Professional Documents
Culture Documents
https://doi.org/10.1007/s10967-018-5863-8(0123456789().,-volV)(0123456789().,-volV)
Abstract
The k0-based internal mono-standard neutron activation analysis (IM-NAA) method was used to analyze large size
archaeological clay brick samples for grouping study. Elemental concentration ratios with respect to Sc were derived using
IM-NAA in conjunction with in situ relative detection efficiency. Preliminary grouping was carried out using bi-plot of Ce/
Sc and La/Sc ratios and the grouping was confirmed by statistical cluster analysis. Concentration results of a large size
sample were compared with analysis of small size replicates by both relative NAA and IM-NAA methods. The method
adopted here is a standard-less one for grouping combined with provenance study of archaeological artifacts.
Keywords Ancient clay bricks IM-NAA Concentration ratio Non-standard geometry Lanthanides Grouping study
123
Journal of Radioanalytical and Nuclear Chemistry
clay ceramics through a non-destructive analytical method 14 were from Visakhapatnam regions (Samples: 5–18) of
is preferred over a wet-chemical method. Analysis using India. In our previous study, clay brick samples from
conventional radioanalytical techniques including X-ray Visakhapatnam region were analyzed by relative INAA
fluorescence [11], ion beam analysis [12], and neutron method [10]. Sample collection locations are illustrated in
activation analysis (NAA) are conducted using a small Fig. 1. Samples were analyzed directly without any
sample size and similar/identical matrix matched standard chemical treatment and destruction. For homogeneity study
[9, 10]. Other non-destructive analytical techniques are as well as to compare the large size sample results obtained
also applied to find the physical and chemical properties of by IM-NAA of one sample, three replicate small size
archaeological objects to achieve better restoration and samples were analyzed by both relative INAA and IM-
conservation [13]. In our previous work, numerous ancient NAA methods. Samples were dried at 100 °C in a hot air
potteries and brick samples were analyzed using relative oven for approximately 24 h to remove moisture content.
and k0-based INAA methods for provenance studies Based upon previous studies on large clay ceramics sam-
[10, 14, 15]. In our work, routinely used small size samples ples, the representative sample size has been found to be
are in the mass rage of 100–250 mg, whereas sample mass 1 g and above [14]. However to get higher counts (or lower
above 10 g has been considered as large size sample. Large counting statistical error) in the peak of interest of corre-
size sample analysis is feasible in NAA because of high sponding gamma-ray, about 10 g of sample is better choice
penetration powers of neutrons and gamma rays. Compared to be analyzed using relatively lower neutron flux
with the analysis of a small size sample (100 mg), the (107 cm-2 s-1). Thus large size samples (11–60 g) were
analysis of a large sample is advantageous for enhanced chosen and doubly sealed in polyethylene for irradiation.
analytical representativeness of results. In the present Samples were irradiated for 4 h with highly thermalized
work, we adopted the k0-based internal mono-standard (99.97%) reactor neutrons with neutron flux of approxi-
NAA (IM-NAA) method to analyze the clay brick samples. mately 107 cm-2 s-1 at the graphite reflector position of
However, this method encounters problems of neutron self- Advanced Heavy Water Reactor (AHWR) Critical Facility
shielding and gamma-ray self-attenuation [16, 17]. These (CF), BARC, Mumbai. Samples were transferred to the
problems can be easily addressed through the IM-NAA laboratory after a cooling time of 2 h and then mounted on
method using in situ detection efficiency [18–21]. The IM- standard Perspex plates for radioactive assay. In the present
NAA method was developed at Radiochemistry Division, method counting geometry/distance with respect to the
Bhabha Atomic Research Center (BARC), Mumbai for detector was flexible because this method uses in situ rel-
large and small sample analyses by using reactor neutrons ative detection efficiency of each sample for calculating
and applied to various matrices of wheat, coal, and nuclear elemental concentrations. Gamma ray measurement was
material samples [14, 20–22]. Our laboratory participated performed using a 40% relative efficiency HPGe detector
in the International Atomic Energy Agency (IAEA) coor-
dinated research project (CRP) for inter comparison exer-
cise of non-standard geometry size pottery replica analysis
using IM-NAA [21]. This method is simpler than the
conventional k0-based NAA method and provides ele-
mental concentration ratio with respect to one of the ele-
ments present in the sample called internal mono-standard.
A priori knowledge of the concentrations of the internal
mono-standard is required to convert relative to absolute
concentration [19]. In the present work, the IM-NAA
method using in situ relative detection efficiency was
applied to large and non-standard geometry clay brick
samples for their chemical composition in order to arrive at
the grouping or provenance through elemental concentra-
tion ratios with respect to Sc as the internal mono-standard.
Experimental
123
Journal of Radioanalytical and Nuclear Chemistry
123
Journal of Radioanalytical and Nuclear Chemistry
Table 1 Nuclear data used for k0-based IM-NAA method calculations [23, 24]
Target element Nuclear reaction Product half life Main c-ray energies, keV (intensity, %) k0,Au (s, %)
23
Na Na(n, c)24Na 14.997 h 1368.63 (99.99), 2754.01 (99.86) 4.68E-02 (0.6), 4.62E-02 (0.9)
41
K K(n, c)42K 12.355 h 1524.6 (18.08) 9.46E-04 (0.6)
45
Sc Sc(n, c)46Sc 83.79 days 889.28 (99.98), 1120.54 (99.99) 1.22E?00 (0.4), 1.22E?00 (1.1)
50
Cr Cr(n, c)51Cr 27.704 days 320.08 (9.91) 2.62E-03 (0.5)
55
Mn Mn(n, c)56Mn 2.5789 h 846.76 (98.85), 1810.73 (26.9) 4.96E-01 (0.6), 1.35E-01 (0.4)
58
Fe Fe(n, c)59Fe 44.495 days 1099.24 (56.5), 1291.59 (43.2) 7.77E-05 (0.5), 5.93E-05 (0.4)
59
Co Co(n, c)60Co 1925.28 days 1173.23 (99.85), 1332.49 (99.98) 1.32E?00 (0.4), 1.32E?00 (0.5)
64
Zn Zn(n, c)65Zn 243.93 days 1115.54 (50.04) 5.72E-03 (0.4)
75
As As(n, c)76As 1.0942 days 559.10 (45.0) 4.83E-02 (1.6)
133 134
Cs Cs(n, c) Cs 2.0652 years 604.72 (97.62), 795.86 (85.46) 4.76E-01 (2.0), 4.15E-01 (2.0)
139
La La(n, c)140La 1.679 days 487.02 (45.5), 1596.21 (95.40) 6.37E-02 (0.9), 1.34E-01 (1.1)
140
Ce Ce(n, c)141Ce 32.511 days 145.44 (48.40) 3.66E-03 (0.9)
151
Eu Eu(n, c)152Eu 13.517 years 344.28 (26.59), 1408.01 (20.87) 1.19E?01 (0.9), 9.36E?00 (0.6)
176
Lu Lu(n, c)177Lu 6.647 days 208.36 (10.36) 7.14E-02
180
Hf Hf(n, c)181Hf 42.39 days 133.02 (43.3) 2.37E-02 (0.6)
232
Th Th(n, c)233Pa 26.975 days 311.90 (38.5) 2.52E-02 (0.5)
Table 2 Results of two representative brick samples of Visakhapat- size samples by IM-NAA, the uncertainties on concentra-
nam and Hyderabad regions by IM-NAA using Sc as internal mono- tion ratios were evaluated from the standard deviation of
standard replicate (N = 3) analyses and the % RSD are in the range
Element ratio x/Sc Ancient brick samples of 2.4–5.0%. In the case of relative INAA, the percentage
Visakhapatnam Hyderabad
combined uncertainties on elemental concentration ratios
with respect to Sc are in the range of 3.9–6.2% and these
Na 119 ± 4 1062 ± 35 values have been arrived from propagation of % RSD
K 1255 ± 42 2182 ± 100 values of replicate analyses and uncertainty on Sc con-
Cr 6.27 ± 0.21 3.62 ± 0.15 centration (3.2% at k = 1). The concentration ratios with
Mn 45.4 ± 2.6 40.3 ± 2.0 respect to Sc of the clay ceramic sample analyzed through
Fe 2943 ± 122 1776 ± 73 the three methods were found to be in good agreement
Co 1.37 ± 0.07 0.8 ± 0.02 (Table 3). The IM-NAA method does not require any
Zn 4.59 ± 0.34 2.84 ± 0.19 external or internal standards for obtaining elemental
As 0.18 ± 0.02 0.26 ± 0.02 concentration ratio. The analysis is more advantageous in
Cs 0.14 ± 0.01 0.15 ± 0.01 large size samples than in small samples by IM-NAA,
La 2.94 ± 0.09 3.83 ± 0.12 because uncertainties due to f, a and Q0 are not included to
Ce 6.21 ± 0.24 6.61 ± 0.23 the combined uncertainty.
Eu 0.071 ± 0.006 0.086 ± 0.007 The elemental concentration ratios (Table 2), including
Lu 0.034 ± 0.002 0.026 ± 0.002 La/Ce ratios, in both locations were found different. The
Hf 0.42 ± 0.01 1.07 ± 0.04 results showed that the origin of samples might be differ-
Th 0.82 ± 0.03 1.79 ± 0.06 ent. Further grouping confirmation was done through Ce/Sc
La/Ce 0.47 0.57 vs. La/Sc bi-plot and multivariate statistical cluster analysis
(CA) programs [26]. The preliminary grouping study was
performed based on bi-plot of Ce/Sc versus La/Sc con-
centration ratio values. La and Ce were selected because of
values are given in Table 3. IAEA RM SL-1 (sediment their similar geochemical properties. These results of the
matrix) was used as the comparator for mass fraction preliminary grouping of clay brick samples resulted in
determination in relative method of INAA [25]. The three broad grouping as demonstrated in Fig. 3. Samples of
uncertainty values for large size sample were obtained in bricks from the Hyderabad region fell in one group: Group
similar way to that given in Table 2 and the combined I (Samples 1-4), and samples from the Visakhapatnam
uncertainty values are in the range of 3.1–8.9%. For small region fell two groups: Groups II (Samples 5–13) and III
123
Journal of Radioanalytical and Nuclear Chemistry
Table 3 Results of one representative brick sample analyzed by relative INAA and IM-NAA methods
Element (x/Sc) Small size sample by relative NAA (N = 3) Small size sample by IM-NAA (N = 3) Large size sample by IM-NAA
123
Journal of Radioanalytical and Nuclear Chemistry
study using concentration ratios of large size sample agreed 4. Guha Thakurta T (2013) The production and reproduction of a
well with the collection history and exhibited favorable monument: the many lives of the Sanchi stupa. South Asian Stud
29:77–109
correlation with small size sample analysis by relative 5. Lopez-arce P, Garcia-guinea J, Gracia M, Obis J (2003) Bricks in
NAA method. Results indicated that one large size repre- historical buildings of Toledo City: characterisation and restora-
sentative sample analysis is sufficient compared to many tion. Mater Charact 50:59–68
replicate small size sample analyses. Cluster analysis using 6. Tite MS (2008) Ceramic production, provenance and use—a
review. Archaeometry 50:216–231
elemental concentration ratios of eleven elements con- 7. IAEA-1501 (2011) Nuclear techniques for cultural heritage
firmed the preliminary grouping arrived by Ce/Sc vs. La/Sc research. IAEA-1501, Vienna
values. Analysis of such ceramic sample with non-standard 8. Goffer Z (1983) Physical studies of archaeological materials.
geometries by IM-NAA along with in situ detection effi- RepProg Phys 46:1193–1234
9. Beal JW, Olmez I (1997) Provenance studies of pottery fragments
ciency is a very powerful approach for grouping combined from Medieval Cairo, Egypt. J Radioanal Nucl Chem 221:9–17
with provenance study. 10. Dasari KB, Acharya R, Lakshmana Das N (2013) Application of
INAA to ancient bricks for grouping study using trace elements.
Acknowledgements Authors from GITAM University thank Dr. P.K. J Radioanal Nucl Chem 298:699–705
Pujari, Head, Radiochemistry Division, BARC for the support and 11. Bendaoud R, Guilherme A, Zegzouti A, Elaatmani M, Coroado J,
encouragement. Authors thankfully acknowledge University Grants Carvalho ML, Queralt I (2013) Elemental mapping of moroccan
Commission-Department of Atomic Energy Council of Scientific enameled terracotta tile works (Zellij) based on X-ray micro-
Research (UGC-DAE CSR), Mumbai Centre for the project and analyses. Appl Radiat Isot 82:60–66
financial assistance and Dr. P. Gayatri, Ex. Director, Department of 12. Dasari KB, Chhillar S, Acharya R, Ray DK, Behera A, Laksh-
Archaeology and Museum, united Andhra Pradesh, Hyderabad for mana Das N, Pujari PK (2014) Simultaneous determination of Si,
providing authentic samples. Authors thank nuclear reactor crew Al and Na concentrations by particle induced gamma-ray emis-
members of the AHWR CF and Dhruva reactor, BARC, Mumbai for sion and applications to reference materials and ceramic
their help during sample irradiation. archaeological artifacts. Nucl Instrum Meth B 399:37–41
13. Adraens A (2005) Non-destructive analysis and testing of
museum objects: an overview of 5 years of research. Spec-
trochimica Act Part B 60:1503–1516
References 14. Dasari KB, Acharya R, Swain KK, Lakshmana Das N, Reddy
AVR (2010) Analysis of large and non-standard geometry sam-
1. Ranaweera MP (2004) Ancient stupas in Sri Lanka—Largest ples of ancient potteries by internal monostandard neutron acti-
brick structures in the world. CHS Newsletter No 70, Construc- vation analysis using in situ detection efficiency. J Radioanal
tion History Society, London Nucl Chem 286:525–531
2. Padma S (2008) Material culture and the emergence of urban 15. Partha Sarathi D, Acharya R, Nair AGC, Lakshminaryana S,
Buddhism in Andhra. In: Padma S, Barber AW (eds) Buddism in Lakshmana Das N, Reddy AVR (2008) Application of instru-
the Krishna River valley of Andhra. State University of New mental neutron activation analysis for chemical composition
York Press, Albany, pp 11–41 analysis of Ancient potteries from Buddhist sites of Andhra
3. Miriello D, Lezzerini M, Chiaravalloti F, Bloise A, Apollaro C, Pradesh: part I. J Nucl Radiochem Sci 9:7–12
Crisci GM (2013) Replicating the chemical composition of the 16. Vasilopoulou T, Tzika F, Koster-Ammerlaan MJJ, Stamatelatos
binder for restoration of historic mortars as an optimization IE (2011) Large sample neutron activation analysis of a reference
problem. Comput Concr 12:553–563 inhomogeneous sample. J Radioanal Nucl Chem 289:731–737
123
Journal of Radioanalytical and Nuclear Chemistry
17. Bode P, Overwater RMW, De Goeij JJM (1997) Large sample 22. Shinde AD, Acharya R, Reddy AVR (2017) Analysis of zirco-
neutron activation analysis: present status and prospects. J Ra- nium and nickel based alloys and zirconium oxides by relative
dioanal Nucl Chem 16:5–11 and internal monostandard neutron activation analysis methods.
18. Sueki K, Kobayashi K, Sato W, Nakahara H, Tomizawa T (1996) Nucl Eng Tech 49:562–568
Nondestructive determination of major elements in large samples 23. De Corte F, Simonits A (2003) Recommended nuclear data for
by prompt c-ray neutron activation analysis. Anal Anal Chem use in the k0 standardization of neutron activation analysis.
68:2203–2209 Atomic Data Nucl Data Tables 85:47–67
19. Nair AGC, Acharya R, Sudarshan K, Gangotra S, Reddy AVR, 24. National Nuclear Data Center. http://www.nndc.bnl.gov. Acces-
Manohar SB, Goswami A (2003) Development of an internal sed 15 Feb 2018
monostandard instrumental neutron activation analysis method 25. IAEA RM SL-1 (1999) Reference sheet on ‘‘Trace and minor
based on in situ detection efficiency for analysis of large and elements in lake sediment Reference Material (RM) IAEA-SL-1,
nonstandard geometry samples. Anal Chem 75:4868–4874 International Atomic Energy Agency (IAEA). IAEA RM SL-1,
20. Acharya R, Nair AGC, Sudarshan K, Reddy AVR, Goswami A Vienna
(2007) Development and applications of the k0-based internal 26. Oliveira PMS, Munita CS, Hazenfratz R (2010) Comparative
mono standard INAA method. Appl Radiat Isot 65:164–169 study between three methods of outlying detection on experi-
21. Acharya R, Swain KK, Dasari KB, Shinde AD, Pujari PK, Reddy mental results. J Radioanal Nucl Chem 283:433–437
AVR (2014) Application of k0-based internal monostandard NAA 27. Johnson RA, Wichern DW (1992) Applied multivariate statistical
for large sample analysis of clay pottery: as a part of inter analysis, 3rd edn. Prentice Hall, New Jersey
comparison exercise. J Radioanal Nucl Chem 300:517–521
123