lur gi cal pro cess lead ing to de ple tion of As and Sb. The cop per metal should contain nei ther Sb nor As, hence both of these el e ments, if orig i nally pres ent in ore, can be pre served only in in clu sions. The con cen tra tions of Ag, Sb, As and Sn in the artefacts in ves ti gated, the pres ence of in clu sions, and their chem i cal com po si tion, are the key in di ca tors for the de ter mi na tion of the min er al og i cal com po si tion of the orig i nal ores. Given the high con cen trations of Sb, As and Ag in the Cu metal and min er al ogy of the in clu sions, the ore must have con tained vary ing pro por tions of Ag-bear ing tetrahedrite (Cu,Fe) 12 Sb 4 S 13 and ten nan tite (Cu,Fe) 12 As 4 S 13 . Min er al og i cal com po si tions of the cop per ores in dicate the de pos its in Slovakia (Špania Dol ina) as the source of metal for the artefacts in ves ti gated. The re sults of Pb and Cu iso to pic anal y ses car ried out for this study sup port those con clu sions.

Antimony and Nickel Impurities in Blue and Green Copper Pigments

“…Three ablation lines were selected on the surface of the sample (E = 5.0 mJ; φ = 100 µm; SR = 50 µm/s; 20Hz). Transient signals were recorded and evaluated for subsequent elemental quantification for the selected isotopes ( 23 S, 35 Cl, 39 K, 43 Ca, 45 Sc, 49 Ti, 51 V, 53 Cr, 55 Mn, 57 Fe, 59 Co, 61 Ni, 65 Cu, 66 Zn, 71 Ga, 75 As, 85 The unpolarized µRaman spectra of minerals were collected in back-scattered geometry with a Horiba Labram HR (Horiba, Ltd., Kyoto, Japan) spectrometer integrated with an Olympus BX 40 confocal microscope. The parameters of Raman measurements were as follows: estimated analytical spot size of ~1-2 µm, 532 nm line of a solid-state Nd-YAG laser (10 mW), 1800 g/mm grating, microscope objective 100×, acquisition time of 20, and accumulation of 2 scans.…”

Chemical composition of small fragments of metals from Castillo de Huarmey (Peru): Chemical analysis in the micro‐area using FE‐SEM‐EDS, FE‐EMPA and XRD

“…2018; Bugaj et al . 2019). All analyses were performed in laboratories at the Faculty of Geology, University of Warsaw.…”

“…The chemical composition of inclusions found in the tested material was also determined using FE-EMPA. This method is not yet widely used in archaeological research, but is gaining in popularity, and it is slowly becoming increasingly appreciated (Pop et al 2011;Doménech-Carbó et al 2018;Bugaj et al 2019). All analyses were performed in laboratories at the Faculty of Geology, University of Warsaw.…”

“…2018; Bugaj et al . 2019) are applied. These are the first analyses of this type carried out on artefacts from this unique archaeological site.…”

“…Additionally, an attempt is made to determine how the studied materials were smelted, especially in comparison with artefacts from other Middle Horizon cultures. For this purpose, scanning electron microscope with energy-dispersive X-ray spectroscopy and field emission (FE-SEM-EDS) (Balta et al 2009;He et al 2011), X-ray diffraction (XRD) (Cura et al 2007) and an electron microprobe analyser with field emission (FE-EMPA) (Frame 2010;Orfanou and Rehren 2015;Doménech-Carbó et al 2018;Bugaj et al 2019) are applied. These are the first analyses of this type carried out on artefacts from this unique archaeological site.…”