To obtain chemical compositional information to elucidate the provenance of cuneiform clay tablets, we conducted non-destructive chemical analysis of clay tablets originating from Iraq and Turkey. Chemical compositional data were obtained using portable X-ray fluorescence analyzers and multivariate analysis was applied for the obtained data. Chemical analysis data were collected for 540 clay tablets stored in the Yale Babylonian Collection of Yale University (in 2009, 2011, and 2012), and 94 clay tablets including bullae and seals stored in the British Museum (in 2013).

Cuneiform clay tablets made during the Mesopotamian period were used as writing media for cuneiform characters. The use of clay tablets dates back to around 3300 BC. A large number of clay tablets were made in the Ur III period (2112 BC to 2004 BC). Economic, administrative, or agricultural information was recorded on the clay tablets. In this research, chemical analysis was conducted on the economic and administrative clay tablets whose information on the provenance was available.

The clay tablets analyzed in this study including bullae and sealings were made in the following 21 areas of Iraq and Turkey: Ur, Larsa, Lagash, Uruk, Umma, Adab, Drehem, Nippur, Kish, Borsippa, Dilbat, Babylon, Sippar, Nusi, Nimrud, Nineveh, Tell Brak, Tell Halaf, Boghazkoy, Kultepe, and Alalakh (Figure 1). The clay tablets originated from the Early Dynasty period (2900 BC to 2340 BC) to the Achaemenid period (547 BC to 331 BC). Table 1 summarizes the provenance, period and sample numbers of the cuneiform clay tablets studied.

Neutron activation analysis has been previously used to analyze clay tablets (Artzy et al., 1976; Dobel et al., 1977; Goren et al., 2009) . However, this method is not favorable because the method is destructive. In contrast, a recently developed portable X-ray fluorescence analyzer (pXRF) is non-destructive and quick, with good sensitivity. In-situ analysis using pXRF has been applied to the various fields including archaeology and artifacts (e.g., Williams-Thorpe et al., 2008; Cesareo et al., 2008 ). Chemical compositional analysis of clay tablets using pXRF has been previously performed by Goren et al. (2010) , mainly on clay tablets from Egypt and Boghazkoy (Hattusa). In this study, we carried out the chemical analysis of clay tablets from Iraq and Turkey. Clay tablets from Egypt were not analyzed in this research.

The pXRFs for the chemical analysis of the clay tablets were the pXRF α4000 (Innov-X Systems, Inc., Waltham, MA, USA), used at Yale University in 2009 and 2011, and the pXRF Delta Premium (Innov-X Systems, Inc.), used at Yale University in 2012 and at the British Museum in 2013. Silica and alumina are the major components of clay tablets (Goren et al., 2010) . Because the pXRF α4000 cannot analyze these components, analysis was conducted using “Soil Mode” in which the other elements can be analyzed with good precision without measurements of Si and Al. Although the pXRF Delta Premium can analyze Si and Al, the analysis was also conducted using “Soil Mode” to correspond with data collection from the pXRF α4000. Analysis with the pXRF α4000 was conducted in “Leap Mode” for light elements (for 1 min) and in “Standard Mode” for heavy elements (for 1 min). Analysis with the pXRF Delta Premium was conducted using three different filters for 20 s, respectively. Before analysis using both analyzers, calibration was carried out using 10 reference rocks (JA-1, JA-2, JB-1b, JB-2, JB-3, JG-1a, JG-2, JGb-1, JR-1, and JR-2) prepared by the Geological Survey of Japan (Imai et al., 1995) . In the pXRF α4000 analysis, calibration showed good precision for the following elements: Ca (3832), K (2294), Fe (2967), Ti (192), Rb (4), Sr (9), Mn (101), and Zn (6). Figures in parentheses are the standard deviation (1σ) (in μg/g) for the calibration of each element. Besides the above elements, Cr, Ni, As, Zr, and Ba were also frequently detected in the clay tablets. Details on the pXRF α4000 analysis were described in Uchida et al. (2011) and Sterba et al. (2011) . Calibration of the pXRF Delta Premium was performed using a method similar to that used for the pXRF α4000. Calibration was conducted with good precision for the following

Abbreviations: ENB, ED, Early Dynasty period (c. 2900-2340 BC); EDIII, Early Dynasty III period (c. 2600-2340 BC); OAkk, Old Akkadian period (2334-2154 BC); UrIII, Ur III period (2112-2004 BC); OB, Old Babylonian period (c. 2000-1595 BC); MB, Middle Balylonian period (c. 1595-1155 BC); ENB, Early Neo-Babylonian period (1155-626 BC); NB, Neo-Babylonian period (626-539 BC); AC, Achaemenid period (547-331 BC); AS, Assyrian period (2025-612 BC); OAss, Old Assyrian period (2025-1393 BC); NAss, Neo-Assyrian period (911-612 BC); Ht, Hittite period (c. 1680- 1190 BC).

elements: Ca (1389), K (549), Fe (364), Ti (65), Rb (2), Sr (5), Mn (73), Zn (6), V (16), Cr (14), Cu (7), As (2), Y (1), Zr (2), and Pb (3). In addition to the above elements, Ni, S, Cl, and Co were also frequently detected in the clay tablets.

The clay tablets were classified into four groups, as presented above, based on the multivariate analyses including the principal component analysis, cluster analysis (Ward’s method), and discriminant analysis. This grouping was determined mainly by the contents of Ca, K, and Fe. In particular the Ca content was essential for the grouping. The Ca content in the clay tablets decreases remarkably in the groups in the following order (Figure 3): the southern area (Alalakh) in Turkey (Group 4: 22.0% in average), the upper stream area of the Tigris and Euphrates River (Group 2: 13.3%), the lower stream area of the Tigris and Euphrates River (Group 1: 11.0%), and the northern and central areas (Boghazkyoy and Kultepe) in Turkey (Group 3: 4.1%). As the raw materials of clay tablets comprised sediments from rivers or canals, their chemical content is likely controlled by the surrounding geology, especially the distribution of limestone.

Goren et al. (2010) conducted non-destructive chemical analysis using pXRF and multivariate analysis for clay tablets mainly from Ugarit (corresponding to Alalakh/Group 4 in this study), Mitanni and Assyria (corresponding to the upper stream area of the Tigris and Euphrates River/Group 2 in this study), Babylonia (corresponding to the lower stream area of the Tigris and Euphrates River/Group 1 in this study), and Hattusa (corresponding to Boghazkyoy and Kultepe/Group 3 in this study). Clay tablets from Egypt were also included in that study. On the basis of multivariate analysis, Goren et al. (2010) classified these clay tablets into five groups: Ugarit, Mitanni, Babylonia, Hattusa, and Egypt. They suggested that the above grouping might appear in a Ti-K diagram. In this context, we drew a Ti-K diagram for all the clay tablets investigated in this study (Figure 6), and found that the four groups were distinguished well with some overlap. Comparison of the compositional data for Ti and K in this study with those from Goren et al. (2010) shows a systematic difference. The concentration levels of K and Ti in the Goren study are significantly lower than those in this study. The difference is especially large for K; the K content found by Goren et al. (2010) is around half of that in this study. Calibration of the pXRF instruments for our study was conducted using reference rocks as mentioned above, whereas Goren et al. (2010) did not calibrate their pXRF. Calibration of pXRF using reference materials is essential (Ross et al., 2014) , and thus this difference is the likely reason for the discrepancy in chemical compositions between the two studies. Discrepancies in the results were also evident for Mn and Rb. Uchida & Watanabe (2014) conducted chemical analysis of clay tablets from the lower stream area of the Tigris and Euphrates River using both an electron probe X-ray microanalyzer (EPMA) and pXRF. The results obtained by EPMA coincide with those obtained by pXRF in this study. Therefore, it is concluded that the results obtained in Goren et al. (2010) are not correct because the pXRF was not calibrated using standard materials.

In summary, the principle component and cluster analyses using the average chemical compositions for K, Fe, and Ca found in clay tablets resulted in their classification into four groups, corresponding to the upper stream area of the Tigris and Euphrates River, the lower stream area of the Tigris and Euphrates River, the northern and central areas in Turkey, and the southern area in Turkey. This grouping was determined mainly by a difference in Ca content dictated by the local geology.

The non-destructive analysis of the clay tablets was conducted at the Yale Babylonian Collection of Yale University, and the British Museum. Prof. B. Foster, Dr. U. Kasten and Dr. E. Payne of Yale University, and Dr. J. Taylor of the British Museum kindly helped and supported us during the investigation. Dr. C. E. Watanabe of Osaka Gakuin University kindly arranged the investigation at Yale University and the British Museum. We express our heartfelt gratitude to all of them. This research was supported in part by a Grant-in-Aid for Scientific Research of the Japan Society for the Promotion of Science (Grant No. 23310190: C. E. Watanabe).

EtsuoUchida,DaikiNiikuma,RyotaWatanabe, (2015) Regional Differences in the Chemical Composition of Cuneiform Clay Tablets. Archaeological Discovery,03,179-207. doi: 10.4236/ad.2015.34015

Chemical compositions of all the clay tablets determined by the portable XRFs