Journal of Nuclear and Radiochemical Sciences, Vol. 9, No.1, pp. 7-12, 2008

Application of Instrumental Neutron Activation Analysis for Chemical Composition
Analysis of Ancient Potteries from Buddhist Sites of Andhra Pradesh: Part I
D. Partha Sarathi,a R. Acharya,b A.G.C. Nair,b S. Lakshminarayana,c N. Lakshmana Das,a and
A.V.R. Reddy*,baCollege of Science, GITAM, Visakhapatnam – 530 045, India
Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai – 400 085, Indiac
Department of Nuclear Physics, Andhra University, Visakhapatnam – 530 002, Indiab

Received: September 3, 2007; In Final Form: December 28, 2007
Instrumental neutron activation analysis (INAA) using high resolution γ-ray spectrometry was used to determine
concentrations of 20 elements in seven clay pottery samples collected from excavated Buddhist sites of four districts of Andhra Pradesh, India. For determining accuracy of the INAA method, two certified reference materials(CRMs) namely SL-1 and Soil-7 obtained from IAEA were analyzed. For establishing the provenance (same ordifferent origin) of pottery samples, Al to Sc concentration ratio as well as statistical cluster analysis was used.
For the cluster analysis, concentration values of selected nine elements namely Sc, Cr, Mn, Fe, Co, Rb, Cs, Ba, and
Hf were used. Soil samples from corresponding sites with known origin were analyzed for the validation of provenance methodology adopted in this study. From these analyses, it was observed that both pottery and soil samples
under study belong to four different groups. To the best of our knowledge, the provenance studies of these ancientpottery samples are reported for the first time.

1. Introduction
Studies on archaeological artifacts constitute an importantarea of research to unravel the past human activities like art,
culture, and trade. Most of the studies focus on the provenanceof the artifacts i.e., whether they belong to same or different
origin or group. Archaeologists investigate through the provenance studies whether chosen artifacts belong to the same ordifferent origin. In the provenance studies, archaeological artifacts like pottery, bricks, stones, coins, and paints are investigated.1-4 Among these artifacts, potteries are most studied.
Studies for provenance are carried out in two ways: either byclassifying samples according to their physical characteristics,
decoration, and style or by chemical composition analysis.1,2
Chemical composition analysis of artifacts is the most important tool for providing useful information like geographicalorigin and manufacturing techniques.3 The chemical composition of a clay pottery is strongly related to the source of clay
and recipe of the making.4 It is known that the concentrationsof major elements like Si, Al, Ca, and Mg may not vary significantly compared to the elements present at trace levels.5 The
variation of trace elements depends on the place and preparation, and hence determination of concentration of trace elements becomes more important. Groups of elements used forthe provenance studies are alkali and alkaline earth elements,
transition elements and rare earth elements (REEs).3,6 Elements
which are non-volatile and immobile, exhibit high stability inclay minerals and therefore are good candidates for cluster
analysis as any changes if found could be attributed to composition of making rather than due to migration, mobility andweathering with time.3,6 The REEs are used for provenancestudy due to their similar geochemical properties as well as
highly insoluble and immobile nature. The alkali and alkaline
earth elements like Na, K, Rb, Cs, and Ba, have similar properties and expected to have correlation among them in clay andpottery samples. Correlations are also reported among the*Corresponding author. E-mail: avreddy@barc.gov.in. Fax:
+91-22-2550 5151

transition elements like Sc, Fe, Co, Cr, Hf, and Mn, which areused for grouping of artifacts. For samples like pottery andbricks, making process involves high temperature treatment ofwet/sun-drenched samples through firing. Therefore, ratios ofconcentrations of non-volatile elements like Al and Sc or elements having similar geochemical properties like La and Ce
are used in the provenance studies of samples like potteries.1, 7
Elemental composition analysis of artifacts demands reliable
results of concentrations at major to trace levels using a sensitive analytical method. Non-destructive nuclear analyticalmethods like neutron activation analysis (NAA), X-ray fluorescence (XRF) and particle induced X-ray emission (PIXE) havebeen used for the analysis of archaeological artifacts like potteries.7-14 These methods have been applied to different samples
with varying degrees of success in terms of sensitivity andmultielement capability. Among these methods, instrumental
NAA (INAA) is the most used method for determining major,
minor, and trace elements due to its high sensitivity, low detection limit, simultaneous multielement capability, negligible
matrix interference, and most importantly non-destructive
nature, i.e., sample is used as it is received without any chemical dissolution. It is an isotope specific technique based onirradiation of samples using reactor neutrons and measuring
the characteristic γ-radiations emitted by the radioisotope produced in irradiation. Often γ-spectrometry having HPGe
detector coupled to multi-channel analyzer (MCA) is used forradioactivity measurement. Use of high flux research reactor
neutrons and high-resolution γ-ray spectrometry makes themethod capable of determining many elements at mg kg–1 to µg
kg–1 level.15,16 The added advantage of INAA over other methods is that it allows simultaneous multiple sample irradiation ina reactor in a single run. Chemical analyses together with statistical data treatment are used as valid method for provenancestudy and have been extensively used in the archaeologicalinvestigations.3,6,9 Multivariate statistical methods like cluster
analyses (CA) and principle component analysis (PCA) aremainly used for this purpose.3,6,9,10,14
In the present study, pottery samples, collected from sevendifferent locations, were analyzed by relative method of INAA

© 2008 The Japan Society of Nuclear and Radiochemical Sciences
Published on Web 02/22/2008

8

SarathiJ. Nucl. Radiochem. Sci., Vol. 9, No. 1, 2008

for their elemental concentrations. IAEA CRMs SL-1 andSoil-7 were analyzed to evaluate the accuracy of the method.
Concentrations of 20 elements which include Al, alkali, alkaline earth, and transition elements were used for grouping of
the pottery samples. Elemental ratios of Al and Sc in pottery
samples were used for the preliminary grouping. Statisticalcluster analysis was carried out using concentrations of nine
key elements (Rb, Cs, Ba, Sc, Cr, Mn, Fe, Co, and Hf) for
establishing the provenance of pottery samples under investigation. Similar studies were carried out for seven soil samples
collected from corresponding sites of potteries as a method
validation of the adopted provenance study, since soil samples
origin was known a priori.
2. Experimental
2.1. Sample collection sites. Although archaeologists so far
have identified more than one hundred and forty Buddhist sites
in Andhra Pradesh, ranging in date from pre-Asoka (4th -3rd
century BC) to Vishnukundin times (4th – 5th century AD),stretching from Dantapuram in the North to Nandalur in theSouth and Kotilingala in the West to Bhattiprolu in the East ofAndhra Pradesh, India,17 initially only seven important sites
were selected. These are excavated Buddhist sites along thesea coast of Visakhapatnam, Srikakulam, and other nearby
places of Andhra Pradesh, India. The location map of the sites
is shown in Figure 1 and additionally, the names of the places
and geological coordinates are given in Table 1.
2.2. Collection of samples. The samples were collectedunder the supervision of personnel from the Department ofArchaeology and Museums, Government of Andhra Pradesh,
India. Pottery samples of different shapes, with length of 6–15
cm weighing about 250 g – 1 kg were collected from the abovesites. Pottery samples were washed off sticking soil, if any,
with water, wiped with soft cloth and sealed in a clean polythene bag with a label. To examine the possibility of correlation of pottery results with soil or clay, sub surface soil samples(about 1 kg) were collected from a depth of about 10 cm. Soilsamples were sun drenched, pebbles were removed and thensealed in clean polythene bags.
2.3. Sample preparation and irradiation. The samples
were powdered using agate pestle and mortar. The samples
were dried at 105 °C in a hot air oven for about 24 h to remove
any moisture content. Sample masses used were in the rangeof 75–150 mg. Samples were heat-sealed using polythene
sheets. Samples were irradiated for 7 h in E8 irradiation position of swimming pool type APSARA research reactor, Bhabha
Atomic Research Centre (BARC), Mumbai for medium andlong-lived activation products. The thermal neutron flux at thisposition was of the order of 5 × 1011 cm–2s–1. Short irradiationsof 1 min duration with samples of ~10 mg mass were carriedout using the pneumatic carrier facility (PCF) of Dhruva
research reactor, BARC for the activation products whose halflives are in the range of 2 min – 3 h. The thermal neutron flux

Figure 1. Location map of collection sites of pottery and soil samples.

at this position was of the order of 5 × 1013 cm –2 s –1. The
International Atomic Energy Agency (IAEA) certified reference material (CRM) SL-3 (Lake Sediment) was used as amultielement comparator. Samples along with the multielement comparator were irradiated in different batches. The
control samples, CRMs SL-1 and Soil-7 were prepared andirradiated along with multielement comparator in the similar
way to that of samples.
2.4. Radioactive assay and calculation of concentration.
After appropriate cooling, irradiated samples were mounted on
Perspex plates and the radioactive assay was carried out using
a 40% relative efficiency HPGe detector coupled to MCA with
8k conversion gain. The detector system had a resolution of
2.0 keV at 1332 keV γ-ray of 60 Co. The irradiated samples,comparator standard and control samples were counted in identical geometry with respect to the detector. Depending on thehalf-lives of radioisotopes, elements were divided into threegroups. The first group contained short-lived isotopes of elements like Al, Ca, Mn, Ti, and V. The second group contained
medium-lived isotopes of As, Br, Na, K, and Ga, and the thirdgroup contained long-lived isotopes of 10 elements like Fe, Cr,
Sc, Cs, Hf, and Rb. Measurement times were 60–1800 s for
short as well as medium-lived activation products and 2–20 h
for medium and long lived products. The measurement of theradioactivity of first group isotopes was made within 3 minafter the end of irradiation. Whereas for second and thirdgroups of elements, measurements began after 1 day cooling

TABLE 1: Name and coordinates of sites chosen for pottery and soil samples
S.N.

ID of Pottery

ID of Soil

Site

Location (Town/District)

LatitudeLongitude

1
2
3
4
5
6

P-1
P-2
P-3
P-4
P-5
P-6

S-1
S-2
S-3
S-4
S-5
S-6

Dantapuram
Jagathipadu
Pavuralakonda
Thotlakonda
Bavikonda
Boppikonda

Srikakulam
Srikakulam
Visakhapatnam
Visakhapatnam
Visakhapatnam
Tuni

18.15 N
18.28 N17.53 N
17.15 N17.14 N
17.21 N84.14 E
84.28 E
83.30 E
83.23 E
83.25 E
82.35 E

7

P-7

S-7

Gullacholangi

Kakinada

16.57 N

82.15 E

Application of Instrumental Neutron Activation Analysis for Chemical

period. The peak areas were evaluated using peak fit software
called PHAST, developed at our institute.18 Relative method of
NAA was used for the calculation of concentrations with an
IAEA CRM, SL-3 as reference standard.
3. Results and Discussion
The relevant nuclear data were taken from the literature.19,20
The concentrations of 20 elements determined from four replicate experiments in all samples and CRMs. The percentage
deviations of the determined concentrations in IAEA CRMs
SL-1 and Soil-7 are within ±8%. The determined values werein good agreement with their certified or information values.
Z-score values in these CRMs were found to be in the range of-2.0 to 1.8, which are found to be well below the accepted valueof ±3.
Results of the elemental concentrations in soil and pottery

J. Nucl. Radiochem. Sci., Vol. 9, No. 1, 2008

sa mple s a r e g iven i n Ta ble s 2 a nd 3, r e sp e ct ively.
Concentrations of major elements Al, Fe, Ti, K, Na, Mn, andBa are in the range of 8.0 to 0.03% whereas other elements arein the mg kg–1 range. The uncertainties reported in these twotables are due to standard deviations at ±1σ confidence level
arrived from four independent sample analysis and are within
10%.
Range, grand mean and % RSD of concentrations for different elements in all the seven pottery samples were calculated
and are given in Table 4. This table also gives similarly evaluated data for seven soil samples. It is observed that the mean
concentrations of As, Br, Ga, Co Hf, Cs, Cr, and Sc in potteries
are lower than soil samples. Concentrations of rest of the 12
elements in pottery samples are either higher or comparable tothat of soil samples. The %RSD concentrations of all elementsof seven pottery samples (column 6, Table 4) vary in the rangeof 11–80%. Similarly, the %RSD of concentrations of all ele-

TABLE 2: Concentrations (mg kg–1 unless mg g–1 is indicated) of elements in seven soil samples
Elements
Na*
Al*
K*
Sc
Ti*
V
Cr
Mn*
Fe*
Co
Ga
As
Br
Rb
Cs
Ba*
Hf
Th
U
Al/Sc
* mg g–1

S-1
2.1 ± 0.1
57.5 ± 2.2
13.5 ± 0.4
8.1 ± 0.4
5.31 ± 0.24
47.2 ± 4.2
64.8 ± 3.2
0.53 ± 0.04
28.2 ± 1.1
12.1 ± 0.9
8.3 ± 1.1
9.7 ± 1.6
2.5 ± 0.2
120.0 ± 2.8
1.3 ± 0.1
0.51 ± 0.01
14.2 ± 1.1
18.6 ± 0.8
1.7 ± 0.1
7099 ± 536

S-2
3.40 ± 0.08
81.6 ± 1.8
11.3 ± 0.8
10.8 ± 0.4
5.62 ± 0.24
44.8 ± 4.4
60.2 ± 3.8
0.77 ± 0.03
27.9 ± 1.0
13.7 ± 0.8
10.8 ± 1.0
11.9 ± 0.8
6.60 ± 0.45
150.0 ± 2.3
1.92 ± 0.12
0.56 ± 0.01
11.5 ± 1.0
15.4 ± 1.0
1.20 ± 0.127556 ± 326

S-3
1.42 ± 0.11
78.6 ± 1.6
11.8 ± 0.7
20.2 ± 0.3
7.8 ± 0.2
120.0 ± 2.5
174.6 ± 2.2
1.36 ± 0.02
54.2 ± 0.6
20.7 ± 0.6
16.4 ± 0.8
11.2 ± 0.7
6.1 ± 0.5
68.5 ± 3.7
1.70 ± 0.15
0.34 ± 0.02
9.6 ± 0.9
23.4 ± 0.7
1.7 ± 0.3
3891 ± 98

S-4
1.22 ± 0.11
84.6 ± 1.8
12.5 ± 0.5
21.6 ± 0.3
6.20 ± 0.32
97.9 ± 3.5
185.0 ± 2.0
0.96 ± 0.03
59.3 ± 0.5
21.2 ± 0.5
28.8 ± 0.5
17.9 ± 0.9
7.9 ± 0.4
102.0 ± 3.0
2.91 ± 0.22
0.36 ± 0.02
15.2 ± 1.2
26.9 ± 0.6
2.40 ± 0.08
3917 ± 100

S-51.10 ± 0.11
73.4 ± 1.7
12.0 ± 0.6
19.2 ± 0.3
6.20 ± 0.32
81.0 ± 3.9
193.0 ± 1.8
0.95 ± 0.03
61.3 ± 0.5
20.9 ± 0.5
28.3 ± 0.5
17.0 ± 1.0
7.6 ± 0.4
98.0 ± 3.0
3.2 ± 0.2
0.35 ± 0.02
17.0 ± 1.0
39.0 ± 0.4
1.9 ± 0.1
3823 ± 107

S-6
2.05 ± 0.1280.3 ± 2.0
11.0 ± 0.8
26.7 ± 0.2
4.90 ± 0.33
85.5 ± 3.8
81.7 ± 2.4
2.10 ± 0.05
42.4 ± 0.5
12.5 ± 0.9
15.4 ± 1.0
7.6 ± 0.6
6.3 ± 0.5
107.8 ± 2.9
1.81 ± 0.12
0.60 ± 0.01
12.8 ± 1.1
29.5 ± 0.61.30 ± 0.123007 ± 78

S-7
6.20 ± 0.06
34.6 ± 2.6
11.7 ± 0.7
21.9 ± 0.3
3.10 ± 0.34
53.1 ± 4.1
46.4 ± 4.4
0.33 ± 0.15
24.9 ± 1.2
9.0 ± 1.0
7.9 ± 1.2
3.8 ± 0.2
4.0 ± 0.6
65.3 ± 3.8
1.01 ± 0.09
0.43 ± 0.01
9.20 ± 0.07
24.6 ± 0.7
1.50 ± 0.11
1580 ± 156

TABLE 3: Concentrations (mg kg–1 unless mg g–1 is indicated) of elements in seven pottery samples
Elements
Na*
Al*
K*
Ca*
Sc
Ti*
V
Cr
Mn*
Fe*
Co
Ga
As
Br
Rb
Cs
Ba*
Hf
Th
U
Al/Sc
* mg g–1

P-1
3.02 ± 0.22
78.3 ± 1.6
20.6 ± 0.9
9.1 ± 0.8
17.6 ± 0.5
3.6 ± 0.5
66.7 ± 2.8
61.8 ± 2.4
0.47 ± 0.06
34.9 ± 0.8
5.0 ± 0.3
12.0 ± 1.0
3.3 ± 0.2
2.7 ± 0.2
162.9 ± 2.4
1.5 ± 0.1
1.62 ± 0.01
12.8 ± 0.6
18.0 ± 1.4
4.5 ± 0.24449 ± 156

P-2
3.9 ± 0.2
77.8 ± 1.4
23.2 ± 0.8
13.1 ± 1.1
12.7 ± 0.8
4.3 ± 0.4
58.0 ± 3.0
66.1 ± 2.9
0.62 ± 0.03
37.1 ± 1.0
5.8 ± 0.3
11.5 ± 0.9
2.6 ± 0.2
2.0 ± 0.2
188.7 ± 2.2
1.7 ± 0.1
0.54 ± 0.04
8.8 ± 0.9
38.2 ± 0.8
3.9 ± 0.26126 ± 401

P-3
4.5 ± 0.2
82.2 ± 1.5
18.5 ± 1.0
9.5 ± 0.8
13.1 ± 0.8
6.7 ± 0.4
88.2 ± 2.5
62.5 ± 3.0
0.66 ± 0.03
37.4 ± 1.0
6.3 ± 0.3
11.8 ± 1.0
3.5 ± 0.2
3.1 ± 0.3
94.4 ± 2.9
1.3 ± 0.1
0.69 ± 0.03
9.5 ± 0.9
29.3 ± 1.2
3.2 ± 0.26275 ± 400

9P-42.31 ± 0.25
62.5 ± 1.4
14.0 ± 0.8
9.6 ± 0.9
14.5 ± 0.7
8.2 ± 0.2
75.4 ± 2.6
70.0 ± 2.7
0.62 ± 0.03
49.0 ± 0.7
6.6 ± 0.2
11.3 ± 0.9
6.1 ± 0.1
2.0 ± 0.2
93.8 ± 2.9
1.2 ± 0.1
0.37 ± 0.02
12.8 ± 0.6
32.8 ± 1.1
2.9 ± 0.24310 ± 230

P-5
2.1 ± 0.23
68.5 ± 1.4
15.2 ± 0.7
7.6 ± 0.6
14.7 ± 0.7
6.31 ± 0.4
82.9 ± 2.4
66.4 ± 2.6
2.70 ± 0.05
45.9 ± 0.6
7.2 ± 0.3
10.8 ± 0.9
6.9 ± 0.1
4.1 ± 0.3
85.3 ± 3.2
1.3 ± 0.1
0.36 ± 0.02
11.6 ± 0.6
25.1 ± 1.3
6.8 ± 0.1
4660 ± 241

P-62.90 ± 0.23
86.5 ± 1.5
18.5 ± 0.8
12.5 ± 1.0
16.4 ± 0.6
7.6 ± 0.3
102.5 ± 2.2
90.5 ± 2.2
0.91 ± 0.02
54.2 ± 0.6
9.3 ± 0.3
13.9 ± 0.8
2.0 ± 0.2
2.6 ± 0.2
91.2 ± 3.0
1.2 ± 0.1
0.37 ± 0.02
13.2 ± 0.7
22.7 ± 1.3
2.3 ± 0.25274 ± 213

P-7
5.8 ± 0.1
66.6 ± 1.8
8.9 ± 0.6
14.4 ± 1.2
21.2 ± 0.5
7.2 ± 0.3
116.9 ± 2.1
143.9 ± 1.4
0.85 ± 0.02
58.0 ± 0.5
10.7 ± 0.6
9.8 ± 1.1
2.3 ± 0.2
3.5 ± 0.3
55.5 ± 4.1
1.5 ± 0.1
0.49 ± 0.04
8.1 ± 1.0
13.8 ± 1.6
3.0 ± 0.2
3113 ± 112

10SarathiJ. Nucl. Radiochem. Sci., Vol. 9, No. 1, 2008

TABLE 4: Mean concentrations (mg kg–1 unless mg g–1 is indicated) of pottery and soil samples
Elements
Min.
2.1
62.5
8.9
7.6
12.7
3.6
58.0
61.8
0.47
34.9
5.0
9.8
2.0
2.0
55.5
1.2
0.36
8.1
13.8
2.3

Na*
Al*
K*
Ca*
Sc
Ti*
V
Cr
Mn*
Fe*
Co
Ga
As
Br
Rb
Cs
Ba*
Hf
Th
U
* mg g–1

Max.
5.8
86.5
23.2
14.4
21.2
8.2
116.9
143.9
2.7
58.0
10.7
13.9
6.9
4.1
188.7
1.7
1.62
13.2
38.2
6.8

Pottery (N = 7)
Mean
SD
3.5
1.3
74.6
8.8
16.9
4.7
10.8
2.5
15.7
2.9
6.2
1.7
84.3
20.3
80.1
29.7
0.97
0.77
45.2
9.0
7.3
2.0
11.6
1.2
3.8
1.9
2.8
0.8
110.2
47.3
1.4
0.2
0.63
0.45
10.9
2.1
25.7
8.4
3.8
1.5

%RSD
38
12
28
23
19
27
24
37
80
20
28
11
50
27
43
13
71
19
33
40

ments of seven soil samples (column 11, Table 4) vary in therange of 23–71% (except 7% for K). The observed large scatter suggests that the origin/source of these pottery as well as
soil samples may not be the same.
For the preliminary information on provenance studies, theelemental concentration ratios of the two non-volatile elements
Al and Sc were evaluated for soil (Table 2) and pottery (Table3) samples under study. The concentration ratios of Al to Sc in
pottery samples are expected to remain constant during pottery
making process as well as afterwards withstanding wear andtear as they are non-volatile elements. The ratios of Al and Sc
values of seven soil samples are shown in Figure 2. From thehistogram of concentration ratios, inter-site distance groupingof the soil samples was done and they fall into four groups: (i)S1 and S2; (ii) S3, S4, and S5; (iii) S6; and (iv) S7.
Although the number of samples is less, it is apparent thatthey (soil samples) belong to four distinct groups. In view ofthis, to validate the visual grouping, the results were subjected
to cluster analysis using STASTISTICA 5.1 statistical package.1,5 We have attempted to group these samples by considering some key elements namely Rb, Cs, Ba, Sc, Cr, Mn, Fe, Co,
9000

Min.
1.1
34.6
11.0
8.1
3.1
44.8
46.4
0.33
24.9
9.0
7.9
3.8
2.5
65.3
1.0
0.29
9.2
15.4
1.2

SD
1.8
18.0
0.8

%RSD
71
26
7

6.4
1.4
28.5
59.5
0.59
16.5
5.1
8.8
5.0
1.9
29.9
0.8
0.11
3.0
7.7
0.4

36
25
38
57
59
36
32
53
44
33
29
41
24
23
30
25

and Hf. Sodium and K were excluded as they are expected tobe mobile during weathering process. The cluster analysis
dendogram of seven soil samples are shown in Figure 3. The
cluster analysis also supports the above finding that they belong
to four groups. The cluster analysis is based on the calculationof the distances between the points representing the samples in
the principal axes. The lengths of the links in the dendogram
are proportional to the distances between the groups of thesamples. From the Figure 3, it is clear that grouping by bothmethods lead to similar conclusion and thus validated our
method of establishing provenance. Further the percentage
deviations between two same and different group samples werecarried out. The normalized %deviations of concentrations of
all elements of S1 with respect to corresponding elements in S7
belonging to farthest locations are in the range of 11–155%
except for Ga (5%) e.g., 11.1% for V and 155% for As. The
normalized %deviations of S1 with respect to S7 were arrived
at by dividing difference between S1 and S7 with S7 and thenmultiplying with 100. In view of large scatter in the normalized deviation, it could be concluded that S1 and S7 are of different origin. Similarly, the calculated normalized %deviationsof concentrations of S4 with respect to S5 are within 10% for
most of the elements, which suggest that they are of similar
origin. It may be noted that S4 and S5 belong to nearby locations. The method of grouping the soil samples was in agree-

7000
14000

6000

12000

5000

Linkage Distance��������������������������������

8000

Soil (N = 7)
Max.
Mean
6.2
2.5
84.6
70.1
13.5
12.0
- Not measured 26.7
18.1
7.8
5.6
120.0
75.6
193.0
105.1
2.1
1.0
61.3
45.8
21.2
15.7
28.8
16.6
17.9
11.3
7.9
5.9
150.0
101.6
3.9
2.0
0.6
0.45
17.0
12.8
39.0
25.3
2.4
1.7

4000
3000
2000
1000
S1

S2

S3

S4

S5

S6

S7

������������
Figure 2. Histogram of concentration ratios of Al to Sc for seven soil
samples.

10000
8000
6000

�������
�������

4000

0�������

�������

2000
S7

S6

S4

S5

S3

S2

S1

Figure 3. Dendogram of seven soil samples obtained by cluster analysis using nine key elements (Sc, Cr, Mn, Fe, Co, Rb, Cs, Ba, andHf).

Application of Instrumental Neutron Activation Analysis for Chemical

J. Nucl. Radiochem. Sci., Vol. 9, No. 1, 2008

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Figure 5. Dendogram of seven pottery samples obtained by cluster
analysis using nine key elements (Sc, Cr, Mn, Fe, Co, Rb, Cs, Ba, andHf).

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Figure 4. Histogram of concentration ratios of Al to Sc for sevenpottery samples.

ment with our pre-knowledge of soil collection and vis-à-vis
soil origin and thus validates our methodology of establishingprovenance.
Similar analysis for pottery samples was carried for establishing grouping/provenance. Both concentration ratio valuesof Al to Sc and statistical cluster analysis results were used forthe grouping of potteries. Histogram of concentration ratios of
Al and Sc values is shown in Figure 4. From this figure, itappears that they fall into four groups as given here: (i) P1, P4,
and P5; (ii) P2 and P3; (iii) P6; and (iv) P7. These results were
subjected to statistical cluster analysis as done for soil samples.
The dendogram of pottery samples obtained by cluster analysis
is given in Figure 5. It is affirmed from the figure that they fall
into same four groups as observed from the concentration ratiosof Al to Sc. From Figure 1, it is clear that P3, P4, and P5 werecollected from nearby locations. However, results of both concentration ratio values of Al to Sc and cluster analysis suggestthat the pottery sample P3 differs from potteries of P4 and P5.
This is taken as a clue that P3 may not have been prepared withthe same source clay as that of P4 and P5. Further the normalized %deviations of concentrations of all elements of P1 withrespect to corresponding elements in P7, belonging to farthest
locations, are in the range of 17–230%. This confirms that P1
and P7 are of different origin. Similarly, the normalized%deviations for P4 with respect to P5 (belonging to nearby
locations) are within 10% for many elements, which suggeststhat they are of similar origin.
4. Conclusions
INAA using reactor neutrons and high resolution γ-ray spectrometry was used to determine concentrations of 20 elementsof significance in ancient pottery samples. Both the results of
Al to Sc concentration ratios and statistical cluster analysis
using nine key elements suggest that the pottery samples analyzed fall into four groups. Similar analyses on soil samples
suggest that they also belong to four groups. Our approach of
establishing provenance or grouping through elemental composition in conjunction with cluster analysis could be used forarriving at the source though the number of samples is less.
Our future work on provenance study is being extended to morenumber of such samples collected from different places ofAndhra Pradesh and its neighbouring states.
Acknowledgements. The authors are thankful to Dr. V.
Venugopal, Director, Radiochemistry and Isotope Group,
BARC and Dr. V.K. Manchanda, Head, Radiochemistry
Division, BARC for their keen interest, encouragement, andsupport for this work. Grateful acknowledgements are due to
Dr. J. Kedareswari, Director, Department of Archaeology andMuseums, Government of Andhra Pradesh for her support andinterest in this work. Authors are thankful to the personnel of
Apsara and Dhruva reactors for the cooperation during theirradiation of samples and also to Dr. R.K. Singhal and Shri
Ajay Kumar, HPD, BARC for help in statistical analysis.
Authors from GITAM Prof. N. Lakshmana Das and D.Partha
Sarathi acknowledge UGC, New Delhi for the financial assist a nce u nder Major Resea rch P roje ct a nd UG C-DA E
Consortium for Scientific Research, Mumbai for the financial
assistance under “Archaeometry studies use INAA” since
September 2006.
References(1) J. W. Beal and I. Olmez, J. Radioanal. Nucl. Chem. 221, 9(1997).
(2) H. R. Tykot, Proc. the international school of physics“Enrico Fermi” Course CLIV; Eds. M. Milazzo and M.
Piacentini, (2004).
(3) F. Monroy-Guzman and P. Fournier, IAEA Technical
Report Series No 416, International Atomic Energy
Agency, Vienna, Chapter-9, 147 (2003).
(4) IAEA Technical Report Series No 416, International Atomic
Energy Agency, Vienna, Chapter-1, 3 (2003).
(5) M. Balla, G. Keomley, and Gy. Rosner, J. Radioanal. Nucl.
Chem. 141, 7 (1990).
(6) I. Rossini, J.C. Abbe, B. Guevara, and R. Tenorio, J.
Radioanal. Nucl. Chem. 170, 411 (1993).
(7) D. Tenorio, M.G. Alamzan-Torres, F. Monroy-Guzman,
N.L. Rodriguez-Garcia, and C. Longoria Luis, J.
Radioanal. Nucl. Chem. 266, 471 (2005).
(8) W.D. James, R. L. Brewing, and H.J. Hafer, J. Radioanal.
Nucl. Chem. 192, 109 (1995).
(9) M. Roumie, P. Reynolds, C. Atallah, E. Bakraji, K.
Zahraman, and B. Nsouli, Nucl. Instrum. Methods B, 249,
612 (2006).
(10) E. H. Bakraji, J. Radioanal. Nucl. Chem. 264, 645 (2005).
(11) K. T. Biro, J. Radioanal. Nucl. Chem. 265, 235 (2005).
(12) E. Witkowska, K. Szczepaniak, and M. Biziuk, J.
Radioanal. Nucl. Chem. 265, 141 (2005).
(13) C. Menninga, L Minc, M. D. Glascock, and C. Descantes
C, J. Radioanal. Nucl. Chem. 266, 235 (2005).
(14) U.M.Vinagre Filho, R.M. Latini, A.V.B. Bellido, A.
Buarque, and A.M. Borges, Brazilian J. of Phys. 35, 779(2005).
(15) R. Acharya, Ph. D. Thesis, University of Mumbai, Mumbai,
India (2000).
(16) R. Acharya and A.V.R. Reddy, IANCAS Bulletin, Indian
Association of Nuclear and Allied Scientist, Bhaba Atomic
Research Centre, Vol II (2), 111 (2003).

12

J. Nucl. Radiochem. Sci., Vol. 9, No. 1, 2008(17) B. Subrahmanyam and E. Sivanagi Reddy, Dantapuram(An early Buddhist site in Andhra Pradesh) published by
Department of archaeology and museums, Government ofAndhra Pradesh, Hyderabad, India (2002).
(18) P.K. Mukhopadhyay, in: Proc. the symposium on Intelligent

SarathiNuclear Instrumentation, Mumbai, India, 2001.
(19) F. De Corte and A. Simonits, J. Radioanal. Nucl. Chem.
133, 43 (1989).
(20) F. De Corte and A. Simonits, Atomic Data Nucl. Data
Tables 85, 47 (2003).