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EDXRF as a routine tool for numismatic studies
Energy dispersive X-ray fluorescence EDXRF, PIXE and neutron activation of 45° with the surface of the sample.
(EDXRF) technique is a well known ana- analysis (NAA) have been in use in other The coins were first washed using dis-
lytical tool for the determination of ele- advanced countries for a long time, no tilled water and then cleaned with alco-
mental concentrations of various types of effort has been made in the past to apply hol. They were then irradiated under K
samples of archaeological, biological, these sophisticated techniques in Indian X-rays of Mo. Fluorescent X-rays emit-
geological or environmental nature. It is numismatic studies. Recently, Hajivaliei ted from the coins due to irradiation were
a non-destructive technique capable of et al.2 and Vijayan et al.3 made attempts detected with an ORTEC LEPS (HPGe)
detecting elements down to the limit of to analyse some ancient Indian coins detector having a resolution of 180 eV at
ppm1. Compared to the other non-destru- with PIXE. We have now analysed a col- 5.89 keV. Figure 3 a–d shows the spectra
ctive methods, namely particle-induced lection of Indian coins, both ancient (5th obtained from the four coins. The time
X-ray emission (PIXE), electron probe century BC–11th century AD) and recent required for a typical run varied from 30
micro-analysis (EPMA), etc., EDXRF is (1975–2000), with our standardless to 45 min.
a simple and less expensive technique. EDXRF system. The obverse and reverse Using pure foils of Ti, Fe, Ni, Cu, etc.
Hence there is greater demand for ana- sides of the four coins analysed here are a good energy calibration curve was ob-
lysing precious archaeological items, shown in Figure 1. In this communica- tained. With this curve, the qualitative
especially old coins using EDXRF. tion, we present the results of these four picture of the coins could be readily
The study of old coins in India is not a coins (see Table 1) to demonstrate how ascertained. For quantitative analysis, we
recent phenomenon. The Indian Institute quickly EDXRF technique can be used in used a program used earlier6 to determine
of Research in Numismatic Studies, numismatic studies. the composition of alloys. In short, the
Nasik, has been doing this job for quite The experiment was performed using a principle is based on the fundamental
sometime. But the main technique used, system described in Mandal et al.4,5 A parameter method7, where physical
related to the compositional analysis of a schematic diagram of the present experi- parameters such as photoelectric cross-
coin, is the specific gravity method by mental arrangement is shown in Figure 2. sections, total mass attenuation cross-
which only coins based on the binary A Kevex 60 watt Tungsten X-ray tube at sections, fluorescence yields, X-ray
alloys could be analysed. Although 35 kV with a current of 0.3 mA was the branching ratio, detector efficiency (cal-
source of primary X-rays. A thick Mo culated theoretically) are given as inputs.
foil was used as a secondary target to get The program then theoretically generates
almost monochromatic X-rays. The inci- fluorescent X-rays and compares the
dent and emergent X-rays make an angle intensities of these fluorescent X-rays
with the experimental ones in an iterative
manner till the final concentration values
converge to a point. The absolute value
of the incident flux or the geometrical
factor is not required in this calculation,
as this program calculates only the rela-
tive concentration of elements with the
assumption that the sum of concentra-
tions of all the elements (as observed
from their X-ray lines) adds up to 100%.
Figure 2. Schematic diagram of the present In this calculation enhancements pro-
experimental set-up.
duced by the Kα, Kβ, Lα and Lβ lines of
higher Z elements has also been consid-
ered. Table 1 shows the compositional
Table 1. Elemental composition (in wt%) of
analyses of the four coins analysed with
the four coins whose spectra are shown in the present EDXRF system. The advan-
Figure 3 a–d tage of the present technique is that one
can calculate the elemental concentration
Coin no. Composition of a coin by exposing it only once under
1 Zn 1.4%, Pb 98.6%
the desired radiation without requiring
(1st century BC) any idea about the geometry and incident
flux. This saves a lot of time compared
2 Fe 2.4%, Cu 72.0%,
(4th century AD) Zn 1.1%, Pb 24.5%
to the method where different calibration
curves are made by exposing different
Figure 1. Obverse and reverse sides of the 3 Ni 26.3%, Cu 73.7%
analysed coins. No. 1, 1st century BC; No. 2, (1976)
4th century AD; No. 3, One rupee Indian coin
To an archaeologist, stratigraphy and
4 Cr 16.6%, Fe 83.4% palaeography of the coins are two main
of 1976; No. 4, One rupee Indian coin of
2000. sources of information to reconstruct the

134 CURRENT SCIENCE, VOL. 85, NO. 2, 25 JULY 2003

. A. and Sen. Saha Institute of Nuclear Physics. 63. 17. c.* charya. M. Nucl. M. this work. K. and d. Vijayan. M... during that period. Hajivaliei. 2002.. Phys. 19. past history. Instrum. e-mail: mano@anp. We are grateful † Department of Physics. 1 (1st century BC). CURRENT SCIENCE. D. Instrum. and Van Espen.. 2. P. A. P. D. Indian J. 2237–2244. 2001. Chem. Rev. Anal. ACKNOWLEDGEMENTS. 41–46. NO. Bidhannagar. 1/AF. 1999. Phys. The X-ray tube was run at 35 kV with a current of 0. P. Coin no. 4. BHATTACHARYA# 81–84. Sarkar. India Received 24 December 2002. 2 (4th century AD). also acknowledged. J. Mitra. Mandal. b. Sarkar. The non-destructive elemen. and Chakravortty. S. P. C. SANTRA# important added information which will 042705–9.. C. Kolkata 700 064. C. M. Sarkar. avail. ability of different metals and also the D. 645–650. Sparks. Spectra from a. 1. Phys.... 25 JULY 2003 135 . He.. Adv. F. AP.. and A. 477–479.3 mA. ted 22 May 2003 *For correspondence. Meth. A.. # 3.. X-ray Anal. B174. Mandal. D. SARKAR#. 2002. 19–52. SCIENTIFIC CORRESPONDENCE Figure 3. A55. Nayak. A76. Mandal.. to Prof. India ods. 1975. C. Coin no. Technical help from P. and Bhatta. K. MANDAL† tal concentration of coins will be an Bhattacharya. Eur.saha.. VOL. et al. 2002. 3 (1976). metallurgical processes which existed 7. Coin no. 4 (2000) excited with Mo K X-rays obtained from a Mo secondary target. Methods. Coin no. V. B150. revised accep- D. V. J. Bhattacharya.... C. 1991. M. D. 85. MITRA# enable him to study the economy. J. 5. 6. Das is Burdwan 713 104.ernet. Nucl. Sen for his encouragement during University of Burdwan.