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NCSR “Demokritos”. Francisca Chaves e. Athens. E-mail addresses: kantarelou@inp.08. Greece i Nuclear Spectrometry and Applications Laboratory.C. Ptolemaic Egypt had a direct access to gold and copper mines (at Nubia and Cyprus. donated to the Numismatic Museum of Athens in the 1890s. Universidad de Sevilla. where only a surface layer of limited depth (from a few micrometers up to a few tens of micrometers) is analyzed. Karydas). Dimosthenis Sokaras a. b) Ag K/L ratio test and c) comparison of experimental and theoretically simulated intensities of the Rayleigh characteristic radiation emitted from the anode. Università degli Studi di Roma “Tor Vergata”.1016/j. but . Austria b a r t i c l e i n f o Article history: Received 25 January 2011 Accepted 3 August 2011 Available online 10 August 2011 Keywords: XRF Ancient coin Silver enrichment Hellenistic coinage a b s t r a c t The application of X-ray Fluorescence (XRF) analysis in a non-invasive manner on ancient silver coins may not provide reliable bulk compositional data due to possible presence of a surface. The present work proposes a set of three complementary analytical methodologies to assess and improve the reliability of XRF data in such cases: a) comparison of XRF data on original and cleaned micro-spots on coin surface. 0584-8547/$ – see front matter © 2011 Elsevier B. Charalambos Zarkadas g. Seibersdorf. a special post-production treatment used mainly during the Roman period [3]. Spain d Numismatic Museum. c.es (F. Therefore.) (Fig. 1). Introduction Surface measurements on ancient silver coins may not result in reliable bulk composition data due to silver enrichment of the near surface layers [1]. Universidad de Sevilla. 7600 AA Almelo. silver enriched layer.. © 2011 Elsevier B. Greece Departamento de Física Aplicada I.V.6]. of Applied Research. Directorate of Conservation of Ancient and Modern Monuments. Spain c Centro Nacional de Aceleradores. fjager@us.⁎. due to economic or technical reasons.Author's personal copy Spectrochimica Acta Part B 66 (2011) 681–690 Contents lists available at ScienceDirect Spectrochimica Acta Part B j o u r n a l h o m e p a g e : w w w. The silver fineness was found to be high.G.V.14] is expected to shed some light on the silver sources available in the Hellenistic Mediterranean. Polikreti). All rights reserved.org (A. 7. c o m / l o c a t e / s a b X-ray Fluorescence analytical criteria to assess the fineness of ancient silver coins: Application on Ptolemaic coinage Vasiliki Kantarelou a. IAEA. Musica e Spettacolo. Alexandros Andreou d. This may be a consequence of the original coin production process [2]. E-41092 Sevilla. Miguel Angel Respaldiza b. e l s ev i e r. The presence of an Ag-enriched layer was excluded for the majority of them. Thomas A. Comparison of the compositional data of such a large number of Ptolemaic coins to those of other silver coins of the same period [13. Despoina Eugenidou d. Several methodologies have been proposed to ensure reliability of surface measurements in silver bulk ⁎ Corresponding author.gr (K. The analyzed coins cover the period between Ptolemy I and Ptolemy V (323–181 B. The Netherlands h Hellenic Ministry of Culture. Elena Kontou d. They were analyzed in-situ by using a milli-probe XRF spectrometer. Most of them are based in the idea of drawing an Ag-profile from the surface to the bulk of the object (LA-ICP-MS [11]. Italy g PANalytical B. 105 53. with very low concentrations of copper and lead. EPMA and PIXE.2011.J. past conservation treatments [1] or corrosion [4]. Kyriaki Polikreti h. Athens. Dept. kpolykreti@culture. A. Edison. Greece e Departamento de Prehistoria y Arqueología. The coins originate from different mints and are attributed to the first five Ptolemaic kings' reign (321–180 B. 153 10. Roma. The composition data provide important information about possible sources of silver during the Ptolemaic period and indications of a gradual coinage debasement after 270 B. Sevilla. Niki Katsikosta d. respectively [15]).). 1.demokritos. All rights reserved.C. Athens (NMA).gr (V. traditional surface techniques like XRF. Pireos 81. Sevilla. Ager). Eighty two Hellenistic silver coins were analyzed by means of a portable XRF spectrometer. i a Institute of Nuclear Physics.000 coins of the Ptolemaic kings and coins of Egypt under the Roman administration [12]. have to be used cautiously in such studies [5. Aghia Paraskevi Attikis. doi:10. Avda.C.7–10].001 composition determination [1. The proposed methodology was applied on 82 silver coins from the collection of Ioannes Demetriou. Kantarelou). PIXE and RBS [1]). The coins are part of the Ioannes Demetriou collection that belongs to the Numismatic Museum (Athens.Karydas@iaea. Francisco José Ager b.V. Greece) which consists of nearly 13. Within this study a set of three complementary XRF methodologies is proposed to be used as an aid for the reliable non-destructive evaluation of silver coin fineness. Andreas Germanos Karydas a. Spain f Dipartimento di Beni Culturali.sab. Patrizia Serafin f.

M: mechanically treated using a pin pick. [23] and King and Northover [24] abraded and then polished the coin edges prior to the application of electron-probe microanalysis in association with wavelength dispersive X-ray spectrometry (EPMA-EDX). HM: mechanically treated (hard treatment). The spatial resolution . state-of-the-art hardware components: an X-ray microfocus Rh-anode tube (spot size 50 × 50 μm. Three stepping motors coupled with the spectrometer head allow three-dimensional movement for elemental mapping and precise setting of the analysis spot at the focal distance of the polycapillary lens. Be window 0. 1. The characteristic X-rays emitted from the sample are detected by a Si-PIN diode X-ray detector (Amptek XR-100CR. the defeat of Carthage by Rome in 206 B. the exciting tube spectrum distribution. etc. Previous analyses of silver coins from different Ptolemaic reigns and mints have been conducted by using a combination of destructive (wet chemical analysis) and non-destructive (Neutron and Deuteron Activation Analyses. A color CCD camera (with approximately ×13 times magnification) combined with a dimmable white LED and a spot laser beam assures reproducible positioning of the measuring probe.R. Two laser spots coupled on the spectrometers head are aligned in such a way to ensure the placement of the analyzed area on the reference plane. Apart from the compositional XRF data for each coin. 30-W maximum power consumption. Pb content less than 1% and Bi content between 20 and 3000 ppm [21].2. The portable milli-XRF spectrometer [25] is based on a sidewindow low power X-ray tube with a Rh anode (75 μm Be window). the uncertainties of the various FPs involved in the calculations (e. including chemical ones. The coins were grouped in five categories. whereas recently XRF analyses of Greek drachmae from the Emporion site in Spain have been also reported [14]. / Spectrochimica Acta Part B 66 (2011) 681–690 Four coins were selected and tiny areas at the coin edges were mechanically cleaned with a thin scraper pin to remove surface corrosion and prepare an area of about 1 mm 2 for the application of the micro-XRF beam. XRF analysis was conducted on both sides of the coins. not to silver mines. production date and reign attributed to the analyzed coins are given in Table 1 (classified as in [12]). improving the sensitivity and precision when minor or trace elements such as Au. 1000B) with 146 eV FWHM at 10 kcps coupled with a digital signal processor. S: superficially cleaned using solvents and cotton swabs.g. For the slightly earlier silver tetradrachms of Philip II and Alexander the Great (minted between 356 and 300 B. Pb) in silver alloys was found to be satisfactory. The evaluation was done by comparing the XRF composition results for reference alloys (Ag–Au and Ag–Cu–Pb) [26. 500 μm Si crystal thickness and 12. based on treatment type: a) U: untreated. The scans over the coin surface areas were performed at the following operational conditions: 50 kV. obverse and reverse. In principle.5 mg/cm 2) and Vanadium (33. The beam spot size at the sample position is about 2. with 165 eV FWHM at MnKα. superficially cleaned using solvents (alcohol and acetone).C.2-mm thickness) and a polycapillary X-ray lens as a focusing optical element (IfG) with a focal distance of about 21. C: chemically treated. atomic fundamental parameters. could justify the interruption of the Hispanic silver supply to Egypt and the total collapse of the silver coinage minting at the area [19. where Carthaginians had control over the mine exploitation or at least the metal trade.2 mm. The only silver source of the period that could export large quantities of silver was the Iberian Peninsula (especially the mines of Sierra Morena) and the area of modern Cartagena [18]. G factor should be element independent. The compositional data for the coins are given in Table 1. The geometrical (G) factor of the spectrometer was determined using pure element or compound targets. Coins preservation state and pre-analysis treatment The mint. However. usually using glass bristle brush. However. Various treatments were applied on these coins in the past.7 mm and the counting interval was set at 3 min. 2. as well as visualization and documentation of the analyzed area. Kantarelou et al.20]. 600 μA. A filter consisting of Ti. The accuracy of quantitative analysis of major and minor elements (Cu.Author's personal copy 682 V. Svoronos 18α [2]. max 1 mA. Walker et al.C.C.). the table includes a small description of preservation state and possible past conservation treatment(s). 2. NAA-DAA) bulk analyses [13]. The source of silver for the immense production of Ptolemaic tetradrachms was probably the rich mines of the Taurus Mountains in Cilicia (south coastal region of Asia Minor) [16]. The micro-probe XRF analysis of four selected coins was carried out using a customized version of an Artax (Bruker AXS) spectrometer.27] to SEM-EDX data for the same material. However. Ptolemy I. The spectrometer composes of commercial. 20 s/step. Tetradrachm and decadrachm from the collection of “Ioannes Demetriou” (Numismatic Museum of Athens). This filter considerably improves “peak to background” ratio in the low energy region up to about 14 keV. The incorporation of the G factor to the quantitative analysis improves accuracy and compensates for most FP method uncertainties. on flat areas of a good preservation state. Ptolemy II. Svoronos 444α [2]. normal incidence. result in an experimental mean G value with a relative standard deviation of 6% (sixteen pure element targets were used for the calibration). Analyses were performed at 40 kV. Top: coin #2. The quantification was based on the Fundamental Parameter (FP) method by means of in-house (N. [22] scraped or abraded small areas of about 1–2 mm 2 at the coin periphery.1. Bottom: coin #25.5%). max 50 kV.).) lost Syria and Palestine and consequently lost access to the precious metal [17]. the compositional results showed a very high fineness (Ag N 97. The X-ray detection chain consists of a thermoelectrically cooled 10mm 2 silicon drift detector (X-Flash.9 × 0. to be analyzed by XRF while Schmitt et al.7 μm Be window) placed at 45° from sample normal.C. CM: mechanically treated after chemical cleaning. Materials and methods 2. obverse and reverse. during the Syrian Wars. Co and Pd was used to improve the quality (monochromaticity) of the excitation beam and avoid diffraction patterns in the spectrum [28]. Ptolemy II (285–246 B.S. step size of 200 or 300 μm and total scanned area of about 0.9 mm 2. Pb and Bi in a silver matrix are analyzed.0 mg/cm 2) foils was interposed in the excitation beam's path. “Demokritos”) developed software. A composite filter made of Nickel (42. Experimental Fig.

02 b 0.02 b 0.100 0.63 0.71 0.17 0.08 0.02 b0.68 0.1 0.37 0.210 0.065 0.02 0.02 b 0.23 0.39 0.02 b 0. Kantarelou et al.460 0.45 0.5 98.7 98.47 0.07 b0.02 b 0.02 b 0.46 0.16 0.02 b 0.02 b 0.02 b 0.02 b 0. M*: Mechanical with Au pin pick in the area of analysis.50 1.02 b 0.55 0.65 0.46 0.07 b0.07 b0.091 0.05 0.18 0.090 0.85 0.58 0.74 0.410 11.0 0.02 2.00 0.02 b 0.02 b 0.02 b0.43 0.110 b 0.24 b0.97 0.56 1.07 0.5 98.41 0.02 b 0.53 0.02 b0.02 b0.100 b 0.61 0.02 b0.025 0.07 b0.02 0.02 b 0.1 98.0 98.02 0.26 0.02 b 0.02 b0.02 b0.140 0.51 1.02 b 0.02 b 0.1 98.3 99.02 b 0.7 99.02 b 0.05 0.02 b 0.21 b0.02 b 0.81 0.77 2.02 b0.047 0.097 0.07 b0.02 0.07 b0.29 0.091 0.02 b0.100 0.24 b0.02 b 0.1 97.24 0.00 b 0.02 b 0.23 0.02 b 0.07 b0.02 b0.28 0.04 b0.86 b0.00 0.60 0.2 99.07 0.66 b0.65 0.17 b 0.72 0.02 b 0.07 b0.02 b 0.07 b0.790 0.02 b 0. C: chemical.072 0.025 b 0.53 0.02 b 0.18 b0.02 CM C + (M) N C CM NO CM S CM CM CM CM CM CM C S C + HM CM C S S CM N CM C + HM CM Notes SR Reverse PL SR SR PL Cu products SR M* (obverse) (continued on next page) .039 0.09 0.02 b0.120 0.26 b 0.02 b 0.02 b 0.02 CM 0.29 b0.12 b 0.42 0.02 b 0.39 b 0.5 0.0 98.02 b 0.02 S S CM S S C + HM CM N C CM C CM C N S? C CM C? CM CM C CM C CM CM CM C CM C C C C CM CM CM C C 0.07 0.36 3.02 0.69 0.27 0.02 b0.0 96.096 0.73 0.110 97.7 0.22 b0.02 0.025 b 0.18 b0.18 0.490 b 0.02 b 0.07 0.02 b 0.02 b 0.170 0.25 b0.C.07 b0.Author's personal copy V.37 0.4 98.9 98.37 0.02 b 0.066 0.02 b0.16 2.02 0.02 b0.02 b 0.100 0.46 3.1 99.02 b 0.61 2.640 0.46 0.00 b0.095 0.6 98.02 b 0.6 97.02 3.4 98.02 b 0. usually with glass bristle brush.02 b0.140 0.1 98.02 b 0.02 b 0.02 b 0.180 0.02 b0.45 0.440 3.43 0.54 0.099 0.33 0.4 97.02 b0.2 94.1 99 98.00 1.57 0.02 b 0.02 b 0.02 b 0.02 b 0.07 b0.79 98.00 b0.02 b0. SR: silver reduction.07 b0.02 b 0.85 0.9 99.02 b 0.250 0.68 0.58 0.025 0.14 0.065 0.00 b0.28 b0.42 0.02 b 0.02 b 0.07 b0.) a 317–311 317–311 311–305 311–305 305–285 305–285 305–285 305–285 305–285 305–285 305–285 305–285 305–285 305–285 285–246 285–246 285–246 285–272 270 270 267 266 258 254 270 281 266 266 285–246 285/4 285/4 279 285/4 255 254 255 285–246 or 247/6–221/20 285–246 or 247/6–221/20 285–246 or 247/6–221/20 285–246 or 247/6–221/20 245 242 221 247/6–221/20 247/6–221/20 245 245 244 243 245 244 242 241 245 244 240 239 230 229 228 225 224 221/20–204/3 221/20–204/3 221/20–204/3 221/20–204/3 Concentrations (%) Ag Cu Au 99.02 b 0.8 99.02 b 0.02 b0.1 99. / Spectrochimica Acta Part B 66 (2011) 681–690 683 Table 1 Concentrations obtained by XRF of the obverse side of the coins. M: mechanical with pin pick.076 0.76 1.02 0.1 98.7 Pb Past cleaning procedure Bi Fe Zn Hg 0.12 0.02 b 0.88 0.02 b 0.02 b 0.02 b 0.02 CM 98.62 0.07 0.73 0.084 0.02 2.07 2.67 0.041 0.00 0.55 0.48 0.50 0.02 b0.07 b0.55 0.290 0.02 b0.1 98.00 0.76 0.02 b0.3 95. (drachms) Mint 1 2 3 4 5 6 7 8 10 11 12 13 14 15 16 17 18 20 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy I Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II Ptolemy II/III 18α 24α 42ε 35β 146ζ 146θ 168δ 168στ 117α 183α 205δ 245β 254α 263α 364α 366α 373β 395β 420α 421α 435α 444α 488α 496α 420α 567β 596α 596β 602β 626α 626β 637ιζ 713β 734α 775α 828α 902β 4 4 4 1/2 4 4 4 4 4 4 4 4 4 4 1 4 4 4 10 4 4 10 10 10 10 4 4 4 1 4 4 4 4 4 4 4 4 Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Egypt Tyre Tyre Tyre Sidon Sidon Ptolemais Gaza Ephesus 41 Ptolemy II/III 903α 4 Ephesus 42 Ptolemy II/III 905γ 4 Ephesus 43 Ptolemy II/III 907α 4 Uncertain 44 45 46 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy III Ptolemy IV Ptolemy IV Ptolemy IV Ptolemy IV 938β 940δ 961α 988α 989α 1013α 1014α 1015α 1019α 1025α 1027α 1031α 1033α 1035α 1036α 1090α 1091α 1102α 1103α 1105α 1108α 1109α 1115α 1122β 1124α 1135α 10 10 10 12 5 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Egypt Egypt Egypt Egypt Egypt Tyre Tyre Tyre Tyre Sidon Sidon Sidon Sidon Ptolemais Ptolemais Marathus Marathus Marathus Marathus Marathus Marathus Marathus Egypt Egypt Egypt Egypt Date (B.35 b 0.430 b 0.02 b 0.00 0.59 0.02 b 0.02 0.74 0.21 0.02 b 0.68 0.74 0.68 0.02 b 0.02 b 0.02 b 0.02 b 0.33 0.3 92.24 0.00 0.02 b 0.033 0.02 b 0.02 b 0.4 0.02 b 0.02 b 0.02 b0.02 b 0.02 b 0.180 0.34 0.47 0.02 b0.9 98.50 0.00 0.03 b0.71 0.77 1.025 0.10 b0.02 b 0.3 99.02 b 0.02 b 0.02 b 0.02 b 0.025 0.02 b 0.07 b0.02 b 0.02 0.02 b 0.00 b 0.04 0.50 0.02 b0.66 2.15 0.31 0.51 0. HM: hard mechanical in the past.6 98.10 0.00 b0.02 b0.8 96.8 97.1 96.70 0.0 0.07 b0.02 b 0.58 0.2 98.8 98.02 b 0.320 0.032 1.64 0.00 1.02 CM 99.02 b0.07 0.66 0.02 b 0.20 0. Abbreviations for cleaning procedures: N: untreated.13 0.75 0.5 97.02 b 0.07 b0.02 b 0.53 0.07 0.07 0.07 0.07 0.54 0.21 b 0.02 b 0.02 b 0.07 b0.07 0.20 0.51 0.07 b0.02 b0.02 b0.71 0.9 0.02 b 0.120 0.110 0.02 b 0.07 b0.025 b 0.08 0.054 0.02 b 0.41 1.2 98.02 b 0.039 1.02 b 0.07 0.9 98.02 b 0.00 0.3 96.130 0.82 0.48 0. Abbreviations for notes: PL: silver plated coin/Cu bulk.02 b 0.57 0.07 b0.32 0.025 0.04 b0.22 b0.00 b0.02 b0.00 1.63 b0.02 b0.9 98.19 0. S: superficial.5 99.02 b 0.84 0.6 0.9 99.78 b0.02 b 0.3 99.02 0.02 b 0.02 b 0.140 0.02 b 0.02 b 0.6 99.67 0.025 0.02 b0.67 0.25 0.07 b0.02 b 0.36 0.02 b 0.210 0.02 b 0.120 b 0.02 b 0.02 b 0.02 b 0.02 b0.2 87.02 3.29 3.0 b 0.120 0.2 92.02 b 0.21 b 0.031 0.16 b 0.02 b 0.9 98.8 99.4 95.02 b0.2 99.02 b 0.02 b0.02 b 0.7 99.042 b 0.02 b0.02 0.02 b 0.02 0.02 b 0.09 0.02 b 0.02 b 0.31 0.00 0. CM: mechanical-after chemical cleaning.02 b 0.100 0.07 0.02 b0.02 b 0.2 98.7 98. solvents and cotton swabs.02 b0.79 0.160 0.1 95.00 b0.9 98. # (N = 86) Reign Svoronos number Denom.69 b0.02 b0.10 0.2 99.02 b 0.07 b0.07 0.02 b0.40 0.31 b 0.2 98.67 0.1 97.32 b 0.240 1.025 0.

160 0. XRF spectra acquired from the surface of a tetradrachm of Ptolemy I (coin #2. Au. Bi was present only in five coins (b0.6 98.75 1.02 b 0.94 0. The area scans were performed on either the obverse or reverse of the coins and at the cleaned edges. further general comments would not be safe. These results may also give useful information on possible association of the minor elements to surface contamination or corrosion.58 b0.07 0. Svoronos 24α 21 [2]) with a milli. Silver and copper Ag and Cu concentrations are given in Table 1.20 0.720 0.) Concentrations (%) Ag Cu Au Pb Bi Fe Zn Hg Past cleaning procedure 4 2 2 2 2 4 4 4 4 4 4 4 Tyre Ascalon Egypt Egypt Egypt Egypt Egypt Cyrene? Cyrene? Cyrene? Cyrene? Unknown Unknown 221/20–204/3 221/20–204/3 210 206 202 195 205/4–180 205/4–180 205/4–180 205/4–180 205/4–180 204/3 196 96.C.07 0.02 b0. Table 2 shows mean values and standard deviations for different reigns and mints.02 ± 0. Comparison of Ag-Kα and Cu-Kα micro-XRF intensities from the clean coin areas to those from the original coin surface (obverse/ reverse) are shown in Table 3. Fe or Pb).07 b0.96 b 0.02 b0. to identify semi-quantitative differences in the elemental composition.18 b 0.04 0.025 1.02 b 0.07 0.02 b0. In conclusion.07 b0. of the micro-XRF spectrometer was determined to be 76–31 μm for characteristic X-rays of energies between 22 and 4.3 96.400 0. The micro-XRF spectrum is the total spectrum of 16 measurements (20 s per step).400 1.96 0. the Ag and Cu concentrations of the foil are not different than those of the bulk silver.02 CM CM S Notes M* SR SR Uncertain mint in Asia Minor or Thrace. Two of the coins. / Spectrochimica Acta Part B 66 (2011) 681–690 Table 1 (continued) # (N = 86) Reign 71 72 73 74 75 76 77 78 79 80 81 82 83 Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy Ptolemy 84 85 86 Ptolemy V Ptolemy V Ptolemy V a Svoronos number IV IV IV IV V V V V V V V V V 1181α 1188α 1209α 1212β 1216α 1226α 1231ε 1262γ 1263α 1264α 1267α 1271α 1283α or 1283β 1289α 1292α 1293α Denom.190 0.04 b0.02 ± 0.00 0.11 b0.4%).02 b0.02 b0.02 b 0. Au was detected in all the analyzed coins.20 b0.2. The asterisks denote the X-ray tube anode scattered characteristic X-ray lines. scanning micro-XRF analysis [30. The intensity maps of Pb-Lα and Fe-Kα Xrays indicate that these elements are distributed non-homogeneously .6 98.510 0. The measurement details can be found in the respective figure captions. It is evident in Fig.21 1. respectively.9 97.51 0.02 b0. respectively [29].02 b0.5 98.0 0.07 b 0.00 0. However.02 b 0. The Ag-Kα intensities calculated from the area scans show a relative standard deviation of 3% (except for coin #4 which shows a standard deviation of 19% possibly due to the presence of Hg). 2.10 3.072 0.014 for the obverse and reverse of the coins.140 b 0.02 b0.02 b0.1 98 0. II and III.Author's personal copy 684 V.02 and 1.02 b0.07 b0.02 b0.19 0.28 0. Such high values could be a result of deliberate addition of copper or use of recycled silver [32]. Cu. Two of the coins from the mint of Tyre (coins #35 and #51) were plated with a rather thick silver foil. no statistically significant difference was observed for the Ag and Cu intensities between the two examined areas. Large differences in Ag concentrations are associated with considerable increase of other minor elements (Zn.8 0.07 b0.02 b 0.48 0.4 98.068 0.02 b0.07 b0.00 1.02 b0.59 0. Pb) spatial distribution and concentration.2 97.78 1.99 0. Four coins of Ptolemy IV and seven coins of Ptolemy V were found with Αu concentrations up to 1% which are higher than the rest of the coins of Ptolemy I.02 b0.02 b 0.05 0.4 1.02 b0.69 0.5 keV.190 0. At the edges of the selected four coins.02 b0.02 b0.1. tetradrachms from the mint of Marathus (Ptolemy III) show high concentration of Cu on both sides (coin #61(10%) and #66 (2.09 0.280 0.00 0.02 b0.02 b0.00 0. whereas the Cu-Kα intensities show much a broader spread mainly due to larger statistical uncertainties in individual measurements.02 b0. 3 shows the absolute differences in Ag and Cu concentrations measured on the two coin sides. The scanning micro-probe XRF analysis results on both coin sides and at the cleaned edges offer a rough estimation of the minor elements (Fe.45 0. Since the rest of the analyzed coins of Ptolemy III from the mint of Marathus do not show high concentrations of Cu. 2.15 b0. Normalization factor values were found to be 1.37 0.5 98. 5).07 0.02 b0.4 98.3 98.4 98.48 b0.5 98.02 b 0. Fig. Results and discussion The element concentrations determined from the milli-probe XRF data are presented in Table 1.5 97.07 0.180 0. therefore it most probably associates with the silver alloy matrix.02 b0.02 b0.03 0.02 0.00 0. Kantarelou et al. 3.02 0.02 CM N C CM S C CM S NO or S C CM N CM 4 4 4 Damascus? Sidon Sidon 205/4–180 205/4–180 205/4–180 98.02 0.31] was applied on areas that unavoidably include untreated sub-areas.60 0.10 0.02 b0.02 b0.02 b0.280 0.02 b0.5% only in nine and eleven coins respectively.50 0.25 0.and a micro-spectrometer.2%). 3. Minor elements Fig.02 b 0.13 b 0.94 0.8%)).6– 3. 3. 4) and Hg-Lα and Zn-Kα for coins #4 and #28 (Fig. The results were compared to those obtained by milli-probe and scanning micro-XRF analyses of flat areas located on both sides of the coins. Fe-Kα and Pb-Lα characteristic X-ray intensities were generated for coin #2 (Fig. 4 that Au intensity does not show large variations. area micro-XRF scans were performed and intensity maps for the Au-Lα.02 b 0.62 b0.520 1. The XRF spectra for coin #2 are shown in Fig.07 b0.98 1. In order to investigate the minor element spatial distribution. whereas Zn and Fe were measured in percentages larger than 0.2%–0. Hg was detected in two coins in concentrations larger than 1% and in minor amounts in a third coin (0. (drachms) Mint Date (B.

2 ± 1.53 ± 0.11 0. Nevertheless. It is also obvious in Fig.58 ± 0.8 99.07 0. Bi Fe Zn Hg 1.11 0.4 0.8 98.19 ± 0. although not completely [37].6 0.18 0. shows minor element concentrations similar to those observed on the chemically treated coins.17 ± 0. it seems that chemical treatment did not affect the concentration of minor elements.3 98.27 ± 0.52 0.70 ± 0.6 98.45 0.86 ± 0.67 ± 0.51 0.6 98. This observation indicates that Hg is related to surface contamination. In literature.06 0.67 ± 0.04 ± 0.9].81 ± 0.06 0.48 1. According to Craddock [36].84 ± 0.22 0.12 ± 0.74 ± 0.14 0.3 98.04 Ptolemy III (22 coins) Ptolemy IV (8 coins) Ptolemy V (12 coins) 0.93 ± 0. Amalgam gilding is not considered possible in such an early period.12 ± 0.04 0.20 1.2 ± 0.2 ± 1.1 98. Hg is attributed either to contamination from the burial environment [34] or to its presence in the raw silver mineral as an impurity [35].5 98.83 ± 1. The Zn-Kα distribution map shows that Zn is much more abundant on the clean area at the coin edge than on the reverse of the coin.16 ± 0. In very few cases large differences were observed between the milliprobe XRF measurements on the two coin sides. Absolute difference of concentrations measured on the obverse and reverse of the coins for Ag and Cu.08 on the surface (Fig.3 99.02 0.68 ± 0.04 ± 0.4 3.2 ± 0. According to [2].11 ± 0. The coin was originally covered by a thick layer of silver corrosion products and treated mechanically with a pin pick for analysis purposes.8 0.28 ± 0.01 0.3. Concentrations (wt. Coin Fig.25 0.44 0.1 97. b) Ag K/L ratio test and c) comparison of experimental and theoretically simulated intensities of the Rayleigh characteristic radiation emitted from the anode.55 ± 0. Surface enrichment in silver According to Beck et al.03 ± 0.2 1.2 ± 1.26 0.04 0.08 0.27 0. variations in Fe are obviously associated to surface contamination from the burial environment.15 0.1 0.15 ± 0.12 0.12 0.52 ± 0.31 1.02 0.66 ± 0.8 ± 4.13 ± 0.72 0. The K/L ratio test was introduced by Linke et al. Further on.41 0. The K/L test is similar to the analytical methodology followed by Klockenkamper et al.1 97.11 0.52 1.12 ± 0.6 0.18 0.13 1.6 ± 0.71 ± 0. Nevertheless.75 ± 0.57 0.57 ± 0.7 ± 0.6 0.4 ± 0.46 ± 0. for Ag–Cu alloys with more than 72% Ag. The behavior of Pb may be explained by its reduced solubility in silver alloy matrices [33].07 ± 0.23 0.1 ± 0.6 98.31 ± 0.04 0. it can be suggested that Zn is associated with the matrix of the silver alloy.5 ± 0.75 ± 0.23 0. Relative X-ray yield treated periphery/surface # Ag-Kα Cu-Kα 2 4 28 76 0.82 ± 0.96 0.56 0.19 0. For silver of higher fineness (higher than 92%) there is no data published to assess possible Ag surface enrichment.11 ± 0.2 98.29 ± 0.3 0.16 1.11 0.14 0.8 ± 1.92 ± 0.11 ± 0.26 .1 98.2 0.243 0. no difference was observed between Ag concentrations of chemically treated and untreated ones.46 ± 0. More specifically.7 0.28 0.2 0.8 ± 1. EPMA-EDS provided the elemental Table 3 The ratio of the Ag-Kα and Cu-Kα micro-XRF intensities among the scraped periphery and the obverse or reverse of the surface. Kantarelou et al.9 2.07 0.27 0.2 0.36 0.4 0.04 1.5 0.11 0.01 0. [7] in order to assess the presence of a surface Ag rich layer in 15th century medieval coins [8.4 ± 1.21 0. / Spectrochimica Acta Part B 66 (2011) 681–690 685 Table 2 Mean concentrations obtained by XRF of the coins sorted by periods and mints.05 2. Mercury was detected in three coins only (coins #4.3 97. the actual surface composition is the composition of the silver-rich primary phase (Ag = 92%). as it was introduced and extensively used later on.5 0.0 0.99 ± 0.66 ± 0.1 95.24 ± 0.63 ± 0. during the Roman period [22].6 ± 0.18 0.%) Reign Mint (# coins) Ag Cu Au Pb Ptolemy I (14 coins) Ptolemy II (26 coins) Egypt (14) Egypt (15) Tyre (3) Sidon (2) Ptolemais (1) Gaza (1) Ephesus (3) Uncertain mint in Asia Minor or Thrace (1) Egypt (5) Tyre (4) Sidon (4) Ptolemais (2) Marathus (7) Egypt (6) Tyre (1) Ascalon (1) Egypt (3) Cyrene ? (4) Unknown (2) Damascus? (1) Sidon (2) 98.6 ± 1. three complementary methodologies were explored in this study to validate the compatibility of XRF data with the hypothesis adopted for the quantification process.4 98.7 0.08 0.1 0.23 0.48 ± 0. in such cases there is no difference between surface and bulk silver compositions. 5 that Hg is significantly more abundant on the coin surface than in the edge.3 ± 3.01 0.99 0.28 ± 0.1 96.01 0. 4).21 0.87 ± 0.0 97.68 0.29 0.45 1.22 0.3 97.83 0.1 ± 1.8 0.2 3.78 0. [10] in the analysis of 218 Roman imperial silver coins.29 ± 0. Zn is usually lost during cupellation.0 ± 0.9 ± 0.68 ± 0.01 0.2 ± 0.6 0. that the coins are made of a homogeneous silver alloy: a) comparison of XRF data on original and cleaned micro-spots on coin surface. #8 and #61).4 0.4 1. Although 75% of the analyzed coins were treated by chemical means in the past. two variants of X-ray spectral analysis were applied in this case.09 ± 0. This is a strong indication against the presence of an Ag-enriched layer.17 0. The relative larger uncertainty of AgKα intensity on coin #4 is a strong indication that Hg is a surface contaminant.88 ± 0.4 0.32 0. whereas its rather occasional presence in some of the coins may indicate that the silver metal has not been purified.12 ± 0.27 ± 0. coin #72.0 ± 0. [2].6 ± 0.05 0. 3.4 ± 0.01 0.Author's personal copy V. On the other hand.6 ± 1. For example.6 ± 2. respectively.86 ± 0.

Although a much higher mean K/L value was calculated for the silver coins (88 ± 11).2 mm step size. 4. Fe and Pb characteristic X-rays from the surface (a. 0. For the complete FP calculation. such as the secondary Ag K to AgLα fluorescence intensity and the cascade K to Lα contribution. c.3 mm step size. d. 0. In Table 4 the experimental and the theoretically calculated Ag Kα/Lα ratio one is presented exhibiting an excellent agreement. Approximately. composition of the first 3 μm of the coin surface layers.8 × 0. e) and the edge (b. the Ag K/L ratio should be even smaller if the enrichment scenario was valid.Author's personal copy 686 V. the half right part of the edge area has been treated mechanically. 25 measurements (n = 25). the large error value does not allow a clear differentiation from the respective mean K/L value for the reference alloys (79 ± 2). 16 measurements (n = 16). Right — edge: analyzed area 0. Simulations . / Spectrochimica Acta Part B 66 (2011) 681–690 Fig. In the case of the coins.9 × 0. whereas the wavelength dispersive mode of XRF analysis determined the elemental compositions in deeper layers. whereas a semi-empirically described exciting tube spectrum distribution was also considered. Spatial distribution of Au. Comparison between the two Ag compositions is expected to reveal the possible presence of an Ag-enriched surface layer. f) of the coin #2.8 mm2.9 mm2. The Ag K/L ratios measured using the AgKα and AgLα intensities of our reference silver alloys and from both sides of the coins are presented in Table 3. all the possible secondary interactions that enhance the Ag Lα intensity were taken into account. Left — surface: analyzed area 0. Kantarelou et al.

the Ag-Lα intensity is expected to reach its saturation level originating from the top Ag rich layer mainly. as measured form from a pure silver alloy. Type of sample Number of measurements or samples AgKα/AgLα Pure Ag CNR-141 CNR-152 CNR-91 Silver coins (obverse) Silver coins (reverse) 5 2 4 8 82 81 78. [7]. CNR — 152: Ag 96. the inter.5%. Pb 1. The K/L ratios for example determined by Linke et al. Composition of the silver reference alloys: CNR — 91: Ag 97. it should be noted as it is also deduced from Fig.5%.5%. if an Ag enriched surface layer exists (of a thickness of 0–10 μm for example). The XRF compositional analysis through the Ag-Lα intensity has similarities to the Ag detection by EPMA-EDS. Approximately the half right part of the edge area has been treated mechanically. 7). respectively. The final K/L value would then be thus smaller than the one expected if the bulk Ag concentration was Table 4 The ratio between Ag-Kα and Ag-Lα intensities. Fig.5 81. Cu 3.0%. complete FP based calculations were performed for the Ag Kα to AgLα intensity ratio assuming a double layered alloy system composed by a pure Ag top layer of variable thickness and a bulk binary Ag/Cu alloy of variable composition. A theoretical estimation of the pure silver Ag-Kα and Ag-Lα intensity ratio is also presented based on fundamental parameter approach accounting properly for all secondary contributions to the Ag-Lα intensity. then useful information for the range of the Ag concentration in the bulk alloy and for the thickness of the top Ag layer can be extracted.1 ± 1.5%.1 78. On the contrary. 5. Cu 1.5%.Author's personal copy V. Further on. Therefore.3 ± 1. the reference silver alloys and the obverse or reverse of the coins.7 78. / Spectrochimica Acta Part B 66 (2011) 681–690 687 Fig. that the K/L ratio for homogenous silver alloys changes about 10% if the Ag content varies in the range 80–100%. change only up to 20% even when the differences between the core and surface Ag concentration are almost 100%.8 — Theory-FP: 79. . c) and the edge (b. 6 show that the information depth for the Ag-Lα intensity does not exceed a thickness of 2 μm for a typical Ag–Cu alloy with a composition of Ag.5%. If the presence of such an internal structure can be confirmed by an independent method and the K/L ratio is decreased less than about 50% of its thick pure Ag target value. whereas the Ag-Kα intensity would be less due to the significant contribution of deeper layers being less abundant in Ag. d) of coins #4 and #28. surface layer. but certainly definite conclusions cannot be extracted. Spatial distribution of Hg and Zn characteristic X-rays from the surface (a. 6 shows that the most penetrating radiation for a typical Ag– Cu alloy is the Rh-Kα Rayleigh scattered radiation. In order to evaluate in a quantitative manner this argument. the ternary Ag–K–Cu–K– AgLα and the Ag K to L cascade contribution were taken into account. 90% of Rayleigh infinite thickness intensity emanate from a depth of about 50 μm. In the FP calculations. 7. The K/L ratios were normalized with respect to the respective pure silver alloy value (Fig. Cu 7.2 87. CNR — 141: Ag 92. 90% of the AgKα intensity is produced from a layer thickness of 40 μm.and intra layer secondary fluorescence Ag-K/Cu-K to Ag-Lα.3 ± 3. 80% or 92%.8 ± 10 88 ± 11 similar to the surface one. The results do not support the existence of an Ag-enriched.2 ± 2. presented in Fig. Kantarelou et al.

in agreement with other results for contemporary silver [22–24]. associated with each measurement (180 s counting time) was about 3. Au and Pb. Fig. Ag = 75% and variable thickness. The intensity of the Rh-Kα Rayleigh scattered radiation was measured for the reference silver alloys and the coins (Fig. purification. The mean Ag value concentration Fig. a surface Ag-enrichment hypothesis was adopted (Ag = 98% in a surface layer of 0–40 μm thickness and Ag = 75% in the bulk). 9. However. Four coins with Ag b 95% have been excluded from the statistics presented. Theoretically estimated Ag-Kα and Rh-Kα intensities (normalized to the respective pure silver intensities) for a double layered silver alloy structure (Ag/Cu binary alloy. It is evident from Fig. if the Ag concentration of the coin bulk was lower than in the surface enriched layer. 8). The data certainly exclude the scenario that assumes Ag surface enrichment in a surface layer of about 10–15 μm and a silver bulk with Ag concentration from about 75% to 92%.057 for the obverse and reverse of the coins. respectively (for Ag N 95%). Experimental data corresponding to Ag concentration less than 95% is also given. The statistical uncertainty. Fe and Zn. Both intensities were normalized to the respective pure silver. using the FP method (including an analytical description of Fig. 9 together with the experimental data from the silver coins analyzed here. respectively (four coins with Ag b 95% were excluded from mean value calculations).4. Smelting. the X-ray tube energy distribution. alloying and corrosion have produced an almost entirely different material. Information depth for Ag-Κα. 9 that the initial hypothesis of an Ag-enriched. . The mean normalized Rayleigh intensity was measured to be 0. we would expect lower Rayleigh intensities than those emanated from a homogenous silver alloy. / Spectrochimica Acta Part B 66 (2011) 681–690 Fig. Kantarelou et al. although a systematic underestimation was observed in comparison with the theoretical estimations.). 3. A theoretical estimation was also performed for the normalized Rayleigh scattered yield based on the differential scattering cross sections (scattering angle = 135°) of Rh-Kα radiation on Ag and Cu elements. surface layer on a bulk alloy of 75% Ag would be compatible with the experimental data only if the enrichment layer was thicker than about 26 μm. The experimental Rh-Kα data was found to be compatible with that from the Ag reference alloys. The dotted line represents a theoretical estimation on the basis of a binary Ag/Au alloy. Ag-Lα and Rh-Kα characteristic X-rays in binary Ag/Cu alloys. 6.Author's personal copy 688 V. Coin alloy composition The major reason for the difficulties in the interpretation of coinalloy analyses is the fact that the present elemental composition is considerably different from that of the silver raw material. Since the elastic scattering cross section scales as a power of the target atomic number. thick target. fluorescence cross sections. secondary fluorescence enhancement etc.936 ± 0. Then the Ag-Kα and Rh-Kα intensities were calculated. The Kα/Lα ratios were normalized with respect to the respective pure silver alloy value. most probably due to possible inaccuracies of theoretical cross sections of Rh-Kα Rayleigh scattering on Cu and Ag atoms. several safely deduced conclusions can be extracted by the XRF data. All coins are made of silver. Experimental and theoretical data have been normalized with respect to the respective pure Ag Rayleigh (Rh-Kα) intensity. thick target intensity and are presented in Fig. Lower thicknesses are expected if the Ag bulk concentration is higher than 75%. top layer. The data were normalized with respect to the Rh-Kα Rayleigh scattered intensity of a pure silver. bulk composition with Ag = 75%) in comparison with the experimental data (within one sigma) deduced by the silver coin measurements (shadowed blocks).5%. The normalized Ag Kα to AgLα intensity ratio calculated for a double layered alloy system composed by a pure Ag top layer of variable thickness and a bulk binary Ag/Cu alloy of variable composition.053 and 0.945 ± 0. Experimental mean Rayleigh (Rh-Kα) intensities measured on obverse and reverse of the coins. 7. For the third test. with minor amounts of Cu. 8.

The lead cupellation process was used in the final stages of silver purification [41] and could reduce copper and lead to less than 1% [40]. The present work proposes a set of three complementary analytical methodologies as a tool to assess the reliability of XRF data in such cases: a) comparison of XRF data on original and cleaned micro-spots on coin surface. which is considered to be a period of high purity silver [13]. The results show that the coins were made by high purity silver whereas a good refining process was applied in general. which are actually chronological: Group 1 includes coins of the reign of Ptolemy I. 689 The mean concentration of Au in the coins is 0. during the reigns of Ptolemies I and II. If we accept that Au is an indicator of the silver source and Pb a technological indicator.. During the reigns of Ptolemies I. produced during the reigns of Ptolemies I to V. It has to be noted that jarosite is related to the primary source of silver in the silver ore deposits in Spain. Fig. This change may reflect a change of the silver source during the reign of Ptolemy IV but such hypothesis needs more evidence.40. whereas Bi was detected in the didrachms.42]. Pb concentrations increase up to 2%. In Fig. Gold in such low concentrations is generally considered as an indicator of the parent ore composition since it is not expected to be affected by smelting and cupellation [21. the XRF technique has proved of great usefulness in the analysis of silver coins. From Ptolemy III to Ptolemy V.7% indicating good refining processes. Its absence from the majority of the coins can be explained by its reduction during the purification process or/and the use of a raw material with low Bi content [38. Regarding other elements.C. the relatively high iron content of many coins.7%. even in this period of Ptolemaic peak power. The elevated amounts of Pb measured in many coins indicate that the refining process was not too detailed. Additionally.8–1% while for the coins issued during the reigns of Ptolemies IV and V. However. Change of copper content versus date of issue for the analyzed coins (Coins #61 and #66 with Cu concentrations of 3 and 11% correspondingly are not plotted). By excluding any surface enrichment scenario. Lead is probably the best indicator of the technological level of purifying processes and such low concentrations indicate effective refining.43]. b) Ag K/L ratio test and c) anode characteristic radiation Rayleigh scattered test. / Spectrochimica Acta Part B 66 (2011) 681–690 Fig. with similar compositions on both coin sides.Author's personal copy V. we can follow a gradual increase in Au concentration over time.39]. 4. being either argentiferous lead ores or silver bearing minerals such as jarosite [38. the amount of Cu in the coins is plotted against date of issue since Cu-content is a good measure of debasement [13]. Group III of Ptolemy III and Group IV includes coins of Ptolemies IV and V. Such high concentrations are observed in two of the Ptolemy III tetradrachms from the mint of Marathus (#61 and #66) and a deliberate addition of copper can be thus concluded. both historical and analytical to be confirmed. with Cleopatra VII to issue staters composed of 2/3 copper and 1/3 silver [13]. The coins are grouped in four groups. a deliberate addition of Cu was found for two of the coins. A slight debasement trend is obvious. Au concentrations never exceed 0. they are drawn to include most of the data for each group. the raw silver mineral provenance. The concentration of iron shows high inhomogeneity as can be seen on the micro-XRF map of coin #2. 11. Mc Kerrel and Stevenson [40] argue that the presence of Cu in concentrations higher than 2–3% in a silver object would be evidence of its deliberate addition. The coins analyzed in this work however cover the period from to 320 to 180 B. In most of the coins the concentration of Cu was found below 1%. copper could also be present as a result of deliberate addition. Pb concentrations are limited to 0. Additionally. Lead concentrations were also found below 1% in most of the cases. However. At the end of the Ptolemaic dynasty silver coinage suffered from severe debasement. Conclusions The full exploitation of the analytical information recorded in an XRF spectrum and the application of appropriate experimental and theoretical FP based methodologies can provide a set of semiquantitative criteria to assess the presence or not of enriched Aglayers on silver coin surfaces. This heterogeneity may be related to surface contamination from the burial environment. (98%) of the coins shows the high purity of early Ptolemaic silver. . Group II those of Ptolemy II. The relatively high Au concentration is similar to the corresponding one of silver coins of the same period. either in small quantities for hardening purposes after cupellation. trace amounts of Bi were detected in just five of the coins. Kantarelou et al. Cu content reflects. or in larger quantities due to monetary policy or economic necessity. This difference may reflect a change of silver source. production processes and finally provenance of the raw materials used. from the Late Bronze Age [39. mainly in coins of Ptolemy IV and Ptolemy V. II and III. 10. probably dictated by monetary policy or economic necessity. Au concentrations are systematically higher than this value. 10. mainly due to its analytical capacity to easily detect the presence of certain minor elements. A plot of Au versus Pb is given in Fig. coins of Ptolemy IV and Ptolemy V show higher concentration of Au.44] although the Pb minerals for jarosite smelting were usually imported. Non-destructive XRF analysis was applied on 82 Hellenistic silver coins. (Coins #28 and #74 with Pb concentrations of 3% are not plotted). which are critical in understanding surface finishing techniques. In addition. In the case of Marathus mint. Pb versus Au for the analyzed coins. from different mints. Ellipses have no statistical significance. 11 and shows small scale composition differences between alloys of different time periods. may be connected to the use of silver bearing jarosite for melting [39].

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