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Spectrochimica Acta Part B 66 (2011) 681690

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. e l s ev i e r. c o m / l o c a t e / s a b

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

composition determination [1,710]. Most of them are based in the


idea of drawing an Ag-prole from the surface to the bulk of the object
(LA-ICP-MS [11], PIXE and RBS [1]). 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 neness.
Eighty two Hellenistic silver coins were analyzed by means of a
portable XRF spectrometer. The coins are part of the Ioannes
Demetriou collection that belongs to the Numismatic Museum
(Athens, Greece) which consists of nearly 13,000 coins of the
Ptolemaic kings and coins of Egypt under the Roman administration
[12]. The analyzed coins cover the period between Ptolemy I and
Ptolemy V (323181 B.C.) (Fig. 1).
Comparison of the compositional data of such a large number of
Ptolemaic coins to those of other silver coins of the same period
[13,14] is expected to shed some light on the silver sources available
in the Hellenistic Mediterranean. Ptolemaic Egypt had a direct access
to gold and copper mines (at Nubia and Cyprus, respectively [15]), but

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682

V. Kantarelou et al. / Spectrochimica Acta Part B 66 (2011) 681690

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

Fig. 1. Tetradrachm and decadrachm from the collection of Ioannes Demetriou


(Numismatic Museum of Athens). Top: coin #2, Ptolemy I, Svoronos 18 [2], obverse
and reverse. Bottom: coin #25, Ptolemy II, Svoronos 444 [2], obverse and reverse. The
compositional data for the coins are given in Table 1.

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

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V. Kantarelou et al. / Spectrochimica Acta Part B 66 (2011) 681690

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)

(continued on next page)

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V. Kantarelou et al. / Spectrochimica Acta Part B 66 (2011) 681690

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

Uncertain mint in Asia Minor or Thrace.

of the micro-XRF spectrometer was determined to be 7631 m for


characteristic X-rays of energies between 22 and 4.5 keV, respectively
[29].
At the edges of the selected four coins, scanning micro-XRF
analysis [30,31] was applied on areas that unavoidably include
untreated sub-areas, to identify semi-quantitative differences in the
elemental composition. The results were compared to those obtained
by milli-probe and scanning micro-XRF analyses of at areas located
on both sides of the coins. 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, Cu, Au, Pb) spatial distribution
and concentration. These results may also give useful information on
possible association of the minor elements to surface contamination
or corrosion. The XRF spectra for coin #2 are shown in Fig. 2.
3. Results and discussion
The element concentrations determined from the milli-probe XRF
data are presented in Table 1. Table 2 shows mean values and
standard deviations for different reigns and mints. Normalization
factor values were found to be 1.02 0.02 and 1.02 0.014 for the
obverse and reverse of the coins, respectively. Fig. 3 shows the
absolute differences in Ag and Cu concentrations measured on the two

coin sides. Large differences in Ag concentrations are associated with


considerable increase of other minor elements (Zn, Fe or Pb).
3.1. Silver and copper
Ag and Cu concentrations are given in Table 1. Two of the coins
from the mint of Tyre (coins #35 and #51) were plated with a rather
thick silver foil. However, the Ag and Cu concentrations of the foil are
not different than those of the bulk silver. Two of the coins,
tetradrachms from the mint of Marathus (Ptolemy III) show high
concentration of Cu on both sides (coin #61(10%) and #66 (2.6
3.8%)). Such high values could be a result of deliberate addition of
copper or use of recycled silver [32]. Since the rest of the analyzed
coins of Ptolemy III from the mint of Marathus do not show high
concentrations of Cu, further general comments would not be safe.
Comparison of Ag-K and Cu-K micro-XRF intensities from the
clean coin areas to those from the original coin surface (obverse/
reverse) are shown in Table 3. The Ag-K 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), whereas the Cu-K intensities show much a broader
spread mainly due to larger statistical uncertainties in individual
measurements. In conclusion, no statistically signicant difference
was observed for the Ag and Cu intensities between the two examined
areas.
3.2. Minor elements

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.

Au was detected in all the analyzed coins. Bi was present only in


ve coins (b0.2%), Hg was detected in two coins in concentrations
larger than 1% and in minor amounts in a third coin (0.2%0.4%),
whereas Zn and Fe were measured in percentages larger than 0.5%
only in nine and eleven coins respectively. Four coins of Ptolemy IV
and seven coins of Ptolemy V were found with u concentrations up
to 1% which are higher than the rest of the coins of Ptolemy I, II and III.
In order to investigate the minor element spatial distribution, area
micro-XRF scans were performed and intensity maps for the Au-L,
Fe-K and Pb-L characteristic X-ray intensities were generated for
coin #2 (Fig. 4) and Hg-L and Zn-K for coins #4 and #28 (Fig. 5).
The area scans were performed on either the obverse or reverse of the
coins and at the cleaned edges. The measurement details can be found
in the respective gure captions. It is evident in Fig. 4 that Au intensity
does not show large variations, therefore it most probably associates
with the silver alloy matrix. The intensity maps of Pb-L and Fe-K Xrays indicate that these elements are distributed non-homogeneously

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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

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)

98.4 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 III (22 coins)

Ptolemy IV (8 coins)

Ptolemy V (12 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

on the surface (Fig. 4). The behavior of Pb may be explained by its


reduced solubility in silver alloy matrices [33]. On the other hand,
variations in Fe are obviously associated to surface contamination
from the burial environment.
Mercury was detected in three coins only (coins #4, #8 and #61).
In literature, Hg is attributed either to contamination from the burial
environment [34] or to its presence in the raw silver mineral as an
impurity [35]. Amalgam gilding is not considered possible in such an
early period, as it was introduced and extensively used later on,
during the Roman period [22]. The relative larger uncertainty of AgK
intensity on coin #4 is a strong indication that Hg is a surface
contaminant. It is also obvious in Fig. 5 that Hg is signicantly more
abundant on the coin surface than in the edge. This observation
indicates that Hg is related to surface contamination.
The Zn-K distribution map shows that Zn is much more abundant
on the clean area at the coin edge than on the reverse of the coin. In
very few cases large differences were observed between the milliprobe XRF measurements on the two coin sides. Nevertheless, it can
be suggested that Zn is associated with the matrix of the silver alloy,
whereas its rather occasional presence in some of the coins may
indicate that the silver metal has not been puried. According to
Craddock [36], Zn is usually lost during cupellation, although not
completely [37].

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

3.3. Surface enrichment in silver


According to Beck et al. [2], for AgCu alloys with more than 72%
Ag, the actual surface composition is the composition of the silver-rich
primary phase (Ag = 92%). For silver of higher neness (higher than
92%) there is no data published to assess possible Ag surface
enrichment. According to [2], in such cases there is no difference
between surface and bulk silver compositions. Nevertheless, three
complementary methodologies were explored in this study to
validate the compatibility of XRF data with the hypothesis adopted
for the quantication process, that the coins are made of a
homogeneous silver alloy: 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.
Although 75% of the analyzed coins were treated by chemical
means in the past, no difference was observed between Ag
concentrations of chemically treated and untreated ones. This is a
strong indication against the presence of an Ag-enriched layer.
Further on, it seems that chemical treatment did not affect the
concentration of minor elements. For example, coin #72, shows minor
element concentrations similar to those observed on the chemically
treated coins. The coin was originally covered by a thick layer of silver
corrosion products and treated mechanically with a pin pick for
analysis purposes.
The K/L ratio test was introduced by Linke et al. [7] in order to
assess the presence of a surface Ag rich layer in 15th century medieval
coins [8,9]. The K/L test is similar to the analytical methodology
followed by Klockenkamper et al. [10] in the analysis of 218 Roman
imperial silver coins. More specically, two variants of X-ray spectral
analysis were applied in this case; EPMA-EDS provided the elemental

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

Fig. 3. Absolute difference of concentrations measured on the obverse and reverse of


the coins for Ag and Cu.

Relative X-ray yield treated periphery/surface

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

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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.

composition of the rst 3 m of the coin surface layers, whereas the


wavelength dispersive mode of XRF analysis determined the
elemental compositions in deeper layers. Comparison between the
two Ag compositions is expected to reveal the possible presence of an
Ag-enriched surface layer. The Ag K/L ratios measured using the AgK
and AgL intensities of our reference silver alloys and from both sides
of the coins are presented in Table 3. Although a much higher mean
K/L value was calculated for the silver coins (88 11), the large error
value does not allow a clear differentiation from the respective mean

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

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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

78.3 1.8 Theory-FP: 79.5


81.1 1.1
78.3 3.7
78.2 2.2
87.8 10
88 11

similar to the surface one. In order to evaluate in a quantitative


manner this argument, complete FP based calculations were
performed for the Ag K to AgL 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. The
K/L ratios were normalized with respect to the respective pure silver
alloy value (Fig. 7). In the FP calculations, the inter- and intra layer
secondary uorescence Ag-K/Cu-K to Ag-L, the ternary AgKCuK
AgL and the Ag K to L cascade contribution were taken into account.
If the presence of such an internal structure can be conrmed by an
independent method and the K/L ratio is decreased less than about
50% of its thick pure Ag target value, 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. The XRF compositional analysis
through the Ag-L intensity has similarities to the Ag detection by
EPMA-EDS. Further on, it should be noted as it is also deduced from
Fig. 7, that the K/L ratio for homogenous silver alloys changes about
10% if the Ag content varies in the range 80100%. The results do not
support the existence of an Ag-enriched, surface layer, but certainly
denite conclusions cannot be extracted. The K/L ratios for example
determined by Linke et al. [7], change only up to 20% even when the
differences between the core and surface Ag concentration are almost
100%.
Fig. 6 shows that the most penetrating radiation for a typical Ag
Cu alloy is the Rh-K Rayleigh scattered radiation; 90% of Rayleigh
innite thickness intensity emanate from a depth of about 50 m.

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V. Kantarelou et al. / Spectrochimica Acta Part B 66 (2011) 681690

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. 8. Experimental mean Rayleigh (Rh-K) intensities measured on obverse and


reverse of the coins, respectively (for Ag N 95%). The dotted line represents a theoretical
estimation on the basis of a binary Ag/Au alloy. Experimental and theoretical data have
been normalized with respect to the respective pure Ag Rayleigh (Rh-K) intensity.
Experimental data corresponding to Ag concentration less than 95% is also given.

the X-ray tube energy distribution, uorescence cross sections,


secondary uorescence enhancement etc.). Both intensities were
normalized to the respective pure silver, thick target intensity and are
presented in Fig. 9 together with the experimental data from the silver
coins analyzed here. It is evident from Fig. 9 that the initial hypothesis
of an Ag-enriched, 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 m. Lower thicknesses are expected if the
Ag bulk concentration is higher than 75%. The data certainly exclude
the scenario that assumes Ag surface enrichment in a surface layer of
about 1015 m and a silver bulk with Ag concentration from about
75% to 92%.
3.4. Coin alloy composition
The major reason for the difculties in the interpretation of coinalloy analyses is the fact that the present elemental composition is
considerably different from that of the silver raw material. Smelting,
purication, alloying and corrosion have produced an almost entirely
different material. However, several safely deduced conclusions can
be extracted by the XRF data. All coins are made of silver, with minor
amounts of Cu, Au and Pb, Fe and Zn, in agreement with other results
for contemporary silver [2224]. The mean Ag value concentration

Fig. 9. Theoretically estimated Ag-K and Rh-K intensities (normalized to the


respective pure silver intensities) for a double layered silver alloy structure (Ag/Cu
binary alloy, top layer, Ag = 75% and variable thickness, bulk composition with
Ag = 75%) in comparison with the experimental data (within one sigma) deduced by
the silver coin measurements (shadowed blocks). Four coins with Ag b 95% have been
excluded from the statistics presented.

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V. Kantarelou et al. / Spectrochimica Acta Part B 66 (2011) 681690

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

The mean concentration of Au in the coins is 0.7%. 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 [21,40,42]. A plot of Au versus Pb is given
in Fig. 11 and shows small scale composition differences between
alloys of different time periods. The coins are grouped in four
groups, which are actually chronological: Group 1 includes coins of
the reign of Ptolemy I, Group II those of Ptolemy II, Group III of
Ptolemy III and Group IV includes coins of Ptolemies IV and V. If we
accept that Au is an indicator of the silver source and Pb a
technological indicator, we can follow a gradual increase in Au
concentration over time. During the reigns of Ptolemies I, II and III,
Au concentrations never exceed 0.81% while for the coins issued
during the reigns of Ptolemies IV and V, Au concentrations are
systematically higher than this value. This change may reect a
change of the silver source during the reign of Ptolemy IV but such
hypothesis needs more evidence, both historical and analytical to
be conrmed. Additionally, during the reigns of Ptolemies I and II,
Pb concentrations are limited to 0.7% indicating good rening
processes. From Ptolemy III to Ptolemy V, Pb concentrations
increase up to 2%.
Regarding other elements, trace amounts of Bi were detected in
just ve of the coins, mainly in coins of Ptolemy IV and Ptolemy V. Its
absence from the majority of the coins can be explained by its
reduction during the purication process or/and the use of a raw
material with low Bi content [38,43].
The concentration of iron shows high inhomogeneity as can be
seen on the micro-XRF map of coin #2. This heterogeneity may be
related to surface contamination from the burial environment.
However, the relatively high iron content of many coins, with similar
compositions on both coin sides, may be connected to the use of silver
bearing jarosite for melting [39]. It has to be noted that jarosite is
related to the primary source of silver in the silver ore deposits in
Spain, from the Late Bronze Age [39,44] although the Pb minerals for
jarosite smelting were usually imported.
4. 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. 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, b) Ag K/L
ratio test and c) anode characteristic radiation Rayleigh scattered
test.
Additionally, the XRF technique has proved of great usefulness in
the analysis of silver coins, mainly due to its analytical capacity to
easily detect the presence of certain minor elements, which are
critical in understanding surface nishing techniques, production
processes and nally provenance of the raw materials used.
Non-destructive XRF analysis was applied on 82 Hellenistic silver
coins, from different mints, produced during the reigns of Ptolemies
I to V. The results show that the coins were made by high purity
silver whereas a good rening process was applied in general. The
elevated amounts of Pb measured in many coins indicate that the
rening process was not too detailed. The relatively high Au
concentration is similar to the corresponding one of silver coins of
the same period. In addition, coins of Ptolemy IV and Ptolemy V
show higher concentration of Au, whereas Bi was detected in the
didrachms. This difference may reect a change of silver source. In
the case of Marathus mint, a deliberate addition of Cu was found for
two of the coins, probably dictated by monetary policy or economic
necessity.

Author's personal copy


690

V. Kantarelou et al. / Spectrochimica Acta Part B 66 (2011) 681690

Acknowledgments
A.G. Karydas would like to thank Despoina Kotzamani and Ignaci
Queralt for their useful comments and suggestions.

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