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X-ray Fluorescence analytical criteria to assess the neness of ancient silver coins:
Application on Ptolemaic coinage
Vasiliki Kantarelou a,, Francisco Jos Ager b, c, Despoina Eugenidou d, Francisca Chaves e,
Alexandros Andreou d, Elena Kontou d, Niki Katsikosta d, Miguel Angel Respaldiza b, Patrizia Seran f,
Dimosthenis Sokaras a, Charalambos Zarkadas g, Kyriaki Polikreti h, Andreas Germanos Karydas a, i
a
Institute of Nuclear Physics, NCSR Demokritos, Aghia Paraskevi Attikis, 153 10, Greece
Departamento de Fsica Aplicada I, Universidad de Sevilla, Sevilla, Spain
c
Centro Nacional de Aceleradores, Avda. Thomas A. Edison, 7. E-41092 Sevilla, Spain
d
Numismatic Museum, Athens (NMA), Athens, Greece
e
Departamento de Prehistoria y Arqueologa, Universidad de Sevilla, Sevilla, Spain
f
Dipartimento di Beni Culturali, Musica e Spettacolo, Universit degli Studi di Roma Tor Vergata, Roma, Italy
g
PANalytical B.V., 7600 AA Almelo, The Netherlands
h
Hellenic Ministry of Culture, Directorate of Conservation of Ancient and Modern Monuments, Dept. of Applied Research, Pireos 81, 105 53, Athens, Greece
i
Nuclear Spectrometry and Applications Laboratory, IAEA, Seibersdorf, 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, silver enriched layer. 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, b) Ag K/L ratio test and c) comparison of experimental and theoretically simulated intensities of the
Rayleigh characteristic radiation emitted from the anode.
The proposed methodology was applied on 82 silver coins from the collection of Ioannes Demetriou, donated
to the Numismatic Museum of Athens in the 1890s. The coins originate from different mints and are attributed
to the rst ve Ptolemaic kings' reign (321180 B.C.). They were analyzed in-situ by using a milli-probe XRF
spectrometer.
The presence of an Ag-enriched layer was excluded for the majority of them. The silver neness was found to
be high, with very low concentrations of copper and lead. 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.C. due to economic or technical reasons.
2011 Elsevier B.V. All rights reserved.
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]. This may be a consequence of the original coin
production process [2], a special post-production treatment used
mainly during the Roman period [3], past conservation treatments [1]
or corrosion [4].
Therefore, traditional surface techniques like XRF, EPMA and PIXE,
where only a surface layer of limited depth (from a few micrometers
up to a few tens of micrometers) is analyzed, have to be used
cautiously in such studies [5,6]. Several methodologies have been
proposed to ensure reliability of surface measurements in silver bulk
Corresponding author.
E-mail addresses: kantarelou@inp.demokritos.gr (V. Kantarelou), fjager@us.es
(F.J. Ager), kpolykreti@culture.gr (K. Polikreti), A.Karydas@iaea.org (A.G. Karydas).
0584-8547/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2011.08.001
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. Walker et al. [22] scraped or abraded small areas
of about 12 mm 2 at the coin periphery, to be analyzed by XRF while
Schmitt et al. [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).
2.2. Experimental
not to silver mines. 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].
However, during the Syrian Wars, Ptolemy II (285246 B.C.) lost
Syria and Palestine and consequently lost access to the precious metal
[17]. 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], where
Carthaginians had control over the mine exploitation or at least the
metal trade. However, the defeat of Carthage by Rome in 206 B.C.
could justify the interruption of the Hispanic silver supply to Egypt
and the total collapse of the silver coinage minting at the area [19,20].
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, NAA-DAA) bulk analyses [13], whereas recently
XRF analyses of Greek drachmae from the Emporion site in Spain have
been also reported [14]. For the slightly earlier silver tetradrachms of
Philip II and Alexander the Great (minted between 356 and 300 B.C.),
the compositional results showed a very high neness (Ag N 97.5%), Pb
content less than 1% and Bi content between 20 and 3000 ppm [21].
2. Materials and methods
2.1. Coins preservation state and pre-analysis treatment
The mint, production date and reign attributed to the analyzed
coins are given in Table 1 (classied as in [12]). Apart from the
compositional XRF data for each coin, the table includes a small
description of preservation state and possible past conservation
treatment(s). Various treatments were applied on these coins in the
past, including chemical ones. The coins were grouped in ve
categories, based on treatment type: a) U: untreated, S: supercially
cleaned using solvents and cotton swabs, M: mechanically treated
using a pin pick, HM: mechanically treated (hard treatment),
C: chemically treated, CM: mechanically treated after chemical
cleaning, usually using glass bristle brush. XRF analysis was conducted
on both sides of the coins, on at areas of a good preservation state,
supercially cleaned using solvents (alcohol and acetone).
The portable milli-XRF spectrometer [25] is based on a sidewindow low power X-ray tube with a Rh anode (75 m Be window).
Analyses were performed at 40 kV, normal incidence. A composite
lter made of Nickel (42.5 mg/cm 2) and Vanadium (33.0 mg/cm 2)
foils was interposed in the excitation beam's path. This lter
considerably improves peak to background ratio in the low energy
region up to about 14 keV, improving the sensitivity and precision
when minor or trace elements such as Au, Pb and Bi in a silver matrix
are analyzed. The beam spot size at the sample position is about
2.7 mm and the counting interval was set at 3 min. The characteristic
X-rays emitted from the sample are detected by a Si-PIN diode X-ray
detector (Amptek XR-100CR, with 165 eV FWHM at MnK, 500 m Si
crystal thickness and 12.7 m Be window) placed at 45 from sample
normal. 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.
The quantication was based on the Fundamental Parameter (FP)
method by means of in-house (N.C.S.R. Demokritos) developed
software. The geometrical (G) factor of the spectrometer was
determined using pure element or compound targets. In principle, G
factor should be element independent. However, the uncertainties of
the various FPs involved in the calculations (e.g. the exciting tube
spectrum distribution, atomic fundamental parameters, etc.), result in
an experimental mean G value with a relative standard deviation of 6%
(sixteen pure element targets were used for the calibration). The
incorporation of the G factor to the quantitative analysis improves
accuracy and compensates for most FP method uncertainties. The
accuracy of quantitative analysis of major and minor elements (Cu,
Pb) in silver alloys was found to be satisfactory. The evaluation was
done by comparing the XRF composition results for reference alloys
(AgAu and AgCuPb) [26,27] to SEM-EDX data for the same
material.
The micro-probe XRF analysis of four selected coins was carried
out using a customized version of an Artax (Bruker AXS) spectrometer. The spectrometer composes of commercial, state-of-the-art
hardware components: an X-ray microfocus Rh-anode tube (spot size
50 50 m, max 50 kV, max 1 mA, 30-W maximum power consumption, Be window 0.2-mm thickness) and a polycapillary X-ray lens as a
focusing optical element (IfG) with a focal distance of about 21.2 mm.
The X-ray detection chain consists of a thermoelectrically cooled 10mm 2 silicon drift detector (X-Flash, 1000B) with 146 eV FWHM at
10 kcps coupled with a digital signal processor. A color CCD camera
(with approximately 13 times magnication) combined with a
dimmable white LED and a spot laser beam assures reproducible
positioning of the measuring probe, as well as visualization and
documentation of the analyzed area. 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. The scans over the coin surface areas
were performed at the following operational conditions: 50 kV,
600 A, 20 s/step, step size of 200 or 300 m and total scanned area
of about 0.9 0.9 mm 2. A lter consisting of Ti, Co and Pd was used to
improve the quality (monochromaticity) of the excitation beam and
avoid diffraction patterns in the spectrum [28]. The spatial resolution
683
Table 1
Concentrations obtained by XRF of the obverse side of the coins. Abbreviations for cleaning procedures: N: untreated, S: supercial, solvents and cotton swabs, M: mechanical with
pin pick, M*: Mechanical with Au pin pick in the area of analysis, HM: hard mechanical in the past, C: chemical, CM: mechanical-after chemical cleaning, usually with glass bristle
brush, Abbreviations for notes: PL: silver plated coin/Cu bulk, SR: silver reduction.
#
(N = 86)
Reign
Svoronos
number
Denom.
(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
18
24
42
35
146
146
168
168
117
183
205
245
254
263
364
366
373
395
420
421
435
444
488
496
420
567
596
596
602
626
626
637
713
734
775
828
902
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
903
Ephesus
42
Ptolemy II/III
905
Ephesus
43
Ptolemy II/III
907
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
938
940
961
988
989
1013
1014
1015
1019
1025
1027
1031
1033
1035
1036
1090
1091
1102
1103
1105
1108
1109
1115
1122
1124
1135
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.C.)
317311
317311
311305
311305
305285
305285
305285
305285
305285
305285
305285
305285
305285
305285
285246
285246
285246
285272
270
270
267
266
258
254
270
281
266
266
285246
285/4
285/4
279
285/4
255
254
255
285246 or
247/6221/20
285246 or
247/6221/20
285246 or
247/6221/20
285246 or
247/6221/20
245
242
221
247/6221/20
247/6221/20
245
245
244
243
245
244
242
241
245
244
240
239
230
229
228
225
224
221/20204/3
221/20204/3
221/20204/3
221/20204/3
Concentrations (%)
Ag
Cu
Au
99.0
96.1
99.4
97.3
99.2
99.2
99.3
95.3
99.3
99.1
98.9
98.2
98.9
99.1
96.8
98.7
98.6
98.8
97.7
99.1
98.9
98.9
98.9
98.2
92.5
99.1
98.8
99.4
98.8
99.2
99.0
98.7
99.1
99.1
98.6
98.5
98.7
0.095
0.250
0.042
b 0.025
b 0.025
0.130
0.039
0.091
0.099
0.100
0.110
0.097
0.160
0.120
0.23
0.066
0.320
0.100
0.490
b 0.025
0.084
0.065
0.091
0.090
0.460
0.140
0.120
b 0.025
0.180
0.180
0.096
0.430
b 0.025
b 0.025
0.110
b 0.025
0.170
0.46
0.51
0.18
0.37
0.54
0.64
0.41
1.00
0.42
0.46
0.48
0.69
0.45
0.43
0.73
0.58
0.70
0.67
0.71
0.63
0.66
0.58
0.53
0.56
1.00
0.54
0.50
0.58
0.50
0.43
0.46
0.76
0.71
0.68
0.68
0.51
0.79
98.9
0.110
97.7
Pb
Past
cleaning
procedure
Bi
Fe
Zn
Hg
0.20
0.09
0.26
0.37
0.23
0.041
0.29
0.37
0.17
0.31
0.48
0.15
0.53
0.33
0.19
0.68
0.33
0.12
0.32
0.28
0.39
0.25
0.14
0.36
3.00
0.24
0.36
0.05
0.55
0.076
0.20
0.08
0.16
0.18
0.57
0.72
0.31
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
0.29
3.00
b0.07
b0.07
b0.07
b0.07
b0.07
0.25
b0.07
b0.07
b0.07
b0.07
b0.07
b0.07
2.00
b0.07
b0.07
0.27
0.78
b0.07
b0.07
0.21
0.31
0.34
0.24
b0.07
0.18
b0.07
b0.07
0.072
0.28
b0.07
b0.07
b0.07
b0.07
0.22
b0.07
b0.02
b0.02
0.03
b0.02
b0.02
0.04
b0.02
b0.02
b0.02
b0.02
b0.02
0.86
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
0.46
3.00
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b 0.02
b 0.02
b 0.02
2.00
b 0.02
b 0.02
b 0.02
3.00
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
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
0.74
0.21
b 0.02
b0.07
b0.02
b 0.02
CM
0.039
1.1
0.32
b 0.02
0.47
0.39
b 0.02
CM
98.5
0.240
1.00
0.26
b 0.02
b0.07
b0.02
b 0.02
CM
99.2
94.8
96.6
99.1
99
98.4
98.0
98.4
95.7
98.9
98.1
95.1
97.2
98.2
98.1
98.2
87.6
97.1
97.9
98.5
98.3
92.9
99.3
96.2
98.5
97.6
0.047
0.210
0.100
b 0.025
b 0.025
0.065
0.290
0.100
0.033
0.054
0.140
0.120
0.140
0.100
0.031
0.410
11.0
0.790
0.640
0.120
0.440
3.0
b 0.025
0.210
0.032
1.0
0.65
0.74
0.81
0.77
1.00
0.53
0.68
0.61
0.82
0.67
0.60
0.74
0.65
0.75
0.59
0.67
0.45
0.50
0.71
0.57
0.76
1.00
0.61
2.00
1.4
0.85
0.13
0.66
2.00
0.16
b 0.02
0.79
0.41
0.50
1.10
0.40
0.77
2.00
1.00
0.73
0.88
0.67
0.47
0.97
0.55
0.84
0.51
1.00
0.10
0.85
0.05
0.17
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
0.21
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b0.07
0.62
0.63
b0.07
b0.07
0.21
b0.07
0.42
0.18
b0.07
0.16
2.00
1.00
b0.07
0.29
b0.07
b0.07
0.55
0.22
b0.07
b0.07
0.10
b0.07
b0.07
b0.07
0.24
b0.02
3.00
b0.02
b0.02
b0.02
b0.02
0.66
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
0.24
0.09
0.04
0.08
0.04
b0.02
b0.02
b0.02
2.00
b0.02
0.69
b0.02
0.12
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
0.35
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
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)
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
Svoronos
number
IV
IV
IV
IV
V
V
V
V
V
V
V
V
V
1181
1188
1209
1212
1216
1226
1231
1262
1263
1264
1267
1271
1283 or
1283
1289
1292
1293
Denom.
(drachms)
Mint
Date
(B.C.)
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
221/20204/3
221/20204/3
210
206
202
195
205/4180
205/4180
205/4180
205/4180
205/4180
204/3
196
96.4
98.5
98.3
96.4
98.5
98.4
98.9
97.2
97.6
98.3
98.5
98.1
98
0.280
0.190
0.068
0.072
0.160
0.140
b 0.025
1.0
0.720
0.280
0.190
0.400
0.520
1.4
1.00
0.50
0.28
0.51
0.25
0.96
0.59
0.78
1.00
1.00
0.98
1.00
0.99
0.21
1.10
3.00
0.75
1.20
0.09
0.60
0.94
0.37
0.19
0.48
0.48
b0.02
b0.02
0.03
0.04
0.05
0.04
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.07
0.11
b0.07
0.20
b0.07
b0.07
b0.07
0.58
b0.07
b0.07
b0.07
b0.07
b0.07
0.96
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
b 0.02
0.13
b 0.02
b 0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
b0.02
CM
N
C
CM
S
C
CM
S
NO or S
C
CM
N
CM
4
4
4
Damascus?
Sidon
Sidon
205/4180
205/4180
205/4180
98.5
97.6
98.8
0.180
0.510
0.400
1.00
0.94
0.69
0.45
0.10
0.15
b0.02
b0.02
b0.02
b0.07
0.62
b0.07
b 0.02
0.18
b 0.02
b0.02
b0.02
b0.02
CM
CM
S
Notes
M*
SR
SR
Fig. 2. XRF spectra acquired from the surface of a tetradrachm of Ptolemy I (coin #2,
Svoronos 24 21 [2]) with a milli- and a micro-spectrometer. The micro-XRF spectrum
is the total spectrum of 16 measurements (20 s per step). The asterisks denote the X-ray
tube anode scattered characteristic X-ray lines.
685
Table 2
Mean concentrations obtained by XRF of the coins sorted by periods and mints.
Concentrations (wt.%)
Reign
Mint (# coins)
Ag
Cu
Au
Pb
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)
98.4 1.3
98.2 1.8
99.0 0.3
99.1 0.1
98.6
98.5
98.4 0.6
98.1
97.6 2.0
97.6 1.3
97.1 1.8
98.2 0.1
95.8 4.1
97.8 1.1
96.4
98.1
98.6 0.3
97.9 0.6
98.0 0.2
98.3
98.2 0.8
0.11 0.05
0.19 0.15
0.24 0.17
0.52 0.23
0.66 0.23
0.55 0.18
0.7 0.02
0.68
0.51
0.88 0.2
1.4
0.86 0.27
0.66 0.12
0.67 0.06
0.67 0.11
0.68 0.22
0.87 0.52
1.4
1.4
0.57 0.36
0.84 0.20
1.09 0.16
1.2
0.82 0.18
0.27 0.14
0.5 0.6
0.12 0.07
0.17 0.01
0.57
0.72
0.28 0.06
0.26
0.71 0.83
0.70 0.31
1.12 0.78
0.81 0.11
0.74 0.27
0.83 1.02
0.99
0.21
0.68 0.56
0.53 0.32
0.48 0.01
0.45
0.13 0.04
Ptolemy IV (8 coins)
0.11
0.11 0.07
0.243
0.12 0.08
0.12 0.12
0.11 0.04
0.07 0.05
2.3 3.8
0.28 0.41
0.28
0.19
0.15 0.01
0.58 0.44
0.46 0.08
0.18
0.46 0.08
Bi
Fe
Zn
Hg
1.2 1.6
0.6 0.7
0.2 0.1
0.31 0.48
1.8 1.9
2.6 0.5
0.22
0.5
0.21
0.04 0.01
0.63 0.01
0.27 0.13
1.2 1.0
0.29
0.29 0.23
0.2
0.4
3.3
0.7
0.16 0.11
0.6 1.2
0.4 0.4
0.96
0.4
0.11
0.04 0.01
0.6
0.1
0.6
0.2
Table 3
The ratio of the Ag-K and Cu-K micro-XRF intensities among the scraped periphery
and the obverse or reverse of the surface, respectively.
Coin
Ag-K
Cu-K
2
4
28
76
0.93 0.04
0.86 0.14
0.99 0.04
1.03 0.04
0.75 0.25
0.92 0.45
1.29 0.52
0.75 0.26
Fig. 4. Spatial distribution of Au, Fe and Pb characteristic X-rays from the surface (a, c, e) and the edge (b, d, f) of the coin #2. Left surface: analyzed area 0.9 0.9 mm2, 0.3 mm step
size, 16 measurements (n = 16), Right edge: analyzed area 0.8 0.8 mm2, 0.2 mm step size, 25 measurements (n = 25). Approximately, the half right part of the edge area has been
treated mechanically.
K/L value for the reference alloys (79 2). In Table 4 the experimental
and the theoretically calculated Ag K/L ratio one is presented
exhibiting an excellent agreement. For the complete FP calculation, all
the possible secondary interactions that enhance the Ag L intensity
were taken into account, such as the secondary Ag K to AgL
uorescence intensity and the cascade K to L contribution, whereas a
semi-empirically described exciting tube spectrum distribution was
also considered. In the case of the coins, the Ag K/L ratio should be
even smaller if the enrichment scenario was valid. Simulations
687
Fig. 5. Spatial distribution of Hg and Zn characteristic X-rays from the surface (a, c) and the edge (b, d) of coins #4 and #28, respectively. Approximately the half right part of the edge
area has been treated mechanically.
presented in Fig. 6 show that the information depth for the Ag-L
intensity does not exceed a thickness of 2 m for a typical AgCu alloy
with a composition of Ag, 80% or 92%. On the contrary, 90% of the AgK intensity is produced from a layer thickness of 40 m. Therefore, if
an Ag enriched surface layer exists (of a thickness of 010 m for
example), the Ag-L intensity is expected to reach its saturation level
originating from the top Ag rich layer mainly, whereas the Ag-K
intensity would be less due to the signicant contribution of deeper
layers being less abundant in Ag. The nal K/L value would then be
thus smaller than the one expected if the bulk Ag concentration was
Table 4
The ratio between Ag-K and Ag-L intensities, as measured form from a pure silver
alloy, the reference silver alloys and the obverse or reverse of the coins. Composition of
the silver reference alloys: CNR 91: Ag 97.0%, Cu 1.5%, Pb 1.5%, CNR 152: Ag 96.5%,
Cu 3.5%, CNR 141: Ag 92.5%, Cu 7.5%. A theoretical estimation of the pure silver Ag-K
and Ag-L intensity ratio is also presented based on fundamental parameter approach
accounting properly for all secondary contributions to the Ag-L intensity.
Type of sample
Number of measurements
or samples
AgK/AgL
Pure Ag
CNR-141
CNR-152
CNR-91
Silver coins (obverse)
Silver coins (reverse)
5
2
4
8
82
81
Fig. 6. Information depth for Ag-, Ag-L and Rh-K characteristic X-rays in binary
Ag/Cu alloys.
Since the elastic scattering cross section scales as a power of the target
atomic number, if the Ag concentration of the coin bulk was lower
than in the surface enriched layer, we would expect lower Rayleigh
intensities than those emanated from a homogenous silver alloy. The
intensity of the Rh-K Rayleigh scattered radiation was measured for
the reference silver alloys and the coins (Fig. 8). The data were
normalized with respect to the Rh-K Rayleigh scattered intensity of a
pure silver, thick target. The statistical uncertainty, associated with
each measurement (180 s counting time) was about 3.5%. A
theoretical estimation was also performed for the normalized
Rayleigh scattered yield based on the differential scattering cross
sections (scattering angle = 135) of Rh-K radiation on Ag and Cu
elements. The mean normalized Rayleigh intensity was measured to
be 0.936 0.053 and 0.945 0.057 for the obverse and reverse of the
coins, respectively (four coins with Ag b 95% were excluded from
mean value calculations). The experimental Rh-K data was found to
be compatible with that from the Ag reference alloys, although a
systematic underestimation was observed in comparison with the
theoretical estimations, most probably due to possible inaccuracies of
theoretical cross sections of Rh-K Rayleigh scattering on Cu and Ag
atoms.
For the third test, a surface Ag-enrichment hypothesis was
adopted (Ag = 98% in a surface layer of 040 m thickness and
Ag = 75% in the bulk). Then the Ag-K and Rh-K intensities were
calculated, using the FP method (including an analytical description of
Fig. 7. The normalized Ag K to AgL 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. The K/L ratios were normalized with respect to
the respective pure silver alloy value.
Fig. 10. 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).
(98%) of the coins shows the high purity of early Ptolemaic silver. At
the end of the Ptolemaic dynasty silver coinage suffered from severe
debasement, with Cleopatra VII to issue staters composed of 2/3
copper and 1/3 silver [13]. The coins analyzed in this work however
cover the period from to 320 to 180 B.C., which is considered to be a
period of high purity silver [13]. In Fig. 10, the amount of Cu in the
coins is plotted against date of issue since Cu-content is a good
measure of debasement [13]. A slight debasement trend is obvious,
even in this period of Ptolemaic peak power.
In most of the coins the concentration of Cu was found below 1%.
By excluding any surface enrichment scenario, Cu content reects, the
raw silver mineral provenance, being either argentiferous lead ores or
silver bearing minerals such as jarosite [38,39]. However, copper
could also be present as a result of deliberate addition, either in small
quantities for hardening purposes after cupellation, or in larger
quantities due to monetary policy or economic necessity. Mc Kerrel
and Stevenson [40] argue that the presence of Cu in concentrations
higher than 23% in a silver object would be evidence of its deliberate
addition. 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.
Lead concentrations were also found below 1% in most of the cases.
Lead is probably the best indicator of the technological level of
purifying processes and such low concentrations indicate effective
rening. The lead cupellation process was used in the nal stages of
silver purication [41] and could reduce copper and lead to less than
1% [40].
Fig. 11. Pb versus Au for the analyzed coins. Ellipses have no statistical signicance;
they are drawn to include most of the data for each group. (Coins #28 and #74 with Pb
concentrations of 3% are not plotted).
689
Acknowledgments
A.G. Karydas would like to thank Despoina Kotzamani and Ignaci
Queralt for their useful comments and suggestions.
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