{"word_count": 3214, "character_count": 31255}
Introduction        The remains of the ancient town of Kabyle are        situated on the eastern edge of the Zaychi vrah hill, near the big        elbow of Tundzha River, ancient Tonzos River. Map of Bulgaria with the        position of the ancient (respectively modern) settlement of Kabyle is        presented in Figure 1. This settlement, which was one of the most        important Thracian towns, was reorganized by Philip II of Macedonia        becoming a strategic and economic center of that area after his        conquest of South-Eastern Thrace in 342-341 BC (Domaradski and Taneva,        1998; Popov, 2002). Later, in 72 BC Kabyle was conquered by the Roman        general Marcus Lucullus (Velkov, 1990). During the 2nd century AD the Kabyle fortress served as residence        of the Cohors II Lucensium, and in the next        century of the Cohors I Athoitorum. Therefore Kabyle was one of the two main Roman        camps in the province of Thracia (Getov, 2003).        Figure 1: Map of Bulgaria where the position of        the ancient settlement of Kabyle is shown.Figure 1 : Carte de la Bulgarie montrant la localisation        de la ville ancienne de Kabyle.                The gold samples from Kabyle were collected from        the “Big tumulus”, located between the modern village of Kabyle and        the remains of the ancient settlement. The “Big tumulus” was about 8 m        in height and 40-45 m in diameter. In the north-eastern part of the        tumulus a pyre-grave was excavated. The body laid along with his        personal belongings, arms and imported vessels (Stoyanov et al., 2010). The funeral could be dated to the        last third of the 4th century BC. It was assumed        that a military officer of the ancient fortress was buried there        (Stoyanov et al., 2010; 2013).        The arms, found in the grave, consist of a sword,        many iron spear heads and butts intended for long thrusting spears and        javelins. Besides, a bronze horse-bit, which was torn to pieces before        being placed under the funeral pyre, was found (Stoyanov et al., 2010; 2013). After Donder, the horse-bit        belongs to type VІІ (cat. Nr. 74-78, Taf. 9) (Donder, 1980), known        from excavated finds in Olynthus, Thebes, Dodona and Peloponnesus. Two        finds were discovered at Starosel and Dolna Koznitsa in Southern        Thrace (modern South-Eastern Bulgaria). Among the remains of the        funeral pyre many parts of a bronze wreath, cut into pieces and        dispersed all over the fireplace were discovered. The wreath consisted        of gilded bronze leafs and gilded clay beads of different forms, as        well as large quantities of bronze beads (Stoyanov et al., 2013). Among the remains of the funeral        pyre also a twig from a second wreath made of gold, as well as small        thin sheets or other gold artifacts were discovered (Stoyanov et al., 2010; 2013). The gold samples investigated        in the present study come from the above group of finds.        Despite the relatively large number in Bulgaria of        golden artifacts dated to the Thracian period, their analytical study        are very rare (e.g. Kuleff et al., 2009).        Archaeometric investigations of this period are also scarce in other        contries (see e.g. Gondonneau et al., 2001;        Guerra, 2004; 2005, 2008; Guerra and Calligaro, 2007; Iliev, 2006;        Junk and Pernicka, 2003, Schlosser et al.,        2009).        In the present work the analytical data obtained        for the gold finds from the pyre-grave in the “Big tumulus” near        Kabyle are reported. The analyses were carried out by ICP-AES        (inductively coupled plasma-atomic emission spectroscopy) and ICP-MS        (inductively coupled plasma-mass spectrometry). The aim of this        investigation is to identify the gold sources by determination of        large number of elements, including microcomponents. Moreover, due to        the lack of literature data, the results obtained in this study will        be a good base for comparison in future investigations.              Materials and methods                  Materials          For the purpose of this study ten gold samples          were analyzed. Their brief description with respect to the          archaeological context is reported in Table 1 while in Figure 2          pictures of several samples are shown. Since the buried man was          initially cremated on a wooden construction of 4x4 m, made in          several levels, the grave inventory was exposed to very high          temperatures, traceable on some of the gold pieces (Stoyanov et al., 2013).          Table 1. Description of the analyzed gold          samples from the grave-tumulus near the ancient town of          Kabyle.Tableau 1. Description des          échantillons d’or analysés provenant des tumulus situés autour de la          ville ancienne de Kabyle.                                    Nr.              Description                                      3000.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil; weight 0.302              g                                      3001a.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; smelted leaf and fruits from              golden wreath; weight 0.333 g (sample from the              leaf)                                      3001b.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; smelted leaf and fruits from              golden wreath; weight 0.333 g (sample from the              stalk)                                      3002a.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden beads from wreath;              weight 0.422 g (sample from stalk)                                      3002b.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden beads from wreath;              weight 0.422 g (sample from acorn)                                      3003.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil; weight 0.189              g                                      3004.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; smelted fruit from golden              wreath; weight 0.473 g                                      3005.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil; weight 0.402              g                                      3006.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil; weight 0.135              g                                      3007.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil and covered with              golden foil clay bead; weight 0.272 g                                      3008.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil – smelted in the              periphery leaf; weight 0.200 g                                      3009.KAB              Village of Kabyle, Big tumulus,              north-eastern part – funeral-pile; golden foil; weight 0.533              g                                Figure 2: Pictures of some of the analysed          gold-samples.Figure 2 : Photographies de          quelques échantillons d’or étudiés.                                    Methods of analysis          For the determination of the major elements Au,          Ag and Cu ICP-AES (Perkin Elmer’s Optima 7000 DV) was used. The          determination of microcomponents was performed by ICP-MS (Perkin          Elmer SCIEX DRC-e system). The concentrations of the following 27          elements were determined (in mg kg-1): As, Bi,          Cd, Co, Fe, Ga, Hg, In, Ir, Mn, Mo, Ni, Pb, Pd, Pt, Re, Rh, Ru, Sb,          Se, Sn, Te, Ti, U, W, Zn, Zr. The weight of each sample was about 5          mg, samples were digested in 3 mL aqua regia (HNO3:HCl = 1:3) and after that diluted to volume of 20          mL with double deionized water. For ICP-MS determination          additionally 1 mL was diluted to 10 mL with double deionized          water.          The formation of AgCl deposit was carefully          controlled. In this case additionally 1 mL concentrated HCl was          added to the digested samples.          Suprapur chemicals and double deionized water          (MilliQ) were used for preparing all solutions. Working          matrix-matched standard solutions were prepared from single standard          solutions (Merck GmbH, Germany) with initial concentration 1000 mg          mL-1 by appropriate dilution.          The validation of the methods was performed          analyzing the standard reference materials Gold NA-Au-30 and          NA-Au-31 (Aurubis AG, Germany). The results are presented in Table          2.          Table 2: Experimental and certified values          for Ag (%) and other 16 elements (mg kg-1) in          SRMs NA-Au-30 and NA-Au-31.Tableau 2 :          Les valeurs expérimentales et certifiés          pour Ag (%) et 16 autres éléments          (mg kg-1) dans SRM NA-Au-30 et NA-Au-31.                                                  NA-Au-30              NA-Au-31                                       Element              Experimental value              Certifiedvalue              Experimentalvalue              Certified value                                      Ag              1.01±0.07              1.00              5.49±0.44              5.45                                      Cu              102±5              99              1075±68              1062                                      As              41±4              43              108±10              112                                      Bi              10.0±0.6              9              106±7              100                                      Cd              8.0±0.4              10              79±4              82                                      Co              9±2              10              118±20              124                                      Fe              32±2              34              796±76              806                                      Mn              8.0±0.2              7              60±5              62                                      Ni              51±2              48              1100±45              1092                                      Pb              10.0±0.4              9              94±5              90                                      Pd              58±2              55              1103±36              1112                                      Pt              56±1              58              1140±29              1152                                      Sb              10.0±0.5              9              110±6              102                                      Se              12±1              10              125±16              114                                      Sn              47±2              50              760±32              772                                      Te              11±1              10              120±11              112                                      Zn              10.0±0.3              11              110±5              114                                            Results and discussions        The results obtained by the analysis of gold        samples from the pyre-grave in the “Big tumulus” near Kabyle are        reported in Table 3, where the concentrations of the major components        (Au, Ag, and Cu) are shown in weight %, while those of the micro        components are in mg kg-1.        Copper and silver are the major metallic impurities        in native gold and most gold ores (Boyle, 1987; Hall et al., 1998; Pohl, 1992). In general, the silver        concentration in ancient gold objects from Europe is within 4 to 45%        (Hauptmann et al., 2010; Kuleff et al., 2009; Pantazis et        al., 2003) with the most common concentrations of about 12-14% Ag        (Hauptmann et al., 2010; Pantazis et al., 2003). The values for copper are within 0.5        and 15% (Hauptmann et al., 2010; Pantazis et al., 2003). Such chemical composition indicates        the presence of a gold alloy containing a significant part of        impurities. The results presented in Table III show different        concentration intervals of the macrocomponents in the studied samples.        Gold concentration between 97.1 and 99.9% is an indication that the        analyzed samples were made of very pure gold alloy which could be        obtained after careful purification of natural gold, most probably        through cementation process (Ramage and Craddock, 2000). The        relatively low silver and copper concentrations (between 0.07-2.3% and        0.005-0.8% respectively) support this conclusion. Considering that a        carat is a 1/24 part of pure metal content in the alloy (when talking        about gold and platinum alloys), it follows that the analyzed gold        from Kabyle has purity of 23.31 to 23.98 carats (respectively from 970        to 998 in fineness). In comparison, the most common commercial forms        of gold nowadays – 14 and 18 carats, are characterized by gold        percentage between 58 and 75%. The low levels of the other measured        elements (Table 3) once again lead to the assumption that the gold        from Kabyle was carefully purified during the manufacturing process        (Ramage and Craddock, 2000). However, the uncertainties of some of the        elemental concentrations (see Table 3) indicate inhomogeneity of the        material. For example, the iron concentration in the samples varied        from 256 to 3396 mg kg-1, that of platinum – 43 to        129 mg kg-1 and of palladium is in the range from        15 to 109 mg kg-1, etc. Such results can be        explained with the very likely partial smelting of the gold pieces        from the wreath during the incineration.        It is believed that concentrations of copper in        ancient gold artifacts exceeding 3% are clear indication for alloying        gold, possibly aiming to reduce its cost, while alloys with less than        1% copper are naturally occuring. Alloys with 1-3% copper could be        natural or human made (Hall et al., 1998). The        Cu concentrations in the analyzed findings are, however, too low –        less than 0.8%, so most probably a very pure gold alloy was used, most        likely obtained after careful purification of natural gold (Ramage and        Craddock, 2000).        It is well known that in alluvial deposits, gold        can be associated with cassiterite (SnO2), iron        hydroxide (Fe(OH)3) and the platinum group        elements (PGEs). Gold ores in reef or lode deposits are often        associated with quartzite and other metallic minerals such as        arsenopyrite (FeAsS), chalcopyrite (CuFeS2),        galena (PbS), sphalerite ((Zn,Fe)S), tellurides and tetrahedrite (Hall        et al., 1998). The presence of traces of Sn in        the studied objects is characteristic of alluvial gold, probably due        to riverbed cassiterite and the absence of Sn is a sign for other gold        sources: mine or refined gold (Kuleff, 2012; Ramage and Craddock,        2000; Vasilescu et al., 2011). Extremely low Te and Sb were found, but        being volatile elements, the refining technology might eliminate them        (Ramage and Craddock, 2000). High concentration of iron was also        measured in the gold samples. Considering that iron objects were found        in the grave (Stoyanov et al., 2013) which        might have been in contact with the gold samples could be accepted as        a reason for its high concentration and its difference between the        samples. It can also be due to the long stay of the samples in the        soil. Since iron is a component of common gangue minerals, it does not        reflect the geographic provenance of the gold (Vasilescu et al., 2011).        Regarding the small number of analyses of gold        artifacts from the same historical period in Bulgaria, comparison with        other results appears to be difficult. The wreath from Kabyle is dated        to the same period with several golden breastplates from Southern        Thrace (see Kuleff et al., 2009) – about 4th century BC. However, in contrast to the Kabyle        wreath, the breastplates were most likely produced of natural (not        purified) gold. For example, the results obtained by analyses of        natural (alluvial) gold from the region (Cojocaru et        al., 2003; Kovachev et al., 2007;        Stefanova et al., 2007) are in very good        accordance with those from the breastplates and they show relatively        high silver and copper concentrations, higher than those measured in        the samples from Kabyle.        Usually concentration ratios between elements of        the platinum group can represent the similarity between the sources of        natural gold and the gold that was used for production of the studied        artifacts. It is very obvious to assume that the ancient goldsmiths        have used only one source of natural gold to make an object. In the        Classical and Hellenistic periods when gold was purified probably        different sources might have been used.        In Figure 3 the distribution of the analyzed gold        samples according to the concentrations of platinum and palladium is        presented. The grouping of the samples shows that at least four        sources of gold were used by the ancient goldsmiths. The scatterplot        in Figure 4 presents the distribution of the samples according the        ratios of Ag/Au and Pd/Pt. Considering the grouping of the samples in        both bivariate plots the assumption of four sources of gold could be        accepted. Samples 3006.KAB, 3007.KAB and 3008.KAB are grouped together        in both scatterplots.        Additionally the samples 3003.KAB and 3005.KAB        forming a group in Figure 3 are separated from the other samples in        Figure 4. Very close concentration values of other trace elements as        Sn, Te, Ti, Zn and Zr are also observed.        Figure 3: Correlation between the        concentrations of platinum and palladium (mg kg-1).Figure 3 : Correlation        entre des concentrations en platine et en palladium (mg kg-1).                Figure 4: Distribution of the analyzed        gold-samples according the Pd/Pt and Ag/Au ratios.Figure 4 : Distribution des échantillons d’or analysés        en fonction des raports Pd/Pt et Ag/Au.                Furthermore, the similar concentrations of Zn and        Zr (see Table 3) of the samples in the respective groups in Figure 3        could also be accepted as a confirmation of the above statement.        Unfortunately, at this stage of investigation it is        impossible to identify the sources of gold used for the preparation of        the golden wreath and the other golden objects found in the pyre-grave        in the tumulus of Kabyle due to the lack of analytical data for the        concentrations of platinum group elements in different gold sources in        Bulgaria. Using only this list of elements it is very difficult to        determine the source of gold used be ancient goldsmiths (see also        Pernicka, 2013). The possible origin of the golden wreath from North        Aegean might be presumed having in mind that the deceased was an        officer of the Macedon garrison of Kabyle, and considering the        discovered golden stater of Philipp II given to the dead man as a Charon’s obolus, as well as the imported pottery        from South and the Thracian amphorae (for details see Stoyanov et al., 2013).        Table 3: Elemental composition of the analyzed        gold samples (mg kg-1) from the grave funeral-pile        from the ancient town of Kabyle.Tableau 3 :        Teneurs mesurées pour les éléments présents dans les échantillons d’or        analysés (en mg kg-1), provenant des tumulus situés autour de la ville        ancienne de Kabyle.                                          Sample                                El.            3000.KAB            3001a.KAB            3001b.KAB            3002a.KAB            3002b.KAB            3003.KAB                                Au[%]            98.16±0.73            98.88±0.59            97.11±0.73            99.76±0.80            99.67±0.70            99.87±0.14                                Ag [%]            1.64±0.48            0.49±0.10            2.33±0.48            0.11±0.03            0.070±0.016            0.070±0.018                                Cu [%]            0.15±0.05            0.09±0.03            0.79±0.04            0.20±0.04            0.005±0.002            0.029±0.009                                As            89.30±20.2            48.3±8.7            60.5±20.2            84.3±8.7            218±27            147±29                                Bi            0.67±0.24            &#60;0.003            &#60;0.003            6.2±1.7            8.9±1.6            &#60;0.003                                Cd            2.93±0.45            &#60;0.01            &#60;0.01            10.3±2.6            23.3±6.5            0.046±0.019                                Co            0.35±0.11            0.60±0.16            0.6±0.1            0.60±0.16            0.50±0.04            9.4±1.4                                Fe            256.3±46.1            403±55            458±46            826±55            772±27            3396±183                                Ga            &#60;0.004            &#60;0.004            &#60;0.004            0.4±0.1            0.2±0.04            3.0±0.5                                In            0.22±0.08            &#60;0.003            &#60;0.003            0.14±0.04            0.3±0.1            0.013±0.006                                Ir            0.067±0.013            0.50±0.08            0.4±0.01            0.30±0.08            0.35±0.06            1.2±0.3                                Mn            15.2±5.0            15.0±4.5            25.4±5.0            23.6±4.5            43.0±8.3            156±23                                Mo            0.050±0.018            0.15±0.05            0.2±0.02            &#60;0.01            0.14±0.06            0.22±0.08                                Ni            0.63±0.19            1.5±0.3            1.3±0.2            &#60;0.06            &#60;0.06            2.3±0.7                                Pb            759±114            6.5±0.6            5.7±0.9            20.7±1.8            23.2±4.8            110±24.3                                Pd            62.7±11.5            109±7            102±12            65±6            108±30            22.7±4.5                                Pt            67.9±6.7            86.3±9.2            88.8±6.7            64±9            129±30            92±29                                Re            &#60;0.001            &#60;0.001            &#60;0.001            &#60;0.001            &#60;0.001            &#60;0.001                                Rh            0.092±0.037            0.19±0.02            0.19±0.04            0.028±0.008            0.07±0.03            0.30±0.09                                Ru            &#60;0.001            &#60;0.001            0.04±0.01            &#60;0.001            &#60;0.001            0.048±0.019                                Sb            0.067±0.032            &#60;0.003            &#60;0.003            &#60;0.003            &#60;0.003            1.5±0.5                                Se            &#60;0.3            &#60;0.3            &#60;0.3            &#60;0.3            &#60;0.3            &#60;0.3                                Sn            6.0±2.1            8.2±3.0            14.4±2.1            2.0±0.7            2.9±0.6            48.3±7.2                                Te            0.33±0.09            0.17±0.04            0.20±0.09            0.05±0.02            1.2±0.2            0.40±0.12                                Ti            9.9±2.1            3.5±0.9            3.6±2.1            35.6±1.9            37.1±0.7            105±11                                U            &#60;0.005            &#60;0.005            &#60;0.005            &#60;0.005            &#60;0.005            0.79±0.12                                W            &#60;0.005            &#60;0.005            &#60;0.005            0.07±0.03            &#60;0.005            &#60;0.005                                Zn            120±58            21±10            16.5±1.8            108±10            235±32            205±31                                Zr            4.7±1.7            2.5±0.6            2.4±0.7            5.5±1.1            17.6±3.6            10.8±2.2                                El.            3004.KAB            3005.KAB            3006.KAB            3007.KAB            3008.KAB            3009.KAB                                Au[%]            98.86±0.14            98.84±0.09            99.05±0.07            99.19±0.50            98.85±0.88            99.42±0.40                                Ag [%]            0.30±0.06            0.65±0.12            0.34±0.05            0.54±0.05            0.82±0.19            0.13±0.04                                Cu [%]            0.14±0.02            0.046±0.005            0.04±0.01            0.025±0.003            0.23±0.04            0.030±0.008                                As            32.9±4.9            113±11.3            62.6±24.3            36.9±8.9            36±14            55±15                                Bi            &#60;0.003            0.69±0.21            &#60;0.003            &#60;0.003            &#60;0.003            0.7±0.3                                Cd            0.073±0.038            0.74±0.18            0.10±0.04            1.02±0.19            1.0±0.4            0.8±0.3                                Co            0.30±0.08            1.90±0.48            0.8±0.1            0.63±0.09            0.35±0.12            0.8±0.2                                Fe            343±37            2120±680            1084±68            1041±98            280±123            1790±226                                Ga            &#60;0.004            2.3±0.6            0.40±0.05            &#60;0.004            &#60;0.004            1.1±0.5                                In            0.60±0.25            0.033±0.015            &#60;0.003            &#60;0.003            0.10±0.04            0.20±0.08                                Ir            0.70±0.08            0.7±0.2            0.87±0.17            0.40±0.12            0.23±0.08            0.19±0.08                                Mn            23.4±4.4            508±53            99±29            47±20            37±13            25±7                                Mo            0.037±0.017            0.29±0.11            0.020±0.008            0.040±0.008            0.45±0.08            0.09±0.03                                Ni            2.5±0.9            3.8±1.2            6.5±2.5            1.1±0.3            1.37±0.42            3.2±0.9                                Pb            123±22            48.1±10.6            15.7±6.2            1.37±0.18            4.2±1.1            13.9±2.6                                Pd            95.2±6.4            15.4±3.1            40±17            54.6±4.6            42.3±20.9            29±12                                Pt            125±16            90±16            62.7±12.4            63.4±9.5            73±29            43±21                                Re            (17±7).10-4            &#60;0.001            (25±12).10-4            &#60;0.001            &#60;0.001            &#60;0.001                                Rh            0.10±0.01            0.27±0.03            0.18±0.06            0.14±0.05            0.065±0.027            0.08±0.03                                Ru            0.043±0.009            0.14±0.03            0.13±0.02            0.022±0.003            0.09±0.04            0.003±0.002                                Sb            0.17±0.06            0.42±0.09            &#60;0.003            &#60;0.003            0.023±0.007            0.20±0.05                                Se            &#60;0.3            &#60;0.3            &#60;0.3            &#60;0.3            &#60;0.3            &#60;0.3                                Sn            14.6±2.7            41.5±6.2            11.2±1.2            3.2±0.5            264±88            18.8±5.5                                Te            0.16±0.05            0.36±0.11            0.57±0.18            0.17±0.06            0.093±0.025            0.42±0.18                                Ti            0.9±0.3            156±16            36±14            6.9±2.9            4.9±2.4            17.5±3.7                                U            &#60;0.005            5.1±0.5            0.097±0.015            0.037±0.005            &#60;0.005            1.8±0.6                                W            &#60;0.005            0.007±0.003            0.057±0.022            &#60;0.005            0.013±0.006            0.010±0.007                                Zn            93.9±16.3            217±22            97±39            39.8±8.0            248±109            171±72                                Zr            1.5±0.5            10.1±2.1            5.3±1.7            2.1±0.9            2.7±2.5            5.1±5.9                                Conclusion        Using ICP-AES and ICP-MS samples from the golden        wreath found in the tumulus of Kabyle were analyzed. Results indicate        that the wreath was produced using very high refined gold alloy (Au        between 97.1 and 99.9%).        Comparosin to other gold finds is difficult,        because of the lack of literature data. In most of the investigations        from the same period the gold objects are found in differerent parts        of Europe and Asia (see Gondonneau et al.,        2001; Guerra, 2004; 2005; Guerra and Calligaro, 2007; Guerra et al., 2008; Hall et al.,        1998; Hauptmann et al., 2010; Iliev, 2006;        Kuleff et al., 2009; Pantazis et al., 2003). Recently, archaeometric        investigation of gold objects from the same period found in Bulgaria        is described in Todorov et al., 2015.        However it could be assumed that the gold objects        investigated in this study are produced from very pure gold, obtain        through the process of purification. Alas, it is currently not        possible to identify the gold sources used by the ancient goldsmiths.        The study provides analytical data to be used for comparison with        other archaeological finds and is a good basis for future        research.