8 NS RECHERCHES ARCHÉOLOGIQUES • L’INSTITUT D’ARCHÉOLOGIE ’ DE L UNIVERSITÉ JAGELLONNE DE CRACOVIE 8 RECHERCHES ARCHÉOLOGIQUES NOUVELLE SERIE L’INSTITUT D’ARCHÉOLOGIE DE L’UNIVERSITÉ JAGELLONNE DE CRACOVIE RECHERCHES ARCHÉOLOGIQUES NOUVELLE SERIE 8 KRAKÓW 2016 © Copyright by Institute of Archaeology of the Jagiellonian University, Kraków 2016 RÉDACTEUR EN CHEF Marek Nowak SÉCRETAIRE DE LA RÉDACTION Marcin S. Przybyła COMITÉ DE RÉDACTION Jan Chochorowski, Krzysztof Ciałowicz, Ulla Lund Hansen, Renata Madyda-Legutko, Vjacheslav I. Molodin, Ewdoksia Papuci-Władyka, Jacek Poleski, Pál Raczky, Paweł Valde-Nowak RÉDACTEURS DU SUJET Wojciech Blajer, Janusz Ostrowski, Krzysztof Sobczyk, Joachim Śliwa COMITÉ DE LECTURE Ján Beljak, Noémi Beljak Pažinová, Tomasz Bochnak, Klára Fischl, Helle W. Horsnæs, Sławomir Kadrow, Mariusz Mielczarek, Martin Schönfelder, Zsuzsanna Siklosi, Marián Soják, Anna Zakościelna ÉDITEURS DE LANGUE Piotr Godlewski, Aeddan Shaw MAQUETTE DE COUVERTURE Wydawnictwo i Pracownia Archeologiczna PROFIL-ARCHEO Magdalena Dzięgielewska MISE EN PAGES Wydawnictwo i Pracownia Archeologiczna PROFIL-ARCHEO Magdalena Dzięgielewska EN COUVERTURE Schéma d’analyse de réseau de 65 sites à partir de la in de l’âge du Bronze moyen (principalement de 1700 à 1400 avant J.-C.). L’ épaisseur du lien est proportionnelle à la valeur du coeficient de Pearson ADRESSE DE LA RÉDACTION Instytut Archeologii Uniwersytetu Jagiellońskiego, ul. Gołębia 11, PL 31-007 Kraków mniauj@interia.pl; mszprzybyla@gmail.com www.farkha.nazwa.pl/RechACrac/ www.archeo.uj.edu.pl/RechACrac/ La version originale des Recherches Archéologique Nouvelle Serie est la version papier “Recherches Archéologiques Nouvelle Serie” est régulièrement sur la liste dans The Central European Journal of Social Sciences and Humanities ISSN 0137-3285 Publikacja inansowana przez Uniwersytet Jagielloński Cette publication est inancée par l'Université Jagellonne CONTENU ÉTUDES Stanisław Wilk: New data about chronology of the impact of the Hunyadihalom-Lažňany horizon on Younger Danubian cultures north of the Carpathian Mountains Stanisław Wilk, Aldona Garbacz-Klempka: Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice, Świętokrzyskie Province, Poland. Typological and physical metallurgy characteristic Marcin S. Przybyła: Middle Bronze Age social networks in the Carpathian Basin Katarzyna Czarnecka: Late La Tène scabbards with openwork decorative ittings Jarosław Bodzek, Jan Bulas, Michał Grygiel, Jacek Pikulski: Roman republican coins found at Zagórzyce, Kazimierza Wielka district, Świętokrzyskie Province 7 29 47 85 143 R A P P O RT S Jan Bulas, Michał Link-Lenczowski, Magdalena Okońska: The Roman Period pottery kiln from Kraków-Górka Narodowa, site no. 6 Michał Wojenka, Jarosław Wilczyński, Albert Zastawny: Archaeological excavations in Żarska Cave in Żary, Kraków district, 2012–2015: an interim report 173 185 Recherches Archéologiques NS 8, 2016, 29–46 ISSN 0137 – 3285 Stanisław Wilk1, Aldona Garbacz-Klempka2 Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice, Świętokrzyskie Province, Poland. Typological and physical metallurgy characteristic Abstract: This article presents a typological and physical metallurgy analysis of copper artifacts found in child grave (no 7) at the Lublin-Volhynian culture cemetery in Książnice (Lesser Poland). The burial, dating to approx. 4050–3940 BC, contains a rich set of copper jewellery: a massive earring, small earring, bracelet - made of copper wire, and two beads made of a rolled piece of metal sheet. As part of metallographic analysis of metal inds from grave 7, site 2 in Książnice, quantitative and qualitative analyses were conducted, regarding chemistry and microstructure of all the ive artifacts. In the artifacts tested, there were identiied the elements signiicant from the perspective of raw material origin and smelting technology: arsenic, antimony, silver, tin, zinc, lead, bismuth, cobalt, nickel and iron. The highest total content of impurities was noted for the bracelet. Against the background of other elements, the arsenic content stands out here and it is 2.1%, and lead 0.26%. For the remaining artifacts, the arsenic content was 0÷0,24%, and lead 0÷0,039%. Antimony (0.098%) and zinc (0.15%) was only recorded for the one of the bead. Also, the highest content of silver (0.05%) was established in this case. In the remaining ornaments, the silver content was below 0.02%. Based on the X-ray luorescent spectroscopy results, chemical proiles were established for the individual, and they were ascribed to raw material groups according to R. Krause: 1) pure copper, 2) arsenic copper and 3) antimony copper (Krause 2003: 90–91, Abb. 40–41). The presented inventory of copper artifacts from grave 7, having many analogies in the Carpathian Basin and the areas to the north and east of the Carpathians, conirms the thesis about wide, trans-Carpathian contacts of the group which was using the necropolis in Książnice at the turn of 5th and 4th millennium BC. Keywords: copper jewellery, metallurgy analysis, graves, Lublin-Volhynian culture, Lesser Poland, archaeometallurgy, X-ray luorescence (XRF) 1. Introduction12 This article presents a typological and physical metallurgy analysis of copper artifacts found in grave 7 at the Lublin-Volhynian culture cemetery in Książnice, Świętokrzyskie Province. Institute of Archaeology, Jagiellonian University; 11 Gołebia St., 31-007 Kraków, Poland; archeowolf@ wp.pl (corresponding author) 2 AGH University of Science and Technology, Faculty of Foundry Engineering, The Historical Layers Research Centre at AGH UST; 23 Reymonta St., 30-059 Kraków, Poland; agarbacz@agh.edu.pl 1 30 Stanisław Wilk, Aldona Garbacz-Klempka Grave 7, explored in August 2008, belonged to a child (girl) at the age of infans II (9–10 years old), deposited in a contracted position, on the left side, with the cranium to the south (Wilk 2015, ig. 5). The burial pit was orientated on the NE-SW axis. To the south and to the west, it has been partially destroyed by an underground trench which constitutes part of a water supply network. The body was equipped with a rich set of copper jewellery (Table I). Under the skull, there was a massive earring made of wire (Fig. 1: A; Wilk 2015, igs 8: A, B; 9: C). At the height of her chest, there was a bead made of a rolled piece of metal sheet (Fig. 1: C; Wilk 2015, igs 8: D; 9: E). Another such bead was discovered during the search through the ill of the water supply trench (Fig. 1: D; Wilk 2015, ig. 9: D). Additionally, on the left humerus, some greenish discolouration was observed – possibly, a trace left by a bracelet (Wilk 2015, ig. 8: A), which was discovered – together with a small circular earring (Fig. 1: B, E; Wilk 2015, ig. 9: A, B)– at the height of the ceiling of the burial pit, in a mole hill, about 30 cm to the east of the pit (Wilk 2015, ig. 4: B). The location of these artifacts – close to the edge of the grave, at the level where the top of the cranium is outlined – indicates that they could have been elements of the burial inventory. 2. Comparative analysis of the artifacts The earrings belong to the most frequently encountered pieces of jewellery in the Lublin-Volhynian culture. We know 21 such artifacts from 14 graves (Zakościelna 2010, 146, table 38; Wilk 2014, 232). They occur individually or in pairs, almost exclusively in female graves, and they can consist of one or multiple coils. One-coil earrings can be divided into two size categories: small ones (up to 50 mm in diameter) and big ones (51–85 mm in diameter). The earrings from grave 7 represent both of the above types. The closest analogy for the Ks/w/4/08 specimen (Fig. 1: E) are the artifacts from grave 390 found at site Grodzisko II in Złota (Sałacińska, Zakościelna 2007, ig. 12:4,5), as well as one of the pair of earrings from grave 1 from site 4 in Gródek on the Bug river (Gąssowski 1954, 84).In the Tiszapolgár culture, a similar earring was found in grave 2 at site Deszk B (Bognár-Kutzián1972, ig. XXXIII:9). While, an artifact of a very similar shape, described as a ring, was found on the phalanges of a child’s hand in grave 9 at site Tiszapolgár-Basatanya (Bognár-Kutzián 1963, pl. XIII:3). In the Cucuteni culture, a similar artifact, described as “an open ring”, occurred at site Târpeşti (Mareş 2012, pl. 42: 2527). While, in the hoard in the village of Brad, two, slightly smaller, specimens were discovered. They were described as elements of a necklace (Ursachi 2012, ig. 33:1). Analogies for the Ks/w/18/08 specimen (Fig. 1: A) were found in graves 2 and 8 at site 2 in Książnice. In grave 2, a massive earring was discovered. It was 72 mm in diameter and it was made of a wire 2 to 4 mm thick, and it weighed 13.1 g (Wilk 2004, ig. 11:2). While, the earring from grave 8, with the diameter of 81 mm and made of the wire 1.7–2.9 mm thick, weighed 8.6 g (Wilk 2014, ig. 11:G). The above described artifacts from the necropolis in Książnice comprise an assembly of the biggest and most massive earrings in the entire Eneolithic in Central Europe. In the Lublin-Volhynian culture, no other earrings can be classiied within the same metric category (51–85 mm in diameter). The biggest are the remaining two ornaments in the shape of a single coil of a lat-convex sheet of metal, measuring approximately 40–44 mm and 49–50 mm (Zakościelna 2010, pl. LXXIX:3,4) from grave 2 in Żuków, and two earrings from a single coil of copper wire, measuring 45–46 and 47 mm, from a grave at site 7 in Garbatówka Kolonia (Polańska 1999, 10, ig. 3:10,12). However, a good context for these inds is lacking, as it was a chance discovery in the grave in which no skeleton had been preserved. Owing to their metric similarity to the ornaments found below the chest of the body buried in grave 8 in Książnice (Wilk 2014, table I, igs 6; 10:F,G), their interpretation as earrings is not so unequivocal. Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 31 Fig. 1. Copper jewellery from the Lublin-Volhynian grave 7 at site 2 in Książnice (photo by S. Wilk) The single-coil copper wire bracelet, Ks/w/3/08 (Fig. 1: B), has analogies among the inds of the Lublin-Volhynian culture from grave 101 in Grodzisko II in Złota (Sałacińska, Zakościelna 2007, ig. 21:17/XIX) and in grave 1 from site 3 in Stefankowice Kolonia (Kokowski, Koman 1985, pl. 332:2). In Wyciąże-Złotniki group, two copper wire bracelets, one of which consisted of one and a half coils, and the other one made as a single coil of wire with its ends overlapping each other, were found in grave I at site 7, 58, 65 in Kraków Nowa Huta-Cło (Kaczanowska, Tunia 2009, ig. 87:2,3). We interpret the ind as a bracelet rather than as a straightened earring, because on the left humerus of the skeleton from grave 7 we can observe some greenish discolouration, suggesting the presence of a bracelet. Also, there are analogies of the same shape found in situ, for example in grave 501 at the cemetery of Durankulak (Todorova 2002, pl. 79:6). Similar bracelet was discovered in feature 461 on the Balaton Lasinja culture settlement at Site 1 in Kaposvár in southwest of Hungary (Somogyi 2002, 342, 351, abb. 3:1). More broadly, the occurrence of earrings and bracelets made of copper wire in the Eneolithic of Central Europe is discussed in the article about grave 8 from Książnice (Wilk 2014, 221–227, 232–234, see the relevant literature there). Beads made of copper sheets are widespread in the Eneolithic societies of the Carpathian Basin and the territories located north and east of the Carpathians. They are divided into tubular beads (cylindrical), made of rolled sheets of copper, spirally coiled beads made of narrow strips of copper (the so-called salta leone, and by some authors also classiied as tubular ones (Mareş 2012, 455), and ring-shaped beads resembling thin slices, made of a slightly thicker material. To the oldest inds of tubular beads belong those found on late Neolithic sites on the Great Hungarian Plain, including those from the Polgár-Csőszhalom tell. They were found there in the layers dated to about 4700–4450 BC BC (Siklósi et al. 2015, 88, ig. 4; pl. 1). A slightly different variant of beads of copper sheets (they are made of thicker sheets, and they are a less regular in shape) were found on Lengyel culture cemeteries in southern Transdanubia, including Mőrágy Tűzkődomb (Zalai-Gaál 1996, ig. 6).In graves 12, 13, 24 and 39 at the cemetery of the Tiszapolgár culture in Tiszapolgár-Basatanya, single cylindrical beads of copper sheets Stanisław Wilk, Aldona Garbacz-Klempka 32 dimensiOns in millimeters (length, width, diameter, thickness) descriptiOn Of the leveling in meters 35 199.91 At the height of the ceiling of the Small circular ear- 22×20 Ø2 burial pit, in a mole hill, about 30 ring Ø 1,5 cm to the east of the pit 1,75 Fig. 1: E 3 Ks/w/7/08 45–55 199.95 At chest height Bead made of a rolled 12 piece of metal sheet Ø 8×7? thickness of (in three pieces) the sheet 1 mm 1,03 Fig. 1: C 4 Ks/w/18/08 45–55 199.84 Under the skull A massive wire ear- 87×86 Ø4 ring Ø2 21,15 Fig. 1: A 5 Ks/w/21/08 55–60 In the water supply trench A bead made of a 12 rolled piece of me- Ø 7×6 thickness of tal sheet the sheet 1 mm 0,41 Fig. 1: D the figure Ks/w/4/08 grams 2 number Of Fig. 1: B weight in 4,79 subject At the height of the ceiling of the Single-coil copper 75×61 Ø3 burial pit, in a mole hill, about wire bracelet Ø2 30 cm to the east of the pit grave 35 199.91 lOcatiOn in the Ks/w/3/08 abOve sea level inventOry 1 number Ordinal number depth in centimeters/ Table I. Characteristic of the copper jewellery from grave 7 at site 2 in Książnice were found; while, in grave 28, two more specimens of such beads were found (Bognár-Kutzián 1963, pls XX: 3; XXII: 2; XXXII: 1; XLVII: 5; XIII:6,7). Moreover, cylindrical beads of copper sheets formed part of two necklaces from Decea Mureşului (Mareş 2002, pl. 60:9, 11). 377 beads made of coiled copper sheets were found in the hoard from Karbuna in Moldova, dated to the A2 period of the Trypolye culture (Sergeev 1963). While, nine barrel-shaped beads made of copper sheets were found in the hoard from Horodnica (Sulimirski 1961, pl. 1), which contained, among other inds, a unique copper diadem decorated with repoussé indentations, whose only analogy is the bracelet from grave 2 in Książnice (Wilk 2004, ig. 11:4,5). On the territories occupied by the Cucuteni culture, tubular beads were found – among other sites – at Traian and Târpeşti (Mareş 2012, pl. 43), as well as in the hoard from the site of Brad (Ursachi 2012, igs 28: 2; 35:4). It is interesting that they almost hardly ever occur in inventories of the cultures of Hamangia and Varna, which are very rich in other copper ornaments (Pernicka et al. 1997). The specimens from grave 7 on site 2 in Książnice differ from other similar artifacts by their elongated shape and relatively large sizes (12 mm in length, and 6–8 mm in diameter). Finds, whose shape resembles that of the beads found in grave 7 (Fig. 1: C, D) are known from features 205 and 288 at the site of Třebestovice 1 (Čtverák, Rulf 1989, ig. 6, 7) and from grave 27 in Jordanów (Seger 1906, pl. VIII:5), which belongs to the Jordanów Śląski culture, as well as from graves LIV, LXX and LXXI from Osłonki (Grygiel 2008, igs 814; 833; 835), representing the Brześć-Kujawski culture. A slightly longer bead of copper sheet was found in feature 11 on site 6 in Kopydłowo (Marciniak et al. 2015, 40, ig. 17). In the Wyciąże-Złotniki group, “a small tubular copper bead”, 9 mm in length, was found in grave I at site 7, 58, 65 in Kraków Nowa Huta-Cło (Kaczanowska 2009, 84; Kaczanowska, Tunia 2009, 267, ig. 87:4). Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 33 However, the overwhelming majority of beads made of copper sheets from the territories situated north of the Carpathians are spirally coiled, or much shorter than the discussed beads. Most often, such beads formed elements of rich necklaces (chokers) made of copper plates, and sometimes they occurred as elements of belts. In the Lublin-Volhynian culture, spirally coiled copper beads occurred only in the grave at site 8 in Mikulin (personal communication, courtesy of Anna Zakościelna). On cemeteries of the Jordanów-Śląski culture, in Jordanów and Domasław, there were numerous tubular and spirally coiled (salta leone) beads (Seger 1906, pl. VII:4, ig. 23; Mozgała, Murzyński 2012, 423, ig. 4:2; Gediga et al. 2012, igs 3: 6; 6:7). Similarly, in graves of the Brześć-Kujawski culture, numerous spirally coiled, small tubular and ring-shaped (resembling thin slices) beads were found, which once constituted elements of chokers (Jażdżewski 1938; Grygiel 2008). In western Lesser Poland, a single bead made of spirally coiled, narrow copper plate was found in a child’s grave (feature 40) at site 24 in Proszowice (Przybyła 2009). 3. The results of metallographic analyses 3.1. Methodology As part of metallographic analysis of metal inds from grave 7, site 2 in Książnice, quantitative and qualitative analyses were conducted, regarding chemistry and microstructure of all the ive artifacts. Because of unique value of the jewellery group from Książnice, the decision was made to resign from preparing proper metallographic samples, and only non-destructive tests were conducted directly on the objects. The surfaces were prepared for the analysis by partial removal of conservation coatings, with the exception of beads (Ks/w/7/08 and Ks/w/21/08), whose condition did not allow taking this step. Macroscopic observations were performed using a NIKON SMZ 745Z stereoscopic microscope with a Nikon Digital Sight DsFi1 microscopic camera and a Nis-Elements BR picture analysis system. Chemical composition tests were conducted using X-ray luorescence spectrometry (XRF) with an energy dispersive X-ray luorescence spectrometer SPECTRO Midex. The microstructure observations were performed with a scanning electron microscope (SEM) Hitachi S- 3400N, equipped with Energy-Dispersive X-ray Spectrometer (EDS) by ThermoNoran, allowing for phase analysis in microareas. Also, microhardness tests were performed using Vickers method. The tests aimed at describing metallographic and material characteristics of the copper jewellery from grave 7 at site 2 in Książnice. The macro-and microobservations of this material resulted in determining the material structure and allowed for qualitative description of the processes the material was subjected to during the manufacturing stages. The scanning microscopy observations were conducted to describe the structure and chemical composition of individual artifacts. This method also allowed for microstructure evaluation with respect to metallic inclusions, defects and discontinuities as well as non-metallic impurities of the samples. The observations were performed on unetched samples. Among the tests carried out, an important role was played by spectroscopy. The X-ray luorescence spectroscopy method made it possible to prepare the qualitative and quantitative characteristics of chemical composition of the objects. In order to analyze varied surfaces of the samples, the excitation radiation was reduced by using the available apertures. The internal camera facilitated the choice of measurement points and photographic documentation of the research, with the measurement points being marked. In the case of archaeological material, also 34 Stanisław Wilk, Aldona Garbacz-Klempka the observation of objects with respect to their condition including identiication of corrosion products is important. This characteristics makes it possible to choose the best conservation methods and it eficiently protects the objects against further destruction. 3.2. The research results In chemical proiles of the tested artifacts, the highest copper concentration was noted for the objects marked as the earring, code number Ks/w/4/08 (99.8%), the bead Ks/w/21/08 (99.6%), the earring Ks/w/18/08 (99.5%) and the bead Ks/w/7/08 (98.8%). The lowest copper content (97.5%) was found in the bracelet Ks/w/3/08. In the artifacts tested, there were also identiied the elements signiicant from the perspective of raw material origin and smelting technology. Arsenic, antimony, silver, tin, zinc, lead, bismuth, cobalt, nickel and iron belong to this group. Looking from the smelting perspective, they belong to the impurities which remained from the ore composition and they are important markers to identify the origin characteristics of the raw material. The highest total content of impurities was noted for the bracelet Ks/w/3/08. Against the background of other elements, the arsenic content stands out here and it is 2.1%, and lead 0.26%. For the remaining artifacts, the arsenic content was 0÷0,24%, and lead 0÷0,039%. Antimony (0.098%) and zinc (0.15%) was only recorded for the bead Ks/w/7/08. Also, the highest content of silver (0.05%) was established in this case. In the remaining ornaments, the silver content was below 0.02%. The tests did not show any mercury content (Hg<0.0010%), but a raised level of cobalt was established (0.50 – 0.73% Co), which points to the fact that maybe the artifacts were made from remelted copper (Pernicka et al. 1997; Adamczak et al. 2015). This is also conirmed by the oxygen content in copper, assessed on the bases of macroscopic observations and microareas analysis (Rzadkosz 2013; Garbacz-Klempka et al. 2016a). The collation of the chemical composition results of the artifacts from grave 7, expressed in weight percentage, is presented in Table II. In Table III there are quantitative results of the bracelets tests, belonging to the Wyciąże-Złotniki group, graves 2 and 4, from site 5 in Kraków Nowa Huta-Wyciąże, and the grave I, at sites 7, 58 and 65 in Kraków Nowa HutaCło. The tests were performed using the same X-ray luorescence spectroscopy method, as in the case of Książnice (Garbacz-Klempka et al. 2016a); also there are qualitative results of the two bracelets tests, from the grave 101 of the Lublin-Volhynian culture from the site Grodzisko II in Złota, conducted by T. Dziekoński with the help of emission spectroscopy (Dziekoński 1962). The impurities distribution in speciic artifacts is presented graphically in charts (Figs 2; 3) The results of chemical composition with the characteristic elements marked are also shown as X-ray luorescence charts (Fig. 4: A–F). The last chart (Fig. 4: F) lists the results of all the ive artifacts, prepared to show the similarities and differences of the chosen elements concentration, arsenic especially. The difference in content of a given element in the alloy is shown here as the difference in impulse intensity where it is identiied on the chart. The spectra for the successive artifacts are differentiated by colour. The metal artifacts from site 2 at Książnice were subjected to macroscopic tests, which showed varied surface, resulting from prehistorical technology or corrosion processes taking place in favourable conditions where they were deposited (Figs 5; 6). The chosen artifacts (two earrings and a bracelet) were tested by light microscopy and scanning microscopy. The microstructure and corrosion-related impurities were observed on the unetched surfaces, which made the microstructure observation more dificult. The areas observed Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 35 are presented in photographs, in succession for Ks/w/3/08 (Fig. 7: A, B), Ks/w/4/08 (Fig. 7: C, D), and Ks/w/18/08 (Fig. 7: E, F). The earing (Ks/w/4/08), observed at the magniication of 500 and 1500x, shows small but numerous areas taken up by copper oxides (Garbacz-Klempka et al. 2016b) Moreover, in the microstructure, outlines of grain crystallites of pure copper are visible (Fig. 7: D). Similar characteristics is shown by the Ks/w/3/08 bracelet microstructure (Fig. 7: A, B), while the Ks/w/18/08 earring (Fig. 7: E, F) showed numerous and small structure discontinuities observed at the 500 and 700× magniications. The impurities are located at the grain boundaries. Arsenic, present in the earring at the level of 0.24%, got solved in copper, creatingαsolid solution (Garbacz-Klempka et al. 2015). The remaining impurities, like lead and oxygen, are visible as darker elements against the background of homogenous structure (Fig. 7: F). The content identiication of the individual microstructure phases was performed on the basis of X-ray luorescence analysis in microareas. The observed inhomogeneity results from corrosive activity of the material, which results in, among others, the creation of copper(I) oxide [Cu2O] and copper(II) oxide [CuO]. The presence of chloride salts accompanied by a limited amount of oxygen, inluences the creation of copper chlorides (II) [CuCl2] (GarbaczKlempka et al. 2016b). Based on the X-ray luorescent spectroscopy results, chemical proiles were established for the individual, and they were ascribed to raw material groups according to R. Krause (Krause 2003: 90–91, ig. 40– 41). The data is presented in Table IV. Chemical analysis results of the beads marked as Ks/w/21/08 and Ks/w/7/08, because of their high degree of destruction, could be encumbered by an error. It would be required to verify the results by repeating the tests after revealing the metallic core. Comparing them with the remaining analysis results, should be treated qualitatively. The classiication results of the copper ornaments from grave 7 at site 2 in Książnice, conducted within the raw material groups, point to their clear diversiication, because the objects discussed can be ascribed to three copper classes: 1) pure copper, 2) arsenic copper and 3) antimony copper. Fig. 2. Impurities distribution in speciic artifacts (wt%) Stanisław Wilk, Aldona Garbacz-Klempka 36 Fig. 3. Differences in the content of selected chemical elements of artifacts from Książnice, Kraków Nowa Huta-Wyciąże and Kraków Nowa Huta-Cło Similar observations are valid for the artifacts from the Wyciąże-Złotniki group, at site 5 from Kraków Nowa Huta-Wyciąże (MAK_W5-125b-50; MAK_W5-125e-50). The only object that was analysed from grave I of the Wyciąże-Złotniki group, at site 7, 58, 65 in Kraków Nowa HutaCło (MAK/NH:C7/16/50) its the chemical proile of the antimony copper group. Very low accuracy of the chemical analysis of the artifacts from grave 101 at the site Grodzisko II in Złota (0.0X or 0.X) conducted by T. Dziekoński at the beginning of the 1960’s (Dziekoński 1962), makes it impossible to assign these artifacts precisely to the proper raw material groups. The observed differences may suggest that the community of the Lengyel-Polgár group from Lesser Poland (Książnice, Kraków Nowa Huta-Wyciąże, Kraków Nowa Huta-Cło), imported the raw material or the ready artifacts from different sources. This tendency corresponds to the diversiication of the copper objects which were discovered at the sites of Brześć-Kujawski culture in Brześć Kujawski and Osłonki (Grygiel 2008). R. Grygiel holds the opinion that copper and ready artifacts arrived there from the South part of Central Europe (Grygiel 2008, 1877). This is in line with the general direction of this trend, which could be identiied for the historical objects from Książnice, Kraków Nowa Huta-Wyciąże and Kraków Nowa Huta-Cło (Krause 2003, 12). The basis for the chemical characteristics presented here was the content of antimony, arsenic, nickel and silver. An important fact is that for antimony and arsenic in the metallurgical process Table II. Chemical composition of the copper jewellery from grave 7 at site 2 in Książnice with XRF method (wt%) sample fe cO ni cu as nb ag sn sb pb bi ∑ Ks/w/18/08 < 0.025 0.060 0.090 99.5 0.24 < 0.020 < 0.020 < 0.051 < 0.051 0.039 < 0.0010 100 Ks/w/4/08 < 0.025 0.050 0.072 99.8 0.047 < 0.020 < 0.020 < 0.051 < 0.051 < 0.020 < 0.0010 100 Ks/w/3/08 < 0.025 0.053 0.069 97.5 2.1 < 0.020 < 0.020 < 0.051 < 0.051 0.26 0.092 100 Ks/w/21/08 0.16 0.052 0.064 99.6 < 0.00051 0.087 < 0.020 < 0.051 < 0.051 < 0.020 < 0.0010 100 Ks/w/7/08 0.073 0.083 98.8 < 0.00051 0.42 0.050 0.27 0.15 0.098 < 0.020 0.0051 100 Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 37 there are the same conditions preserved for evaporation and absorption into slag, therefore their mutual relationship in the ore deposits and ready-made product stays at the same level. The copper ornaments that were researched contain some impurities and porosity. This results from technology imperfection, which – because of problems connected with removing the redundant elements – caused their arrest in the solution. In the course of the research, against the homogenous copper background, numerous small imperfections were revealed, in the form of irregular precipitates or their clusters. These precipitates are mainly localized at the grain boundaries. Also, some natural admixtures were identiied, present in the ores and products. In the bracelet Ks/w/3/08 silver precipitates were identiied, which occur in copper. The remaining impurities are located in the solution and at the grain boundaries (Garbacz-Klempka et al. 2016b). Table III. Chemical composition of the copper jewellery from: Wyciąże-Złotniki group cemetery at site 5 in Kraków Nowa Huta-Wyciąże, site 7, 58, 65 in Kraków Nowa Huta-Cło (Garbacz-Klempka et al. 2016a, tables 1–3) and cemetery of the Lublin-Volhynian culture at site Grodzisko II in Złota (Dziekoński 1962, 103, table II.1) (wt%) sample fe cO NH:W5/125b/50 0.07 0.05 NH:W5/125e/50 0.04 0.06 ni cu as nb ag sn sb pb ∑ bi 0.080 99.6 0.13 < 0.020 0.020 < 0.051 0.070 < 0.020 0.020 100 0.080 97.4 < 0.00051 < 0.020 0.48 < 0.051 1.4 < 0.020 0.56 100 0.070 99.5 0.030 < 0.020 0.020 < 0.051 0.16 < 0.020 0.050 100 NH:C7/16/50 0.09 0.04 Złota 13/59/10 0.X traces 0.0X X 0.0X Złota 13/59/11 0.X traces 0.0X X 0.0X – 0.X – 0.X – 0.X – 0.X traces 0.X – traces 0.X – Table IV. Classiication of the artifacts from the grave 7 at site 2 in Książnice and similar items from graves at site 5 in Kraków Nowa Huta-Wyciąże, from grave II at site 7, 58, 65 in Kraków Nowa Huta-Cło (Garbacz-Klempka et al. 2016a, tables 1–3), and grave 101 at site Grodzisko II in Złota (Dziekoński 1962, 103, table II.1), within groups of raw materials by R. Krause (Krause 2003, 90–91, igs 40–41) sample as sb ag ni Ks/w/18/08 0.24 ±0.02 < 0.051 N/A < 0.020 N/A 0.090 ±0.003 Ks/w/4/08 0.047 ±0.04 < 0.051 N/A < 0.020 N/A 0.072 ±0.002 Ks/w/3/08 2.1 ±0.4 < 0.051 N/A < 0.020 N/A 0.069 ±0.004 Ks/w/21/08 < 0.00051 N/A < 0.051 N/A < 0.020 N/A 0.064 ±0.001 Ks/w/7/08 < 0.00051 N/A 0.098 0.050 0.083 N/A MAK/W5-125b-50 0.13 ±0.03 0.070 N/A N/A ±0.001 0.020 ±0.006 0.080 ±0.03 MAK/W5-125e-50 < 0.00051 N/A 1.4 MAK/NH:C7/16/50 0.030 ±0.01 0.16 ±0.3 ±0.07 0.48 0.020 ±0.05 ±0.0 0.080 ±0.005 0.070 ±0.01 Złota 13/59/10 0.0X – 0.X – 0.X – 0.0X – Złota 13/59/11 0.0X – 0.X – 0.X – 0.0X – cOpper class Arsenical copper with Ni and Bi Pure copper with slight traces of As and Ni Arsenical copper with Ni and Bi Pure copper with slight traces of As and Ni Antimonical copper Arsenic copper with Ni and Bi Antimonical copper Antimonical copper Not applicable due to a low precision of the measurements Not applicable due to a low precision of the measurements 38 Stanisław Wilk, Aldona Garbacz-Klempka Fig. 4. A – XRF spectra for Ks/w/3/08, determined for copper, arsenic, lead, nickel, and bismuth; B – XRF spectra for Ks/w/4/08, determined for copper, arsenic, and nickel; C – XRF spectra for Ks/w/7/08, determined for copper, tin, antimony, and iron; D – XRF spectra for Ks/w/18/08, determined for copper, arsenic and lead, nickel; E – XRF spectra for Ks/w/21/08, determined for copper and iron; F – summary plot From the perspective of impurities content, four of the artifacts tested showed signiicant similarity, but one of them, the bracelet Ks/w/3/08 (Fig. 4:A) signiicantly differs in respect to the arsenic content (2.1%) and lead (0.26%). There is no antimony in the artifacts under investigation, with the exception of the bead Ks/w/7/08, containing 0.09%Sb. Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 39 Fig. 5. Macroscopic pictures of the copper artifacts from grave 7 at site 2 in Książnice, A – bracelets Ks/w/3/08 (10×), B – bracelets Ks/w/3/08 (50×), C – earring Ks/w/4/08 (10×), D – earring Ks/w/4/08 (50×), E – earring Ks/w/18/08 (10×), F – earring Ks/w/18/08 (50×) (photo by A. Garbacz-Klempka) The chemical characteristics of the earrings and beads from grave 7 in Książnice is similar to the bracelet NH:W5/125b/5, from the site 5 in Kraków Nowa Huta-Wyciąże, however, it clearly differs from the other bracelet (NH:W5/125e/5) in the antimony content (1.37%), silver (0.48%) and bismuth (0.56%). The bracelets from the grave 101 from the site Grodzisko II in Złota, from T. Dziekoński research, had a determined content of antimony, arsenic, silver and nickel (Dziekoński 1962: 40 Stanisław Wilk, Aldona Garbacz-Klempka Fig. 6. Macroscopic pictures of the copper artifacts from grave 7 at site 2 in Książnice. A, B, C – bead Ks/w/21/08 (10×), D – bead Ks/w/21/08 (50×), E – fragment of bead Ks/w/7/08 (10×), F – fragment of bead Ks/w/7/08 (50×) (photo by A. Garbacz-Klempka) 103, table II.1). Low accuracy of the research results from Złota does not allow for comparing them with newer analyses of metallographic analyses. It seems that the ornaments from grave 7 in Książnice were made by hammering from cast. An indirect proof in this case is a signiicant content of copper oxide [Cu2O], identiied in the microscopic tests and in chemical analysis in microareas. The microhardness tests of the chosen artifacts using the Vickers0,02 method showed the values within the 98÷101 mHV0,02 range. Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 41 Fig. 7. BSE pictures of microstructure of the copper artifacts from grave 7 at site 2 in Książnice. A – bracelet Ks/w/3/08 (500×), B – bracelet Ks/w/3/08 (1000×), C – earring Ks/w/4/08 (1500×), D – earring Ks/w/4/08 (500×), E – earring Ks/w/18/08 (500×), F – earring Ks/w/18/08 (500×) (photo by M. Perek-Nowak) In the microscopic tests also a number of extensive changes were noticed in the structure of the sample, which were caused by corrosive conditions connected with long deposition in soil. In the internal pores of the material, oxide and chlorine compounds were present. The localization of these corrosion products was the effect of precipitates segregation at the boundaries of matrix phases. Structure changes are visible at the grain boundaries that points to the intercrystalline corrosion character. 42 Stanisław Wilk, Aldona Garbacz-Klempka 4. Conclusion Based on the data from the location of the copper artifacts and the traces left by some of them (greenish discolouring) on the skeleton, the authors propose a reconstruction of how the jewellery described in the article could have been worn by the girl buried in grave 7 in Książnice (Fig. 8). At irst glance, attention is drawn to the earrings sewn onto a textile or leather band worn on the head. The bigger one, found under the skull, was worn at the height of the left temple. The smaller one, found near the burial pit – at the height of the top of the skull – was worn at the height of the right temple. The bracelet was worn on the left arm, a little above the elbow. The entire jewellery set is complemented with two copper beads strung on a leather thong or a string, hanging on the chest. The presented inventory of copper artifacts from grave 7 conirms the thesis about wide, trans-Carpathian contacts of the group which was using the necropolis in Książnice at the beginning of the 4th millennium BC. Among the 17 burials found so far at the cemetery, as many as 7 are equipped with 23 copper artifacts altogether (bracelets made of wire and copper sheets, wire earrings, wire necklaces, spectacle-shaped pendants, an earring, an axe, a hatchet, a chisel and an awl). It is the biggest collection of such artifacts in Lesser Poland, and one of the biggest in all Poland (Wilk 2014; 2015). The planned further research on the assembly of copper specimens from Książnice will allow us to determine its chemical characteristics, as well as its typological links with related assemblages from Polish and other Central European territories. Acknowledgements Fig. 8. Reconstruction of the way of wearing copper jewellery discovered in grave 7 at site 2 in Książnice (drawn by K. Kielijańska) The physical metallurgy analysis was conducted as part of statutory research program No 11.11.170.318 (Analysis no. 11) at the Faculty of Foundry Engineering at the University of Science and Technology in Kraków (AGH UST) as an interdisciplinary collaboration conducted at the Historical Layers Research Centre, the University of Science and Technology (AGH UST). Eneolithic copper jewellery from grave 7 of the Lublin-Volhynian culture at site 2 in Książnice... 43 Eneolityczna biżuteria miedziana z grobu nr 7 kultury lubelsko-wołyńskiej na stanowisku 2 w Książnicach, woj. świętokrzystkie. Charakterystyka typologiczna i metalurgiczna Niniejszy artykuł prezentuje typologiczną i metaloznawczą analizę zabytków miedzianych znalezionych w grobie dziecięcym (nr 7) na cmentarzysku kultury lubelsko-wołyńskiej w Książnicach (Małopolska). Pochówek, datowany na przełom V i IV tysiąclecia BC (4050–3940 BC), zawierał bogaty zestaw biżuterii miedzianej, na który składały się: duża, masywna zausznica, mała zausznica i bransoleta – wykonane z drutu, oraz dwa paciorki ze zwiniętej blachy miedzianej. W ramach badań metaloznawczych, przeprowadzono ilościowe i jakościowe, analizy chemiczne i mikrostrukturalne wszystkich pięciu zabytków. W badanych zabytkach zidentyikowano pierwiastki, istotne z punktu widzenia pochodzenia surowca i technologii wytopu. Należą do nich: arsen, antymon, srebro, cyna, cynk, ołów, bizmut, kobalt, nikiel i żelazo. Sumarycznie największą zawartość zanieczyszczeń zarejestrowano dla bransolety. Na tle innych pierwiastków wyróżnia się tu arsen, który wynosi 2,1% i ołów 0,26%. Dla pozostałych zabytków stężenie arsenu wynosiło 0÷0,24%, a ołowiu 0÷0,039%. Antymon (0,098%) i cynę (0,15%) zarejestrowano jedynie dla jednego z paciorków. W tym przypadku wykazano również najwyższą zawartość srebra (0,05%). W pozostałych ozdobach stężenie srebra wynosiło poniżej 0,02%. Na podstawie wyników analizy spektroskopii luorescencji rentgenowskiej dokonano ustalenia proili chemicznych analizowanych zabytków oraz zaklasyikowano je do grup surowcowych wg R. Krause: (1) miedzi czystej, (2) miedzi arsenowej oraz (3) miedzi antymonowej (Krause 2003: 90 – 91, ryc. 40 – 41). Zaprezentowany inwentarz zabytków miedzianych z grobu 7, mający liczne analogie w Kotlinie Karpackiej i na terenach położonych na północ i wschód od łuku Karpat, potwierdza tezę o szerokich transkarpackich kontaktach grupy użytkującej nekropolę w Książnicach na przełomie V i IV tysiąclecia BC. References Adamczak K. Garbacz-Klempka A., Kowalski Ł., 2015 Miedziana siekiera z Białego Boru, gm. Grudziądz w świetle nowych analiz, Rocznik Grudziądzki, 23, pp. 169–178. 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