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The preliminary study on kiln identification of Chinese ancient Qingbai wares by ICP-AES
Journal of Cultural Heritage 11 (2010) 482–486
Case study
The preliminary study on kiln identification of Chinese ancient Qingbai wares by ICP-AES Zhu Tiequan ∗ , Wang Changsui , Wang Hongmin , Mao Zhenwei College of Sociology and Anthropology, Sun Yat-sen University, XinGangxi Rd135, Guangzhou, Guangdong 510275, China
a r t i c l e
i n f o
Article history: Received 24 November 2009 Accepted 8 March 2010 Available online 28 April 2010 Keywords: ICP-AES technique Qingbai wares Kiln identification
a b s t r a c t The kilns identification of the Qingbai wares has caught the attention of many archaeological experts. Using ICP-AES method, the major and minor/trace composition of 28 Qingbai wares excavated from different districts were determined. The experimental results show that wares produced in the same location have a great similarity in the content of trance elements; meanwhile the major element K2 O, and 12 of all trance elements including Li, Rb, Cs, B, Ti, Hf, V, Sr, Zr, Pb, Nb, Ta, etc., have a remarkable provenance characteristics, which demonstrates a great potential in chemical discrimination of the Qingbai wares from different kilns. Crown Copyright © 2010 Published by Elsevier Masson SAS.
1. Introduction According to historical literature and archaeological discoveries, Qingbai (bluish-white) wares, with another name “Yingqing”, were firstly produced in the Five Dynasties (907–960BP), then became prosperous when it came to the Song Dynasty (960–1279BP), and finally declined after the Yuan Dynasty (1271–1368BP) [1]. Generally the Qingbai wares have glittering and translucent glaze, with the white and exquisite body, so in the history they were proverbially called “artificial jade”. And in the mean time, the Qingbai wares also adopted the fine handcrafts of carving, scratching, and printing, which deepened their artistic influence and, in some sense, made it one of the most famous types of Chinese porcelains. The kilns of Qingbai wares were widely distributed in the south of China, covering provinces of Hubei, Jiangxi, Anhui, Fujian, Guangxi and so on [2,3]. Moreover, the currently excavated Qingbai wares are not only in a large amount, but also in a rather wide distribution – some of them were excavated as far as in southeast Asia and north Africa [4]. So for a long period, the research on the Qingbai wares, especially on their kiln identification, has been the focus of both archaeologists and ancient ceramic researchers. For a long time, many researchers attempted to find out the provenance characteristics of the Qingbai wares by observation of the shapes, size, color, handcraft, decoration and so on, and they have got some good results so far [5–7]. However, lots of historical literature indicated that in the period of Song and Yuan
∗ Corresponding author. Tel.: +86 020 84115158/+86 020 84113313 (M); fax: +86 020 84115158. E-mail address: [email protected] (Z. Tiequan).
Dynasty, the cultural and technological interactions between different districts were quite frequent because of the convenient traffic. So it was natural for people of a kiln to learn and imitate the productions of other kilns, in hope of improving the quality and increasing sale of their production, which would directly result in the similarity of the appearances of productions from different kilns, and meanwhile, make an obstacle to the kiln identification of Qingbai wares with the method of visual observation alone. As most ancient kilns used raw materials mined from the local area, differences in the elemental and isotopic composition of raw materials between various localities may leave distinctive signatures in their finished products. Due to the above theory, many experts in science field have been trying to characterize Qingbai wares in terms of major elements since early 1980s, They found some elements such as Al and K carry the characteristics of a certain kiln [2,8–10]. Nevertheless, it was still difficult to distinguish the Qingbai wares of all the kilns to use the major elements only. Recently, the trace elements played an important role in the provenance research of ancient ceramics, among the variety of analytical methods used, such as NAA [11], EDXRF [12], ICP-AES [13], PIXE [14], and SRXRF [5]. Inductively Coupled Plasma Atomic Emitting Spectroscopy (ICP-AES) has some excellent analytical characteristics such as high precision, selectivity and sensitivity, as well as low detection limits, large linear dynamic range, and only slight matrix effects [15]. In this paper, we analyzed the bodies of 28 pieces of bluish-white porcelain fragments using ICP-AES, and by virtue of various statistical methods, we attempted to find out the provenance characteristics of the Qingbai wares from different kilns in terms of both the major and trace elements.
1296-2074/$ – see front matter. Crown Copyright © 2010 Published by Elsevier Masson SAS. doi:10.1016/j.culher.2010.03.001
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Table 2 The major elements composition of body of the bluish white porcelains by ICP-AES (wt%). SiO2
Fig. 1. The graphical location of kilns that being sampled.
2. Experimental 2.1. Samples In this experiment, 28 pieces of Qingbai wares shards of eight different kilns (their graphical location was shown in Fig. 1) were graciously offered by Quanzhou Municipal Museum of Fujian Province, Anhui Provincial Archaeological Institute, and Hubei Provincial Archaeological Institute and Jiangxi Provincial Archaeological Institute. The archaeological information of all samples and their appearance description are listed in details in Table 1. 2.2. Sample preparation and analysis The glaze of the porcelain shard was completely removed by grinding on a diamond lap. The porcelain bodies are cleaned with ethanol solution in an ultrasonic bath and then dried. Approximately 0.5–1 g of each sample was cleaned with a brush and washed with distilled water and alcohol in an ultrasonic vessel, then dried at the room temperature. Each specimen was crush and ground with an agate mortar and pestle into fine powder to ensure better homogeneity, filtered with copper sieve mesh of 0.074 mm and sealed in a plastic bag for ICP-AES analysis. The analytical procedure of ICP-AES on the ancient ceramics is recorded in the literatures [16,17]. Our experiment was carried out on a JY38S inductive plasma atomic emission spectrometer (JobinYvon, French), in Hubei Geological Research Laboratory, Wuhan Synthetic Analytical Center of Rock and Mineral (Wuhan city,
QS1 QS2 QS3 QS4 QS6 QS7 QS8 LC1 LC2 LC3 FC1 FC2 FC3 LJW3 LJW5 LJW8 LJW9 HT1 HT3 HT4 HT5 DH1 DH2 SJ5 SJ6 SJ7 AX1 AX2
72.25 71.99 70 71.99 72.25 72.59 73.08 72.25 73.08 72.85 72.85 74.49 71.24 76.82 74.15 76.25 75.07 74.75 73.92 75.07 75.07 72.85 73.08 71.5 73.08 77.08 74.75 75.33
Al2 O3 18.58 19.41 19.52 18.4 18.89 17.91 19.32 19.46 18.63 19.68 19.75 19.03 18.78 14.87 15.16 14.91 17.37 17.1 18.74 16.2 16.38 17.23 17.46 20.83 20.27 17.07 17.73 17.32
TFe2 O3 1.17 0.92 1.06 0.77 0.67 1.5 1.0 0.8 0.63 0.73 0.79 0.89 0.97 0.57 0.9 0.7 0.87 0.61 0.7 0.97 0.76 0.34 0.31 1.43 0.83 0.99 1.49 1.44
MgO 0.27 0.25 0.27 0.25 0.23 0.28 0.32 0.55 0.61 0.61 0.85 0.73 0.65 0.28 0.28 0.38 0.25 0.23 0.18 0.2 0.22 0.13 0.12 0.2 0.43 0.28 0.27 0.18
CaO
Na2 O
K2 O
0.45 0.42 0.39 0.76 0.76 0.32 0.5 0.74 0.49 0.81 0.59 0.57 0.89 0.6 1.23 1.13 0.88 1.48 0.6 0.45 0.64 0.38 0.17 0.22 0.21 0.13 0.28 0.34
0.22 0.13 0.19 0.12 0.09 0.09 0.11 0.86 0.86 0.94 1.2 0.92 2.05 0.13 1.59 0.27 0.84 1.02 1.66 2.67 1.63 0.09 0.09 0.05 0.04 0.04 0.07 0.07
4.6 3.98 4.17 4.02 4.78 3.88 3.85 1.42 1.67 1.76 1.88 1.57 1.33 3.45 2.71 3.23 3.01 3.43 3.12 2.52 3.04 4.95 4.35 3.55 2.69 2.32 3.07 2.71
Hubei province, China); Standard soils of GBW07401, GBW07402, GBW07408 were used as the reference standards to check the accuracy and precision of the analytical result, and the expected precision of major elements is less than 5% RSD, and that of trace elements is less than 10% RSD . The results of 32 chemical elements for body of the sample are listed in Tables 2 and 3, including seven major elements (SiO2 , Al2 O3 , Na2 O, MgO, K2 O and CaO) and 25 trace elements (Ti, Mn, P, Li, Rb, Cs, Sr, Co, Cu, Ni, Zn, Pb, Cr, Sc, Hf, Zr, Sb, Ta, V, Nb, U, Th, Ba, Ga and B). 3. Discussion 3.1. The characteristics of the major elements It is abundantly shown in the literature about Chinese ancient porcelains that bodies of porcelain produced in south China have common characteristics of comparatively higher content of silica (65–75%) and lower alumina (15–25%) [9,18], which is usually applied to the chemical distinguishing between porcelains of south and north China. As for the porcelains produced in different southern districts, it is, in principle, relatively more difficult to distinguish
Table 1 The archaeological information of all samples and its outside appearance. Number of sample
Kiln location
Dating of stratigraphy
Appearance
QS1, QS3, QS7 QS4, QS2, QS6, QS8
Qingshan kiln, Wuchang, Hubei Qingshan kiln, Wuchang, Hubei
Five Dynasties – North Song
White glaze with blue, white body White glaze with blue, white body with gray
FC1, FC2, FC3 LC1, FC2, LC3
Fanchang kiln, Fanchang, Anhui Luochong kiln, Fanchang, Anhui
Five Dynasties – North Song
White glaze with green, white body with gray White glaze with yellow, white body with gray
HT1, HT4 HT5 HT3
Hutian kiln, Jingdezhen, Jiangxi
Song Dynasty Yuan Dynasty
White glaze with blue (except the HT1of white glaze with yellow), white body with gray
LJW3, LJW5, LJW8, LJW9
Liujiawan kiln, Jingdezhen, Jiangxi
Song-Yuan Dynasty
White glaze with blue, white body
DH1, DH2 AX1 AX2 SJ1, SJ2, SJ3
Dehua kiln, Fujian Anxi kiln, Fujian
Yuan Dynasty
White glaze with slight yellow, white body White glaze with blue, white body with gray White glaze with green, white body with gray White glaze with blue, white body with slight gray
Southern Song Shuiji kiln, Fujian
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Table 3 The trance elements compositions of body of the bluish –white porcelains by ICP-AES (g/g).
QS1 QS2 QS3 QS4 QS6 QS7 QS8 LC1 LC2 LC3 FC1 FC2 FC3 LJW3 LJW5 LJW8 LJW9 HT1 HT3 HT4 HT5 DH1 DH2 SJ5 SJ6 SJ7 AX1 AX2
QS1 QS2 QS3 QS4 QS6 QS7 QS8 LC1 LC2 LC3 FC1 FC2 FC3 LJW LJW LJW8 LJW9 HT1 HT3 HT4 HT5 DH1 DH2 SJ5 SJ6 SJ7 AX1 AX2
Mn
Ti
P
Li
181 119 89.7 135 102 137 140 253 174 209 377 189 261 543 612 679 622 221 590 588 237 332 171 443 347 177 514 482
1020 732 885 733 651 923 805 1050 975 1074 1042 996 1055 188 350 249 245 267 172 280 281 319 393 395 166 370 511 572
201 175 178 237 165 117 224 98.8 88.4 93 116 173 238 149 124 343 466 225 50.3 168 152 63.4 71.1 97.1 143 107 157 97
51.5 42.2 42.8 47 38.3 48.2 34.6 32 21.4 24.2 44.1 30.8 23.4 417 161 807 139 421 98.4 309 291 7.39 7.56 16.6 35.5 20.6 11.4 8.6
Cr
Sc
Hf
14.3 9.45 11.2 10.4 9.1 18.4 11.2 10.8 10.6 11.3 10.9 9.28 11.5 5.97 11.9 6.77 8.36 6.51 8.51 11 6.55 5.86 7.3 7.11 7.83 6.85 4.66 6.09
11.1 11.7 12.8 10.9 10.6 12 12.2 11.9 10.2 11.6 12.3 10.9 12.2 8.27 9.98 8.19 9.81 9.08 9.28 9.14 8.81 9.91 11.1 13 13.7 0.83 10.9 8.56
8.75 9.02 9.68 9.24 9.29 9.42 9.44 11.3 10.3 11.1 10.4 9.57 11.3 5.78 6.04 5.55 5.71 4.94 7.22 4.61 5.41 8.59 7.94 10.5 6 5.9 6.97 5.97
Zr 209 208 231 218 211 227 225 315 279 306 284 254 322 169 183 156 145 151 171 130 169 228 201 278 165 162 221 182
Rb 276 277 273 254 311 263 269 65.8 70 75.1 99 74.2 56.6 353 295 291 339 359 445 307 337 216 191 289 331 182 167 152
Sb 0.143 0.061 0.091 0.045 0.071 0.052 0.066 0.047 0.044 0.103 0.049 0.098 0.046 0.156 0.065 0.306 0.09 0.163 0.162 0.152 0.129 0.046 0.112 0.058 0.048 0.058 0.047 2.669
Cs
Sr
10.3 15.1 12.3 8.15 11.7 11.7 15.2 3.08 3.27 3.64 6.91 4.62 3.16 61.4 51 73.6 63.9 52.1 63.6 52.5 51.5 3.63 3.59 5.41 4.92 4.31 8.25 8.66
33.4 31 35.4 50 53.3 30.1 34.6 92.1 88.3 107 86.9 91.6 155 20.2 46.9 38.6 37.9 53.2 31.1 43.1 39.2 50.8 36.7 15.6 10.9 6.68 23.5 15.7
Ta 6.58 6.41 5.36 7.06 8.06 5.73 5.59 1.87 3.05 1.84 1.66 2.6 3.41 6.16 5.26 6.75 3.17 3.74 9.27 3.1 2.76 2.93 2.64 1.19 16.8 4.34 1.33 1.43
between them because the mineral materials of the south used to produce different types of porcelains show little difference in the content of major elements [19]. Moreover, the short distance and convenient traffic promoted the technical communication between southern districts, which inevitably resulted in the potters of different kilns adopting the similar technique of porcelainsmaking including pretreatment of raw materials, recipes, molding, decorating, firing and so on. However, there still exists some slight differences. As is shown in Fig. 2, it is easy to tell that samples from Jingdezhen, Jiangxi Province, have the characteristics of lower Al2 O3 with exception of Sample HT3 of the Yuan Dynasty, which is totally in agreement with the analytical results
V 15.8 10.7 13.6 12 10.2 17.8 13.6 18.2 15.9 18 17.5 16.7 17.9 6.18 10.2 5.61 6.3 4.5 5.61 7.97 5.67 8.63 8.1 10.6 11.2 8.95 9.53 8.59
Co
Cu
4.72 3.38 4.26 4.53 4.18 5.12 4.47 4.6 4.07 4.83 4.5 4.89 5.11 4.39 5.27 2.1 3.13 2.43 2.69 4.14 2.95 4.1 5.81 7.33 7.52 3.2 3.82 4.9
20.2 12.9 32.7 12.9 9.15 8.59 8.01 5.87 5.73 6.18 6.05 6.93 7.24 6.11 5.86 10.2 5.88 5.36 5.45 5.99 4.88 6.22 5.89 6.28 13.6 12 6.71 5.48
Nb
U
Th
78.7 82.7 84.2 83.6 90.5 84.1 84.8 41 43.3 44.7 47 42.9 44 29.5 22.5 29.8 24.1 15.2 40.2 20.2 16.4 27.7 30.2 39.5 83.6 78.1 15.3 14.8
8.3 8.21 8.16 7.13 7.04 7.01 8.16 7.59 8.1 7.74 9.06 8.23 7.34 6.55 6.14 12.2 8.61 11.4 6.24 6.16 9.13 2.35 2.38 7.4 4.85 3.34 2.51 2.6
51.2 74.6 59.3 45.2 45.4 44.2 68.4 48.9 48.9 49.2 47.3 49.5 48.4 8.13 8.77 8.87 8.73 4.77 6.56 4.3 6.27 28.2 28.6 45.2 23.4 10.6 25.6 26.5
Ni
Zn
Pb
7.86 6.04 7.4 7.01 7.89 8.93 8.02 10.2 8.26 8.51 9.42 9.74 9.17 7.92 10.7 3.01 6.57 4.66 3.04 6.96 5.83 3.06 3.83 7.05 22.2 5.98 3.98 4.01
39.7 40.7 43.5 48.4 32.5 44.3 39.5 50.5 40.6 46.7 38.6 43.4 35.9 59.6 45.6 38.2 37.6 48.9 45.6 32.5 31.2 67.3 47.7 29 40.9 29.6 68.8 54.5
41.7 26.2 12.1 28.2 13.0 17.9 21.9 4.2 3.5 3.5 6.4 6.4 7.0 23.1 13.9 4.8 24.2 31.3 24.9 23.7 16.6 59.8 82.1 96.8 59.7 40.6 82.5 97.5
Ba 113 96.1 96 87.1 89.5 84.4 109 153 157 167 114 92.6 119 97.5 145 150 155 166 377 64 145 399 328 76.1 110 26.9 240 227
Ga
B
31.2 30.9 38.4 36.8 31.9 31.8 30.9 34.8 31.3 36.1 33.4 28.8 28.9 28.1 27.2 22.2 26.3 31 53.9 27.1 27.5 15.9 28.5 24.2 39 27.5 16.3 19.4
65.9 71.1 70.1 50.5 65.9 95.4 70.5 31.7 28.2 28.8 28.3 29.8 28.5 579 219 557 356 377 321 196 243 20.8 22.7 17.9 17.8 18.7 18.2 17.4
of other researchers [8–10]. As is well known, in the period of the Song and Yuan Dynasty, people began to adopt the admixture of porcelains clay and kaolin clay (high content of Al2 O3 ) as the material of porcelain body in south China, which could technically improve the quality of the porcelains [1]. And that’s why porcelain bodies of Jiedezhen in the Yuan Dynasty are relatively higher in content of Al2 O3 . In addition, we could see that K2 O of all samples from Fanchang County of Anhui province is in the range of 1.33–1.88%, which is remarkably lower than that of other kilns. According to Prof. Feng’s previous work [2], the local porcelain of Fangchang County has the characteristic of lower K2 O (0.16%). So lower content of K2 O could be regarded as one of the
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Fig. 4. Scatter plot of the three factors showing the grouping of 28 samples. Fig. 2. The scattering plot of K2 O and Al2 O3 showing the grouping of 28 samples.
characteristics of Qingbai wares from Fanchang County of Anhui Province. 3.2. The characteristic of trace elements In this work, multivariate statistical analyses such as cluster analysis and factor analysis were applied aiming at finding out the provenance characteristics of the Qingbai wares. The grouping that resulted from chemical analysis of the samples is presented in the dendrogram of Fig. 3. This shows the result of aggregative HCA using as similarity measure the mean Euclidean distance among the concentrations of 25 elements, the linking criterion used was the average between-groups linkage. The result of clustering is the separation of the samples into four groups which represents four
individual districts to produce the Qingbai wares. Fig. 2 shows the scatter plot of pottery samples from different kilns based on fact analysis (FA) by using the principle component analysis of SPSS. The FA was conducted on the entire data set consisting of all 28 wares, and three factors subsume 70.74% of the total variance in the data set (F1 30.665%, F2 22.243%, F3 16.827%), the result just matches with that of the cluster analysis (Fig. 4). So it could be concluded that Qingbai wares produced in the same area show great similarity in the content of its trace elements. As we all know, both cluster analysis and factor analysis, which belong to the synthetic analysis, reflect the characteristics, not of the individual element, but of the combination of all the trace elements. Seen from the data in Table 3, we find out that 12 of all the 25 trace elements including Li, Rb, Cs, B, Ti, Hf, V, Sr, Zr, Pb, Nb and Ta, have the distinctive provenance characteristics. As shown in Table 3, to be specific, samples from Jingdezhen of Jiangxi have higher content of Li (98–484 g/g), Rb (290–445 g/g), Cs (51–73.6 g/g) and B (196–579 g/g), and lower content of Nb (15.2–40.2 g/g) and Ta (4.3–8.87 g/g); samples of both Fanchang of Anhui province and Qingshan of Hubei province have higher content of Ti (650–1055 g/g), V (10.5–17.9 g/g), Hf (8.75–11.3 g/g), while those of Anhui provincial also have lower content of Pb (3.5–7 g/g) and Rb (57–99 g/g), and higher content of Zr (254–315 g/g) and Sr (83–155 g/g); samples from Fujian Province have higher content of Pb (40–97 g/g). 4. Conclusions
Fig. 3. Hierarchical cluster analysis dendrogram obtained on the basis of 25 trance elements using average linkage.
With the aid of ICP-AES technique, the major and minor/trace compositions of 31 Qingbai wares excavated from different districts were determined. The experimental results show that wares produced in the same location have a great similarity in their trace elements, and in the meantime, the major element K2 O, and 12 of all the trace elements including Li, Rb, Cs, B, Ti, Hf, V, Sr, Zr, Pb, Nb and Ta, have an remarkable provenance characteristics, which demonstrates a great potential in chemically distinguishing the Qingbai wares of different kiln. However, due to the limit of the sample amount and their unclear dating information, so the differences appeared in the samples of different times in a specific kiln aren’t discussed in this paper. Our next move is to collect much more samples with detailed dating and kiln information for a further research, and meanwhile, we will also attempt some other nondestructive methods and revise their analytical results with those of ICP-AES, and eventually realize the kiln identification of the Qingbai wares.
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Acknowledgement This research is supported by National Science Foundation of China (No. 10135050), Chinese Academy of Science (KJCX-No4) and University of Science and Technology of China (985-2-201). References [1] X.M.J. Feng, General discussion on the Qingbai Wares of Song & Yuan dynasty, proceedings of Chinese ancient ceramic, press of cultural relics (Beijing), (1982) 201–209. [2] M. Feng, G.N. Li, X. Ling, et al., The Preliminary Study on the Qingbai Wares of Fanchan kiln, 2 (2004) 29–32. [3] The Chinese Ceramic Society, History of Chinese ceramic[M], Press of Cultural Relics (Beijing), (1982) 264. [4] H.F. Tian, The exports on Chinese Ancient ceramic, press of Forbidden City, 58–61. [5] S.L. Feng, X.Q. Feng, Q. Xu, Analysis of ancient fine white porcelains By SRXRF and preliminary study of the discriminating criteria, J. Nucl. Tech. 25 (2002) 827–832. [6] R.H. Li, The preliminary study on the glaze due of Qingbai Wares and its shape of Hutian kiln, cultural relics of Southern china 3 (2003) 79–82. [7] K.N.J. Song, The general discussion on the difference of Qingbai Wares between jingdezhen and Fanchang kilns, Chinese Cultural Relics & Archaeology 1 (2001) 74–77. [8] Y.C. Chen, H. Chen, Study on the Qingbai Wares of Qingshan kiln in Wuchang area 4 (1994) 92–96. [9] J.Z. Li, History of Chinese science and technology. Volume of ceramic, Science Press of Beijing 9-10 (1998) 325–333.
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Case study
The preliminary study on kiln identification of Chinese ancient Qingbai wares by ICP-AES Zhu Tiequan ∗ , Wang Changsui , Wang Hongmin , Mao Zhenwei College of Sociology and Anthropology, Sun Yat-sen University, XinGangxi Rd135, Guangzhou, Guangdong 510275, China
a r t i c l e
i n f o
Article history: Received 24 November 2009 Accepted 8 March 2010 Available online 28 April 2010 Keywords: ICP-AES technique Qingbai wares Kiln identification
a b s t r a c t The kilns identification of the Qingbai wares has caught the attention of many archaeological experts. Using ICP-AES method, the major and minor/trace composition of 28 Qingbai wares excavated from different districts were determined. The experimental results show that wares produced in the same location have a great similarity in the content of trance elements; meanwhile the major element K2 O, and 12 of all trance elements including Li, Rb, Cs, B, Ti, Hf, V, Sr, Zr, Pb, Nb, Ta, etc., have a remarkable provenance characteristics, which demonstrates a great potential in chemical discrimination of the Qingbai wares from different kilns. Crown Copyright © 2010 Published by Elsevier Masson SAS.
1. Introduction According to historical literature and archaeological discoveries, Qingbai (bluish-white) wares, with another name “Yingqing”, were firstly produced in the Five Dynasties (907–960BP), then became prosperous when it came to the Song Dynasty (960–1279BP), and finally declined after the Yuan Dynasty (1271–1368BP) [1]. Generally the Qingbai wares have glittering and translucent glaze, with the white and exquisite body, so in the history they were proverbially called “artificial jade”. And in the mean time, the Qingbai wares also adopted the fine handcrafts of carving, scratching, and printing, which deepened their artistic influence and, in some sense, made it one of the most famous types of Chinese porcelains. The kilns of Qingbai wares were widely distributed in the south of China, covering provinces of Hubei, Jiangxi, Anhui, Fujian, Guangxi and so on [2,3]. Moreover, the currently excavated Qingbai wares are not only in a large amount, but also in a rather wide distribution – some of them were excavated as far as in southeast Asia and north Africa [4]. So for a long period, the research on the Qingbai wares, especially on their kiln identification, has been the focus of both archaeologists and ancient ceramic researchers. For a long time, many researchers attempted to find out the provenance characteristics of the Qingbai wares by observation of the shapes, size, color, handcraft, decoration and so on, and they have got some good results so far [5–7]. However, lots of historical literature indicated that in the period of Song and Yuan
∗ Corresponding author. Tel.: +86 020 84115158/+86 020 84113313 (M); fax: +86 020 84115158. E-mail address: [email protected] (Z. Tiequan).
Dynasty, the cultural and technological interactions between different districts were quite frequent because of the convenient traffic. So it was natural for people of a kiln to learn and imitate the productions of other kilns, in hope of improving the quality and increasing sale of their production, which would directly result in the similarity of the appearances of productions from different kilns, and meanwhile, make an obstacle to the kiln identification of Qingbai wares with the method of visual observation alone. As most ancient kilns used raw materials mined from the local area, differences in the elemental and isotopic composition of raw materials between various localities may leave distinctive signatures in their finished products. Due to the above theory, many experts in science field have been trying to characterize Qingbai wares in terms of major elements since early 1980s, They found some elements such as Al and K carry the characteristics of a certain kiln [2,8–10]. Nevertheless, it was still difficult to distinguish the Qingbai wares of all the kilns to use the major elements only. Recently, the trace elements played an important role in the provenance research of ancient ceramics, among the variety of analytical methods used, such as NAA [11], EDXRF [12], ICP-AES [13], PIXE [14], and SRXRF [5]. Inductively Coupled Plasma Atomic Emitting Spectroscopy (ICP-AES) has some excellent analytical characteristics such as high precision, selectivity and sensitivity, as well as low detection limits, large linear dynamic range, and only slight matrix effects [15]. In this paper, we analyzed the bodies of 28 pieces of bluish-white porcelain fragments using ICP-AES, and by virtue of various statistical methods, we attempted to find out the provenance characteristics of the Qingbai wares from different kilns in terms of both the major and trace elements.
1296-2074/$ – see front matter. Crown Copyright © 2010 Published by Elsevier Masson SAS. doi:10.1016/j.culher.2010.03.001
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Table 2 The major elements composition of body of the bluish white porcelains by ICP-AES (wt%). SiO2
Fig. 1. The graphical location of kilns that being sampled.
2. Experimental 2.1. Samples In this experiment, 28 pieces of Qingbai wares shards of eight different kilns (their graphical location was shown in Fig. 1) were graciously offered by Quanzhou Municipal Museum of Fujian Province, Anhui Provincial Archaeological Institute, and Hubei Provincial Archaeological Institute and Jiangxi Provincial Archaeological Institute. The archaeological information of all samples and their appearance description are listed in details in Table 1. 2.2. Sample preparation and analysis The glaze of the porcelain shard was completely removed by grinding on a diamond lap. The porcelain bodies are cleaned with ethanol solution in an ultrasonic bath and then dried. Approximately 0.5–1 g of each sample was cleaned with a brush and washed with distilled water and alcohol in an ultrasonic vessel, then dried at the room temperature. Each specimen was crush and ground with an agate mortar and pestle into fine powder to ensure better homogeneity, filtered with copper sieve mesh of 0.074 mm and sealed in a plastic bag for ICP-AES analysis. The analytical procedure of ICP-AES on the ancient ceramics is recorded in the literatures [16,17]. Our experiment was carried out on a JY38S inductive plasma atomic emission spectrometer (JobinYvon, French), in Hubei Geological Research Laboratory, Wuhan Synthetic Analytical Center of Rock and Mineral (Wuhan city,
QS1 QS2 QS3 QS4 QS6 QS7 QS8 LC1 LC2 LC3 FC1 FC2 FC3 LJW3 LJW5 LJW8 LJW9 HT1 HT3 HT4 HT5 DH1 DH2 SJ5 SJ6 SJ7 AX1 AX2
72.25 71.99 70 71.99 72.25 72.59 73.08 72.25 73.08 72.85 72.85 74.49 71.24 76.82 74.15 76.25 75.07 74.75 73.92 75.07 75.07 72.85 73.08 71.5 73.08 77.08 74.75 75.33
Al2 O3 18.58 19.41 19.52 18.4 18.89 17.91 19.32 19.46 18.63 19.68 19.75 19.03 18.78 14.87 15.16 14.91 17.37 17.1 18.74 16.2 16.38 17.23 17.46 20.83 20.27 17.07 17.73 17.32
TFe2 O3 1.17 0.92 1.06 0.77 0.67 1.5 1.0 0.8 0.63 0.73 0.79 0.89 0.97 0.57 0.9 0.7 0.87 0.61 0.7 0.97 0.76 0.34 0.31 1.43 0.83 0.99 1.49 1.44
MgO 0.27 0.25 0.27 0.25 0.23 0.28 0.32 0.55 0.61 0.61 0.85 0.73 0.65 0.28 0.28 0.38 0.25 0.23 0.18 0.2 0.22 0.13 0.12 0.2 0.43 0.28 0.27 0.18
CaO
Na2 O
K2 O
0.45 0.42 0.39 0.76 0.76 0.32 0.5 0.74 0.49 0.81 0.59 0.57 0.89 0.6 1.23 1.13 0.88 1.48 0.6 0.45 0.64 0.38 0.17 0.22 0.21 0.13 0.28 0.34
0.22 0.13 0.19 0.12 0.09 0.09 0.11 0.86 0.86 0.94 1.2 0.92 2.05 0.13 1.59 0.27 0.84 1.02 1.66 2.67 1.63 0.09 0.09 0.05 0.04 0.04 0.07 0.07
4.6 3.98 4.17 4.02 4.78 3.88 3.85 1.42 1.67 1.76 1.88 1.57 1.33 3.45 2.71 3.23 3.01 3.43 3.12 2.52 3.04 4.95 4.35 3.55 2.69 2.32 3.07 2.71
Hubei province, China); Standard soils of GBW07401, GBW07402, GBW07408 were used as the reference standards to check the accuracy and precision of the analytical result, and the expected precision of major elements is less than 5% RSD, and that of trace elements is less than 10% RSD . The results of 32 chemical elements for body of the sample are listed in Tables 2 and 3, including seven major elements (SiO2 , Al2 O3 , Na2 O, MgO, K2 O and CaO) and 25 trace elements (Ti, Mn, P, Li, Rb, Cs, Sr, Co, Cu, Ni, Zn, Pb, Cr, Sc, Hf, Zr, Sb, Ta, V, Nb, U, Th, Ba, Ga and B). 3. Discussion 3.1. The characteristics of the major elements It is abundantly shown in the literature about Chinese ancient porcelains that bodies of porcelain produced in south China have common characteristics of comparatively higher content of silica (65–75%) and lower alumina (15–25%) [9,18], which is usually applied to the chemical distinguishing between porcelains of south and north China. As for the porcelains produced in different southern districts, it is, in principle, relatively more difficult to distinguish
Table 1 The archaeological information of all samples and its outside appearance. Number of sample
Kiln location
Dating of stratigraphy
Appearance
QS1, QS3, QS7 QS4, QS2, QS6, QS8
Qingshan kiln, Wuchang, Hubei Qingshan kiln, Wuchang, Hubei
Five Dynasties – North Song
White glaze with blue, white body White glaze with blue, white body with gray
FC1, FC2, FC3 LC1, FC2, LC3
Fanchang kiln, Fanchang, Anhui Luochong kiln, Fanchang, Anhui
Five Dynasties – North Song
White glaze with green, white body with gray White glaze with yellow, white body with gray
HT1, HT4 HT5 HT3
Hutian kiln, Jingdezhen, Jiangxi
Song Dynasty Yuan Dynasty
White glaze with blue (except the HT1of white glaze with yellow), white body with gray
LJW3, LJW5, LJW8, LJW9
Liujiawan kiln, Jingdezhen, Jiangxi
Song-Yuan Dynasty
White glaze with blue, white body
DH1, DH2 AX1 AX2 SJ1, SJ2, SJ3
Dehua kiln, Fujian Anxi kiln, Fujian
Yuan Dynasty
White glaze with slight yellow, white body White glaze with blue, white body with gray White glaze with green, white body with gray White glaze with blue, white body with slight gray
Southern Song Shuiji kiln, Fujian
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Table 3 The trance elements compositions of body of the bluish –white porcelains by ICP-AES (g/g).
QS1 QS2 QS3 QS4 QS6 QS7 QS8 LC1 LC2 LC3 FC1 FC2 FC3 LJW3 LJW5 LJW8 LJW9 HT1 HT3 HT4 HT5 DH1 DH2 SJ5 SJ6 SJ7 AX1 AX2
QS1 QS2 QS3 QS4 QS6 QS7 QS8 LC1 LC2 LC3 FC1 FC2 FC3 LJW LJW LJW8 LJW9 HT1 HT3 HT4 HT5 DH1 DH2 SJ5 SJ6 SJ7 AX1 AX2
Mn
Ti
P
Li
181 119 89.7 135 102 137 140 253 174 209 377 189 261 543 612 679 622 221 590 588 237 332 171 443 347 177 514 482
1020 732 885 733 651 923 805 1050 975 1074 1042 996 1055 188 350 249 245 267 172 280 281 319 393 395 166 370 511 572
201 175 178 237 165 117 224 98.8 88.4 93 116 173 238 149 124 343 466 225 50.3 168 152 63.4 71.1 97.1 143 107 157 97
51.5 42.2 42.8 47 38.3 48.2 34.6 32 21.4 24.2 44.1 30.8 23.4 417 161 807 139 421 98.4 309 291 7.39 7.56 16.6 35.5 20.6 11.4 8.6
Cr
Sc
Hf
14.3 9.45 11.2 10.4 9.1 18.4 11.2 10.8 10.6 11.3 10.9 9.28 11.5 5.97 11.9 6.77 8.36 6.51 8.51 11 6.55 5.86 7.3 7.11 7.83 6.85 4.66 6.09
11.1 11.7 12.8 10.9 10.6 12 12.2 11.9 10.2 11.6 12.3 10.9 12.2 8.27 9.98 8.19 9.81 9.08 9.28 9.14 8.81 9.91 11.1 13 13.7 0.83 10.9 8.56
8.75 9.02 9.68 9.24 9.29 9.42 9.44 11.3 10.3 11.1 10.4 9.57 11.3 5.78 6.04 5.55 5.71 4.94 7.22 4.61 5.41 8.59 7.94 10.5 6 5.9 6.97 5.97
Zr 209 208 231 218 211 227 225 315 279 306 284 254 322 169 183 156 145 151 171 130 169 228 201 278 165 162 221 182
Rb 276 277 273 254 311 263 269 65.8 70 75.1 99 74.2 56.6 353 295 291 339 359 445 307 337 216 191 289 331 182 167 152
Sb 0.143 0.061 0.091 0.045 0.071 0.052 0.066 0.047 0.044 0.103 0.049 0.098 0.046 0.156 0.065 0.306 0.09 0.163 0.162 0.152 0.129 0.046 0.112 0.058 0.048 0.058 0.047 2.669
Cs
Sr
10.3 15.1 12.3 8.15 11.7 11.7 15.2 3.08 3.27 3.64 6.91 4.62 3.16 61.4 51 73.6 63.9 52.1 63.6 52.5 51.5 3.63 3.59 5.41 4.92 4.31 8.25 8.66
33.4 31 35.4 50 53.3 30.1 34.6 92.1 88.3 107 86.9 91.6 155 20.2 46.9 38.6 37.9 53.2 31.1 43.1 39.2 50.8 36.7 15.6 10.9 6.68 23.5 15.7
Ta 6.58 6.41 5.36 7.06 8.06 5.73 5.59 1.87 3.05 1.84 1.66 2.6 3.41 6.16 5.26 6.75 3.17 3.74 9.27 3.1 2.76 2.93 2.64 1.19 16.8 4.34 1.33 1.43
between them because the mineral materials of the south used to produce different types of porcelains show little difference in the content of major elements [19]. Moreover, the short distance and convenient traffic promoted the technical communication between southern districts, which inevitably resulted in the potters of different kilns adopting the similar technique of porcelainsmaking including pretreatment of raw materials, recipes, molding, decorating, firing and so on. However, there still exists some slight differences. As is shown in Fig. 2, it is easy to tell that samples from Jingdezhen, Jiangxi Province, have the characteristics of lower Al2 O3 with exception of Sample HT3 of the Yuan Dynasty, which is totally in agreement with the analytical results
V 15.8 10.7 13.6 12 10.2 17.8 13.6 18.2 15.9 18 17.5 16.7 17.9 6.18 10.2 5.61 6.3 4.5 5.61 7.97 5.67 8.63 8.1 10.6 11.2 8.95 9.53 8.59
Co
Cu
4.72 3.38 4.26 4.53 4.18 5.12 4.47 4.6 4.07 4.83 4.5 4.89 5.11 4.39 5.27 2.1 3.13 2.43 2.69 4.14 2.95 4.1 5.81 7.33 7.52 3.2 3.82 4.9
20.2 12.9 32.7 12.9 9.15 8.59 8.01 5.87 5.73 6.18 6.05 6.93 7.24 6.11 5.86 10.2 5.88 5.36 5.45 5.99 4.88 6.22 5.89 6.28 13.6 12 6.71 5.48
Nb
U
Th
78.7 82.7 84.2 83.6 90.5 84.1 84.8 41 43.3 44.7 47 42.9 44 29.5 22.5 29.8 24.1 15.2 40.2 20.2 16.4 27.7 30.2 39.5 83.6 78.1 15.3 14.8
8.3 8.21 8.16 7.13 7.04 7.01 8.16 7.59 8.1 7.74 9.06 8.23 7.34 6.55 6.14 12.2 8.61 11.4 6.24 6.16 9.13 2.35 2.38 7.4 4.85 3.34 2.51 2.6
51.2 74.6 59.3 45.2 45.4 44.2 68.4 48.9 48.9 49.2 47.3 49.5 48.4 8.13 8.77 8.87 8.73 4.77 6.56 4.3 6.27 28.2 28.6 45.2 23.4 10.6 25.6 26.5
Ni
Zn
Pb
7.86 6.04 7.4 7.01 7.89 8.93 8.02 10.2 8.26 8.51 9.42 9.74 9.17 7.92 10.7 3.01 6.57 4.66 3.04 6.96 5.83 3.06 3.83 7.05 22.2 5.98 3.98 4.01
39.7 40.7 43.5 48.4 32.5 44.3 39.5 50.5 40.6 46.7 38.6 43.4 35.9 59.6 45.6 38.2 37.6 48.9 45.6 32.5 31.2 67.3 47.7 29 40.9 29.6 68.8 54.5
41.7 26.2 12.1 28.2 13.0 17.9 21.9 4.2 3.5 3.5 6.4 6.4 7.0 23.1 13.9 4.8 24.2 31.3 24.9 23.7 16.6 59.8 82.1 96.8 59.7 40.6 82.5 97.5
Ba 113 96.1 96 87.1 89.5 84.4 109 153 157 167 114 92.6 119 97.5 145 150 155 166 377 64 145 399 328 76.1 110 26.9 240 227
Ga
B
31.2 30.9 38.4 36.8 31.9 31.8 30.9 34.8 31.3 36.1 33.4 28.8 28.9 28.1 27.2 22.2 26.3 31 53.9 27.1 27.5 15.9 28.5 24.2 39 27.5 16.3 19.4
65.9 71.1 70.1 50.5 65.9 95.4 70.5 31.7 28.2 28.8 28.3 29.8 28.5 579 219 557 356 377 321 196 243 20.8 22.7 17.9 17.8 18.7 18.2 17.4
of other researchers [8–10]. As is well known, in the period of the Song and Yuan Dynasty, people began to adopt the admixture of porcelains clay and kaolin clay (high content of Al2 O3 ) as the material of porcelain body in south China, which could technically improve the quality of the porcelains [1]. And that’s why porcelain bodies of Jiedezhen in the Yuan Dynasty are relatively higher in content of Al2 O3 . In addition, we could see that K2 O of all samples from Fanchang County of Anhui province is in the range of 1.33–1.88%, which is remarkably lower than that of other kilns. According to Prof. Feng’s previous work [2], the local porcelain of Fangchang County has the characteristic of lower K2 O (0.16%). So lower content of K2 O could be regarded as one of the
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Fig. 4. Scatter plot of the three factors showing the grouping of 28 samples. Fig. 2. The scattering plot of K2 O and Al2 O3 showing the grouping of 28 samples.
characteristics of Qingbai wares from Fanchang County of Anhui Province. 3.2. The characteristic of trace elements In this work, multivariate statistical analyses such as cluster analysis and factor analysis were applied aiming at finding out the provenance characteristics of the Qingbai wares. The grouping that resulted from chemical analysis of the samples is presented in the dendrogram of Fig. 3. This shows the result of aggregative HCA using as similarity measure the mean Euclidean distance among the concentrations of 25 elements, the linking criterion used was the average between-groups linkage. The result of clustering is the separation of the samples into four groups which represents four
individual districts to produce the Qingbai wares. Fig. 2 shows the scatter plot of pottery samples from different kilns based on fact analysis (FA) by using the principle component analysis of SPSS. The FA was conducted on the entire data set consisting of all 28 wares, and three factors subsume 70.74% of the total variance in the data set (F1 30.665%, F2 22.243%, F3 16.827%), the result just matches with that of the cluster analysis (Fig. 4). So it could be concluded that Qingbai wares produced in the same area show great similarity in the content of its trace elements. As we all know, both cluster analysis and factor analysis, which belong to the synthetic analysis, reflect the characteristics, not of the individual element, but of the combination of all the trace elements. Seen from the data in Table 3, we find out that 12 of all the 25 trace elements including Li, Rb, Cs, B, Ti, Hf, V, Sr, Zr, Pb, Nb and Ta, have the distinctive provenance characteristics. As shown in Table 3, to be specific, samples from Jingdezhen of Jiangxi have higher content of Li (98–484 g/g), Rb (290–445 g/g), Cs (51–73.6 g/g) and B (196–579 g/g), and lower content of Nb (15.2–40.2 g/g) and Ta (4.3–8.87 g/g); samples of both Fanchang of Anhui province and Qingshan of Hubei province have higher content of Ti (650–1055 g/g), V (10.5–17.9 g/g), Hf (8.75–11.3 g/g), while those of Anhui provincial also have lower content of Pb (3.5–7 g/g) and Rb (57–99 g/g), and higher content of Zr (254–315 g/g) and Sr (83–155 g/g); samples from Fujian Province have higher content of Pb (40–97 g/g). 4. Conclusions
Fig. 3. Hierarchical cluster analysis dendrogram obtained on the basis of 25 trance elements using average linkage.
With the aid of ICP-AES technique, the major and minor/trace compositions of 31 Qingbai wares excavated from different districts were determined. The experimental results show that wares produced in the same location have a great similarity in their trace elements, and in the meantime, the major element K2 O, and 12 of all the trace elements including Li, Rb, Cs, B, Ti, Hf, V, Sr, Zr, Pb, Nb and Ta, have an remarkable provenance characteristics, which demonstrates a great potential in chemically distinguishing the Qingbai wares of different kiln. However, due to the limit of the sample amount and their unclear dating information, so the differences appeared in the samples of different times in a specific kiln aren’t discussed in this paper. Our next move is to collect much more samples with detailed dating and kiln information for a further research, and meanwhile, we will also attempt some other nondestructive methods and revise their analytical results with those of ICP-AES, and eventually realize the kiln identification of the Qingbai wares.
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