- Email: [email protected]
mass spectrometry
Journal of Archaeological Science: Reports 18 (2018) 85–89
Contents lists available at ScienceDirect
Journal of Archaeological Science: Reports journal homepage: www.elsevier.com/locate/jasrep
Analysis of Japanese Jōmon period red lacquerwares by pyrolysis gas chromatography/mass spectrometry ⁎
T
⁎
Shinichi Takahashia, Meesook Sungb, , Takayuki Hondaa, Rong Lua, , Jaekook Jungc, Tetsuo Miyakoshia a
Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashi-Mita, Tama-ku, Kawasaki-shi 214-8571, Japan Department of Biochemistry, Institute for Clinical and Translational Research, College of Medicine, Catholic Kwandong University, Beomil-ro 579 Beon-gil 24, Gangneung 210-701, Republic of Korea c Department of Architecture, College of Engineering, Catholic Kwandong University, Beomil-ro 579 Beon-gil 24, Gangneung, 210-701, Republic of Korea b
A R T I C L E I N F O
A B S T R A C T
Keywords: Lacquerware Fe2O3 HgS Cross-section Py-GC/MS
Sixteen lacquerwares excavated from the Minamikonuma ruins located in Saitama City, Saitama Prefecture, Japan, were analyzed by mean of cross-section observation, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT/IR), energy dispersive X-ray fluorescence (EDXRF), and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). The results showed that Fe2O3 was used as a red pigment in the relatively cheap lacquerwares or in the under layers, and HgS was used as another red pigment in an advanced stage. The characteristic urushiol products were detected in direct and derivative pyrolysis GC/MS of all sixteen lacquerwares and suggested that these Jōmon period lacquerwares were coated with lacquer sap collected from Toxicodendron vernicifluum lacquer trees.
1. Introduction Many historically important products, especially lacquerwares, have been excavated from ancient ruins all over the world (Wei et al., 2012; Igo et al., 2015; Miyazato et al., 2013; Honda et al., 2016). Analysis of these relics can reveal an ancient culture and technology. In general, archeology entails observation of relics and reference to the record of the ruins, but the obtained information is usually limited and lacks accuracy. Therefore, chemical analysis is necessary to clarify historical materials and fabrication techniques of relics (Kumanotani, 1995; Lu et al., 2013a). Lacquerwares dating from the Jōmon period have been examined, and the results indicated that lacquer was first used in the Jōmon period (approximately 14,000 BC to 500 BC) (Sakaguchi, 2009; Hall, 2004; Habu et al., 2011). Because the Jōmon period is very long and different periods should have different properties, it is important to analyze a series of samples to understand the history of Japanese lacquer craft techniques and technology. Previously, we reported the analysis of several Japanese Jōmon period lacquerwares, and the lacquer craft technique and technology were discussed (Lu et al., 2013b; Yuasa et al., 2015; Lu et al., 2015). In order to completely understand the lacquer culture of the long Jōmon period and confirm the previous results, in this study, 16 kinds lacquerwares excavated from the Minamikonuma
⁎
ruins located in Saitama City, Saitama Prefecture, Japan, were analyzed by cross-section observations, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT/IR), energy dispersive X-ray fluorescence (EDXRF), and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), and the results are discussed. 2. Experimental 2.1. Materials Sixteen samples belonging to different eras of the Jōmon period excavated from the Minamikonuma ruins (5000–2300 BC) were analyzed in this study as shown in Fig. 1. These samples were supplied by the Saitama City Board of Education and Saitama City ruins investigation committee, and the shapes of samples were earrings, bowls, and scoops (see Table 1). 2.2. Cross-section observation Cross-sections of all samples were observed using an optical microscope (ECLIPSE LV100N POL, Nikon) as previously reported (Lu et al., 2006; Yuasa et al., 2015; Lu et al., 2015; Honda et al., 2016).
Corresponding authors. E-mail addresses: [email protected] (M. Sung), [email protected] (R. Lu).
https://doi.org/10.1016/j.jasrep.2018.01.013 Received 10 November 2017; Received in revised form 5 January 2018; Accepted 7 January 2018 2352-409X/ © 2018 Elsevier Ltd. All rights reserved.
Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
No.1
No.2
No.5
No.4
No.3
No.6
No.7
No.9
No.8
No.10
No.11
No.12
No.14
No.15
No.13
No.16
Fig. 1. Photos of 16 samples.
ATR estimation frequency was 128 Hz using a Ge tip.
2.3. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT/IR)
2.4. Energy dispersive X-ray fluorescence (EDXRF) and scanning electron microscope (SEM)
ATR-FT/IR spectroscopy was performed using a Nicolet iN 10 instruments (Thermo Fisher Scientific Co., Ltd., Japan). The measurement range was 675–4000 cm−1, the resolution was set to 8 cm−1, and the
The elements of the cross section were analyzed by energy 86
Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
Table 1 Analyzed results of 16 samples. No.
Material no.
Category
Periodization (Jōmon period)
Layers
Pigments
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
1126 1127 1131 1061A 1061B 1145 1172 1132 1136 1138 1180 1193 1176 1178 1 1194
Bowl Scoop Earring Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl
Last part Last part Last part Latter part Latter part Latter part Latter part Latter part Latter part Latter part Middle-latter part Middle-latter part Middle part Middle part Middle part Middle part
4 3 5 4 3 3 3 3 3 7 2 2 2 2 3 3
Red ion oxide, Red ion oxide, Red ion oxide, Red ion oxide Red ion oxide Red ion oxide Cinnabar Red ion oxide Red ion oxide, Red ion oxide Red ion oxide Red ion oxide Red ion oxide Red ion oxide Red ion oxide Red ion oxide
dispersive X-ray fluorescence (EDXRF) with an XGT-5200 series instrument (Horiba, Co., Ltd., Tokyo, Japan). The tube voltage and current were set to 50 kV and 1.0 mA, respectively. SEM observation was performed using a VE-9800 instrument (Keyence).
Lacquer species cinnabar cinnabar cinnabar
T. vernicifluum
cinnabar
different layers of all samples are summarized in Table 1. It can be observed that in the metaphase of the Jōmon period, the lacquerwares were almost all one layer and only Fe2O3 was used as the red pigment. The reason can be attributed to the fact that mercury had not been mined and used in this period. In contrast to the simple manufacturing process in the metaphase of the Jōmon period, lacquerwares excavated from later and advanced stages of the Jōmon period usually contained 2–7 layers, suggesting an elaborate manufacturing process that required more time and higher technique. Because HgS is more expensive than iron oxide and usually found in the top coating layer (Kitano, 2007), considering the manufacturing process, it can be concluded that the more superior the lacquerware, the more coating layers, and the more superior the lacquerware, the more often HgS was used in the top coating layer.
2.5. Pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) Py-GC/MS measurements were performed according to our previous report (Lu et al., 2006). The derivatization reagent, tetramethylammonium hydroxide pentahydrate (TMAH·5H2O) (Tokyo Kase Co., Ltd., Tokyo, Japan) was used directly without further purification. The sample and TMAH·5H2O were mixed in a mortar, and the reaction solution was added to the sample cup for measurement. 3. Result and discussion
3.2. Py-GC/MS 3.1. Cross-section observation 3.2.1. Direct Py-GC/MS All 16 samples were pyrolyzed at 500 °C by direct pyrolysis, and the characteristic products at m/z = 108 chromatograms were analyzed and compared with standard lacquers (Lu et al., 2006; Lu et al., 2013a, 2013b). Fig. 3 shows the m/z = 108 chromatograms of samples No. 3 and 11 (Table 1). Compared with the characteristic products of standard lacquers, both these samples have characteristic peaks of urushiol of 3-heptylphenol at peak 7 and 3-pentadecylphenol at peak 15. That is, both samples No. 3 and 11 were coated with the sap collected from a T. vernicifluum lacquer tree. A m/z 202 chromatogram revealing the characteristic product of HgS was detected from samples No. 1, 2, 3, 7, and 9, suggesting that these samples contained cinnabar as a red pigment, consistent with EDXRF results. The Hg isotopes ranged from 196 to 204 (figure not
Cross-section observation can reveal the paint layers of lacquerwares. Combined with EDXRF, the pigments used in each layer can be identified. Fig. 2A is a cross-section of bowl sample No. 3, dating from an advanced stage of the Jōmon period. Six layers (a–f) are visible from ATR-FT/IR analysis, and different pigments can be identified in different layers by light polarization analysis. The EDXRF analysis detected iron oxide in layers b–f and mercury and sulfur in layer f, suggesting that red iron oxide (Fe2O3) and cinnabar (HgS) were used as a red pigment. Fig. 2B is the cross-section of bowl sample No. 11, which dates to metaphase of the Jōmon period. It showed two layers (a, b) and Fe2O3 was detected as a red pigment in layer b by EDXRF analysis. The results of investigation of layers and different pigments in
Fig. 2. Cross-section of samples No. 3 (A) and No. 11 (B).
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Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
Fig. 3. Ion chromatograms (m/z 108) of sample No. 3 and No. 11.
Fig. 4. Ion chromatogram (m/z 151) of sample No. 2.
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Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
This work was supported in part by the research fund of Catholic Kwandong University, Korea, and the cooperative research program of the MEXT-Supported Program for the Strategic Research Foundation at Private University\ies of Japan. This work was financially supported by the Japan Society for the Promotion of Science (JSPS), and in part by a Grant-in-Aid for Scientific Research (KAKENHI) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan.
shown). Elemental Hg is a reduction product of HgS, which dissociates into Hg and S in the Py-GC/MS analysis. In nature, the isotopes of Hg are 196 (0.15%), 198 (9.97%), 199 (16.87%), 200 (23.1%), 201 (13.18%), 202 (29.86%), and 204 (6.87%), respectively. 3.2.2. Derivative Py-GC/MS In direct Py-GC/MS, only samples No. 1, 3, 4, 5, 6, 7, 10, 11, and 15 yielded high resolution chromatograms. Therefore, samples No. 2, 8, 9, 12, 13, 14, and 16 were examined by derivative Py-GC/MS using TMAH·5H2O as a derivative agent. After derivatization with TMAH·5H2O, two hydroxyl groups of urushiol, methylated urushiol and veratroles, were obtained at m/z = 151. Fig. 4 is the ion chromatogram at m/z = 151 of sample No. 2. Compared with the standard lacquer, the 3-pentadecylveratrole (V15) was identified to derive from urushiol collected from a T. vernicifluum lacquer tree.
References Habu, L., Matsui, A., Yamamoto, N., Kanno, T., 2011. Shell midden archaeology in Japan: aquatic food acquisition and long-term change in the Jōmon culture. Quat. Int. 239, 19–27. Hall, M.E., 2004. Pottery production during the Late Jōmon period: insights from the chemical analyses of Kasori B pottery. J. Archaeol. Sci. 31, 1439–1450. Honda, T., Lu, R., Kamiya, Y., Nakai, S., Miyakoshi, T., 2016. Identification of Ryukyu lacquerwares by pyrolysis-gaschromatography/mass spectrometry and 87Sr/86Sr isotope ratio. J. Anal. Appl. Pyrolsis 117, 25–29. Igo, S., Honda, T., Lu, R., Kamiya, Y., Miyakoshi, T., 2015. Application of derivatization pyrolysis gas chromatography/mass spectrometry to analysis of archaeological lacquerwares. J. Anal. Appl. Pyrolsis 114, 302–307. Kitano, N., 2007. Studies on the red iron oxide coating of ancient wooden structure (II): fundamental research on the production and use of pipe-shaped red iron oxide. Kokogaku to Shizenkagaku 56, 41–63 (in Japanese). Kumanotani, J., 1995. Urushi (Oriental lacquer)—a natural aesthetic durable and futurepromising coating. Prog. Org. Coat. 26, 163–195. Lu, R., Kamiya, Y., Miyakoshi, T., 2006. Applied analysis of lacquer films based on pyrolysis–gas chromatography/mass spectrometry. Talanta 70, 370–376. Lu, R., Yoshida, T., Miyakoshi, T., 2013a. Oriental lacquer: a natural polymer. Polym. Rev. 53, 153–191. Lu, R., Honda, T., Kamiya, Y., Yoshida, K., Miyakoshi, T., 2013b. Analysis of Japanese Jōmon lacquer-ware by pyrolysis-gas chromatography/mass spectrometry. J. Anal. Appl. Pyrolysis 103, 68–72. Lu, R., Honda, T., Sato, M., Yoshida, K., Miyakoshi, T., 2015. Determination of provenance and species of Japanese Jōmon lacquer by pyrolysis-gas chromatography/mass spectrometry and 87Sr/86Sr isotope ratio. J. Anal. Appl. Pyrolysis 113, 84–88. Miyazato, M., Lu, R., Honda, T., Miyakoshi, T., 2013. Lao lacquer culture and history—analysis of Lao lacquer wares. J. Anal. Appl. Pyrolysis 103, 17–20. Sakaguchi, T., 2009. Storage adaptations among hunter–gatherers: a quantitative approach to the Jōmon period. J. Anthropol. Archaeol. 28, 290–303. Wei, S., Ma, O., Schreiner, M., 2012. Scientific investigation of the paint and adhesive materials used in the Western Han dynasty polychromy terracotta army, Qingzhou, China. J. Archaeol. Sci. 39, 1628–1633. Yuasa, K., Honda, T., Lu, R., Hachiya, T., Miyakoshi, T., 2015. Analysis of Japanese ancient lacquerwares excavated from Jōmon period ruins. J. Anal. Appl. Pyrolysis 113, 73–77.
4. Conclusion Sixteen lacquerware samples belonging to the Jōmon period excavated from the Minamikonuma ruins were analyzed. In the crosssection analysis, a simple one-layer coating was found in the lacquerwares belonging to the metaphase of the Jōmon period, and only Fe2O3 was used as the red pigment. In contrast, the lacquerwares belonging to later and/or advanced stages of the Jōmon period had 2–7 coating layers, and HgS was used as another red pigment. The characteristic urushiol products were detected by direct and derivative pyrolysis GC/ MS, suggesting that all lacquerwares were coated with lacquer sap collected from a T. vernicifluum lacquer tree. A water field remnant was discovered, and it revealed that the ancient Jōmon people probably acquired and used pigments near the ruins. Sand was found as an admixture for adhesion between damaged pieces of earthenware from other ruins, and such technology was used not only for earthenware but also for wood plants, and this would be an important case in considering repair technology in the other Jōmon period. Acknowledgments The authors thank the Saitama City Board of Education and Saitama City Ruins Committee, Saitama, Japan, for donating the Jōmon relics.
89
Contents lists available at ScienceDirect
Journal of Archaeological Science: Reports journal homepage: www.elsevier.com/locate/jasrep
Analysis of Japanese Jōmon period red lacquerwares by pyrolysis gas chromatography/mass spectrometry ⁎
T
⁎
Shinichi Takahashia, Meesook Sungb, , Takayuki Hondaa, Rong Lua, , Jaekook Jungc, Tetsuo Miyakoshia a
Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashi-Mita, Tama-ku, Kawasaki-shi 214-8571, Japan Department of Biochemistry, Institute for Clinical and Translational Research, College of Medicine, Catholic Kwandong University, Beomil-ro 579 Beon-gil 24, Gangneung 210-701, Republic of Korea c Department of Architecture, College of Engineering, Catholic Kwandong University, Beomil-ro 579 Beon-gil 24, Gangneung, 210-701, Republic of Korea b
A R T I C L E I N F O
A B S T R A C T
Keywords: Lacquerware Fe2O3 HgS Cross-section Py-GC/MS
Sixteen lacquerwares excavated from the Minamikonuma ruins located in Saitama City, Saitama Prefecture, Japan, were analyzed by mean of cross-section observation, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT/IR), energy dispersive X-ray fluorescence (EDXRF), and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). The results showed that Fe2O3 was used as a red pigment in the relatively cheap lacquerwares or in the under layers, and HgS was used as another red pigment in an advanced stage. The characteristic urushiol products were detected in direct and derivative pyrolysis GC/MS of all sixteen lacquerwares and suggested that these Jōmon period lacquerwares were coated with lacquer sap collected from Toxicodendron vernicifluum lacquer trees.
1. Introduction Many historically important products, especially lacquerwares, have been excavated from ancient ruins all over the world (Wei et al., 2012; Igo et al., 2015; Miyazato et al., 2013; Honda et al., 2016). Analysis of these relics can reveal an ancient culture and technology. In general, archeology entails observation of relics and reference to the record of the ruins, but the obtained information is usually limited and lacks accuracy. Therefore, chemical analysis is necessary to clarify historical materials and fabrication techniques of relics (Kumanotani, 1995; Lu et al., 2013a). Lacquerwares dating from the Jōmon period have been examined, and the results indicated that lacquer was first used in the Jōmon period (approximately 14,000 BC to 500 BC) (Sakaguchi, 2009; Hall, 2004; Habu et al., 2011). Because the Jōmon period is very long and different periods should have different properties, it is important to analyze a series of samples to understand the history of Japanese lacquer craft techniques and technology. Previously, we reported the analysis of several Japanese Jōmon period lacquerwares, and the lacquer craft technique and technology were discussed (Lu et al., 2013b; Yuasa et al., 2015; Lu et al., 2015). In order to completely understand the lacquer culture of the long Jōmon period and confirm the previous results, in this study, 16 kinds lacquerwares excavated from the Minamikonuma
⁎
ruins located in Saitama City, Saitama Prefecture, Japan, were analyzed by cross-section observations, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT/IR), energy dispersive X-ray fluorescence (EDXRF), and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), and the results are discussed. 2. Experimental 2.1. Materials Sixteen samples belonging to different eras of the Jōmon period excavated from the Minamikonuma ruins (5000–2300 BC) were analyzed in this study as shown in Fig. 1. These samples were supplied by the Saitama City Board of Education and Saitama City ruins investigation committee, and the shapes of samples were earrings, bowls, and scoops (see Table 1). 2.2. Cross-section observation Cross-sections of all samples were observed using an optical microscope (ECLIPSE LV100N POL, Nikon) as previously reported (Lu et al., 2006; Yuasa et al., 2015; Lu et al., 2015; Honda et al., 2016).
Corresponding authors. E-mail addresses: [email protected] (M. Sung), [email protected] (R. Lu).
https://doi.org/10.1016/j.jasrep.2018.01.013 Received 10 November 2017; Received in revised form 5 January 2018; Accepted 7 January 2018 2352-409X/ © 2018 Elsevier Ltd. All rights reserved.
Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
No.1
No.2
No.5
No.4
No.3
No.6
No.7
No.9
No.8
No.10
No.11
No.12
No.14
No.15
No.13
No.16
Fig. 1. Photos of 16 samples.
ATR estimation frequency was 128 Hz using a Ge tip.
2.3. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT/IR)
2.4. Energy dispersive X-ray fluorescence (EDXRF) and scanning electron microscope (SEM)
ATR-FT/IR spectroscopy was performed using a Nicolet iN 10 instruments (Thermo Fisher Scientific Co., Ltd., Japan). The measurement range was 675–4000 cm−1, the resolution was set to 8 cm−1, and the
The elements of the cross section were analyzed by energy 86
Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
Table 1 Analyzed results of 16 samples. No.
Material no.
Category
Periodization (Jōmon period)
Layers
Pigments
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
1126 1127 1131 1061A 1061B 1145 1172 1132 1136 1138 1180 1193 1176 1178 1 1194
Bowl Scoop Earring Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl Bowl
Last part Last part Last part Latter part Latter part Latter part Latter part Latter part Latter part Latter part Middle-latter part Middle-latter part Middle part Middle part Middle part Middle part
4 3 5 4 3 3 3 3 3 7 2 2 2 2 3 3
Red ion oxide, Red ion oxide, Red ion oxide, Red ion oxide Red ion oxide Red ion oxide Cinnabar Red ion oxide Red ion oxide, Red ion oxide Red ion oxide Red ion oxide Red ion oxide Red ion oxide Red ion oxide Red ion oxide
dispersive X-ray fluorescence (EDXRF) with an XGT-5200 series instrument (Horiba, Co., Ltd., Tokyo, Japan). The tube voltage and current were set to 50 kV and 1.0 mA, respectively. SEM observation was performed using a VE-9800 instrument (Keyence).
Lacquer species cinnabar cinnabar cinnabar
T. vernicifluum
cinnabar
different layers of all samples are summarized in Table 1. It can be observed that in the metaphase of the Jōmon period, the lacquerwares were almost all one layer and only Fe2O3 was used as the red pigment. The reason can be attributed to the fact that mercury had not been mined and used in this period. In contrast to the simple manufacturing process in the metaphase of the Jōmon period, lacquerwares excavated from later and advanced stages of the Jōmon period usually contained 2–7 layers, suggesting an elaborate manufacturing process that required more time and higher technique. Because HgS is more expensive than iron oxide and usually found in the top coating layer (Kitano, 2007), considering the manufacturing process, it can be concluded that the more superior the lacquerware, the more coating layers, and the more superior the lacquerware, the more often HgS was used in the top coating layer.
2.5. Pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) Py-GC/MS measurements were performed according to our previous report (Lu et al., 2006). The derivatization reagent, tetramethylammonium hydroxide pentahydrate (TMAH·5H2O) (Tokyo Kase Co., Ltd., Tokyo, Japan) was used directly without further purification. The sample and TMAH·5H2O were mixed in a mortar, and the reaction solution was added to the sample cup for measurement. 3. Result and discussion
3.2. Py-GC/MS 3.1. Cross-section observation 3.2.1. Direct Py-GC/MS All 16 samples were pyrolyzed at 500 °C by direct pyrolysis, and the characteristic products at m/z = 108 chromatograms were analyzed and compared with standard lacquers (Lu et al., 2006; Lu et al., 2013a, 2013b). Fig. 3 shows the m/z = 108 chromatograms of samples No. 3 and 11 (Table 1). Compared with the characteristic products of standard lacquers, both these samples have characteristic peaks of urushiol of 3-heptylphenol at peak 7 and 3-pentadecylphenol at peak 15. That is, both samples No. 3 and 11 were coated with the sap collected from a T. vernicifluum lacquer tree. A m/z 202 chromatogram revealing the characteristic product of HgS was detected from samples No. 1, 2, 3, 7, and 9, suggesting that these samples contained cinnabar as a red pigment, consistent with EDXRF results. The Hg isotopes ranged from 196 to 204 (figure not
Cross-section observation can reveal the paint layers of lacquerwares. Combined with EDXRF, the pigments used in each layer can be identified. Fig. 2A is a cross-section of bowl sample No. 3, dating from an advanced stage of the Jōmon period. Six layers (a–f) are visible from ATR-FT/IR analysis, and different pigments can be identified in different layers by light polarization analysis. The EDXRF analysis detected iron oxide in layers b–f and mercury and sulfur in layer f, suggesting that red iron oxide (Fe2O3) and cinnabar (HgS) were used as a red pigment. Fig. 2B is the cross-section of bowl sample No. 11, which dates to metaphase of the Jōmon period. It showed two layers (a, b) and Fe2O3 was detected as a red pigment in layer b by EDXRF analysis. The results of investigation of layers and different pigments in
Fig. 2. Cross-section of samples No. 3 (A) and No. 11 (B).
87
Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
Fig. 3. Ion chromatograms (m/z 108) of sample No. 3 and No. 11.
Fig. 4. Ion chromatogram (m/z 151) of sample No. 2.
88
Journal of Archaeological Science: Reports 18 (2018) 85–89
S. Takahashi et al.
This work was supported in part by the research fund of Catholic Kwandong University, Korea, and the cooperative research program of the MEXT-Supported Program for the Strategic Research Foundation at Private University\ies of Japan. This work was financially supported by the Japan Society for the Promotion of Science (JSPS), and in part by a Grant-in-Aid for Scientific Research (KAKENHI) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of Japan.
shown). Elemental Hg is a reduction product of HgS, which dissociates into Hg and S in the Py-GC/MS analysis. In nature, the isotopes of Hg are 196 (0.15%), 198 (9.97%), 199 (16.87%), 200 (23.1%), 201 (13.18%), 202 (29.86%), and 204 (6.87%), respectively. 3.2.2. Derivative Py-GC/MS In direct Py-GC/MS, only samples No. 1, 3, 4, 5, 6, 7, 10, 11, and 15 yielded high resolution chromatograms. Therefore, samples No. 2, 8, 9, 12, 13, 14, and 16 were examined by derivative Py-GC/MS using TMAH·5H2O as a derivative agent. After derivatization with TMAH·5H2O, two hydroxyl groups of urushiol, methylated urushiol and veratroles, were obtained at m/z = 151. Fig. 4 is the ion chromatogram at m/z = 151 of sample No. 2. Compared with the standard lacquer, the 3-pentadecylveratrole (V15) was identified to derive from urushiol collected from a T. vernicifluum lacquer tree.
References Habu, L., Matsui, A., Yamamoto, N., Kanno, T., 2011. Shell midden archaeology in Japan: aquatic food acquisition and long-term change in the Jōmon culture. Quat. Int. 239, 19–27. Hall, M.E., 2004. Pottery production during the Late Jōmon period: insights from the chemical analyses of Kasori B pottery. J. Archaeol. Sci. 31, 1439–1450. Honda, T., Lu, R., Kamiya, Y., Nakai, S., Miyakoshi, T., 2016. Identification of Ryukyu lacquerwares by pyrolysis-gaschromatography/mass spectrometry and 87Sr/86Sr isotope ratio. J. Anal. Appl. Pyrolsis 117, 25–29. Igo, S., Honda, T., Lu, R., Kamiya, Y., Miyakoshi, T., 2015. Application of derivatization pyrolysis gas chromatography/mass spectrometry to analysis of archaeological lacquerwares. J. Anal. Appl. Pyrolsis 114, 302–307. Kitano, N., 2007. Studies on the red iron oxide coating of ancient wooden structure (II): fundamental research on the production and use of pipe-shaped red iron oxide. Kokogaku to Shizenkagaku 56, 41–63 (in Japanese). Kumanotani, J., 1995. Urushi (Oriental lacquer)—a natural aesthetic durable and futurepromising coating. Prog. Org. Coat. 26, 163–195. Lu, R., Kamiya, Y., Miyakoshi, T., 2006. Applied analysis of lacquer films based on pyrolysis–gas chromatography/mass spectrometry. Talanta 70, 370–376. Lu, R., Yoshida, T., Miyakoshi, T., 2013a. Oriental lacquer: a natural polymer. Polym. Rev. 53, 153–191. Lu, R., Honda, T., Kamiya, Y., Yoshida, K., Miyakoshi, T., 2013b. Analysis of Japanese Jōmon lacquer-ware by pyrolysis-gas chromatography/mass spectrometry. J. Anal. Appl. Pyrolysis 103, 68–72. Lu, R., Honda, T., Sato, M., Yoshida, K., Miyakoshi, T., 2015. Determination of provenance and species of Japanese Jōmon lacquer by pyrolysis-gas chromatography/mass spectrometry and 87Sr/86Sr isotope ratio. J. Anal. Appl. Pyrolysis 113, 84–88. Miyazato, M., Lu, R., Honda, T., Miyakoshi, T., 2013. Lao lacquer culture and history—analysis of Lao lacquer wares. J. Anal. Appl. Pyrolysis 103, 17–20. Sakaguchi, T., 2009. Storage adaptations among hunter–gatherers: a quantitative approach to the Jōmon period. J. Anthropol. Archaeol. 28, 290–303. Wei, S., Ma, O., Schreiner, M., 2012. Scientific investigation of the paint and adhesive materials used in the Western Han dynasty polychromy terracotta army, Qingzhou, China. J. Archaeol. Sci. 39, 1628–1633. Yuasa, K., Honda, T., Lu, R., Hachiya, T., Miyakoshi, T., 2015. Analysis of Japanese ancient lacquerwares excavated from Jōmon period ruins. J. Anal. Appl. Pyrolysis 113, 73–77.
4. Conclusion Sixteen lacquerware samples belonging to the Jōmon period excavated from the Minamikonuma ruins were analyzed. In the crosssection analysis, a simple one-layer coating was found in the lacquerwares belonging to the metaphase of the Jōmon period, and only Fe2O3 was used as the red pigment. In contrast, the lacquerwares belonging to later and/or advanced stages of the Jōmon period had 2–7 coating layers, and HgS was used as another red pigment. The characteristic urushiol products were detected by direct and derivative pyrolysis GC/ MS, suggesting that all lacquerwares were coated with lacquer sap collected from a T. vernicifluum lacquer tree. A water field remnant was discovered, and it revealed that the ancient Jōmon people probably acquired and used pigments near the ruins. Sand was found as an admixture for adhesion between damaged pieces of earthenware from other ruins, and such technology was used not only for earthenware but also for wood plants, and this would be an important case in considering repair technology in the other Jōmon period. Acknowledgments The authors thank the Saitama City Board of Education and Saitama City Ruins Committee, Saitama, Japan, for donating the Jōmon relics.
89