表紙25号オモテ

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1 Res. Org. Geochem. 25, 1 13 (2009) * ** ** ***, a ****, b ** Abstract It is ordinarily considered that hydrocarbons production from kerogen in nature is carried out in reduced environments. Heating experiments on living pollen and spores as a simulation of organic maturation have been generally conducted in open system under the air and nitrogen gas. In order to investigate the influence of air and nitrogen gas on thermal alteration of pollen, living pollen grains of Pinus thunbergii were heated in open system to 290 under the air and to 453 under the nitrogen gas. The temperature to begin abrupt weight loss, contraction and color darkening (decrease in statistical Thermal Alteration Index) of pollen grains heated under the air is lower than that heated under the nitrogen gas. The pollen grains heated at the temperature higher than 180 under the air might be oxidized by atmospheric oxygen, because atomic O/C ratio of those grains are higher than those heated under the nitrogen gas. Our results support that inert gas including nitrogen gas is better than the air as the atmosphere of heating experiments for simulation of organic maturation. * An influence of the air and the nitrogen gas as the atmosphere on heating experiments of living pollen for simulation of organic maturation ** ujiie@cc.hirosaki-u.ac.jp (Yoshihiro Ujiié), Tel: , Fax: Takehiro Aizawa, Miyabi Sugawara, Yoshihiro Ujiié: Graduate School of Science and Technology, Hirosaki University, Bunkyo-cho 3, Hirosaki, Aomori , Japan. *** Yuuki Arata: Department of Earth and Environmental Sciences, Faculty of Science and Technology, Hirosaki University, Bunkyo-cho 3, Hirosaki, Aomori , Japan. **** Akiko Omura: Department of Geology, Faculty of Science, Shinshu University, Asahi 3-1-1, Matsumoto, Nagano , Japan a NEC Embedded System Operations Unit, NEC Communication Systems Ltd., Shimonumabe 1753, Nakahara-ku, Kawasaki, Kanagawa , Japan. b Center for Advanced Marine Research, Ocean Research Institute, the University of Tokyo, Minamidai , Nakanoku, Tokyo , Japan. 1

2 1. Tissot and Welte, 1984 Gutjahr, 1966; Marshall, 1991; Yule et al., 1999; Ujiié et al., 2003; 2003; 2003 Gutjahr, 1966; Ujiié et al., 2003; 2003; 2003 Lewan and Ruble 2002 Lewan and Ruble 2002 Pinus thunbergii 1992 Tissot et al., Pinus thunbergii Ujiié et al., Pinus Abies Picea Podocarpus TG-DTA TG8120 Thermo Plus mg Ujiié et al., /min ml/min Table 1 Table 2 2

3 Heating temperature ( ) Table 1. Weight loss, size, elemental composition and brightness of pollen grains heated under the air. Weight loss (%) Size (μm) Size Elemental composition Brightness 95% Weight(%) Atomic ratio confidence sttai limit (μm) H C N O ash H/C N/C O/C 95% confidence limit n.a n.a n.a.: not analyzed Table 2. Weight loss, size, elemental composition and brightness of pollen grains heated under the nitrogen gas. Size Elemental composition Brightness Weight loss (%) Size 95% Weight(%) Atomic ratio confidence sttai (μm) limit (μm) H C N O ash H/C N/C O/C Heating temperature ( ) 95% confidence limit CHN MT-5 24 LIBROR LM-20 2 mg 190 ml/min 20 ml/min ma, 65 ma, 120 ma p- C=52.17 % H=4.38% N=20.28% O=23.17% 190 ml/min

4 Table 3. Intensities of absorbance of functional groups of the equal number of pollen grains. Atmosphere Heating temperature ( ) OH Intensity of absorbance aliphatic CH2 C=O aromatic C=C A-Factor air air air air air air N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas N2 gas ma C=68.85 % H=4.95% O=26.20% 3.3. Merck Entellan neu 1996 Ujiié 2001 BHS-323, IF-8500 TVIP-4100, Image Command 4198, NEC PC- 9821BP nm LBD statistical Thermal Alteration Index sttai Ujiié, 2001 sttai

5 FTS-60A/ kg/cm % cm -1, 2 cm -1 Quant/32 OH 3450 cm -1 CH cm -1 C=O 1710 cm -1 C=C 1605 cm -1 4 Tissot et al., 1974 Rouxhet et al % 100 /100 Table Table 1 Table 2 Fig % Fig Fig Table 1 Table 2 Fig μm μm 0 60 weight loss (%) 50 size (μm) Fig. 1. Changes in weight loss of heated pollen grains as a function of heating temperature. Fig. 2. Changes in size of heated pollen grains as a function of heating temperature. 5

6 μm μm Fig μm μm μm Fig H/C, N/C, O/C Table 1 Table % 52.2% 2.89% 34.4% 4.19% H/C 1.76, N/C atomic H/C ratio atomic N/C ratio Fig. 3. Changes in atomic H/C ratio for heated pollen grains as a function of temperature. Fig. 4. Changes in atomic N/C ratio of heated pollen grains as a function of heating temperature. 200 atomic O/C ratio sttai Threshold zone of intense oil generation Fig. 5. Changes in atomic O/C ratio of heated pollen grains as a function of heating temperature. 0 Fig. 6. Changes in sttai of heated pollen grains as a function of heating temperature. Threshold zone of intense oil generation is after Ujiié (2001). 6

7 0.047, O/C 0.49 Table 1 H/C Fig Fig. 3 N/C Fig Fig. 4 O/C Fig Fig Fig statistical Thermal Alteration Index (sttai) sttai Table 1 Table 2 sttai Fig. 6 sttai OH aliphatic CH 2 C=O aromatic C=C aromatic C=C aliphatic CH 2 OH aliphatic CH 2 C=O aromatic C=C aromatic C=C aliphatic CH 2 aliphatic CH 3 aliphatic CH 3 aromatic CH aromatic CH absorbance absorbance Wavenumbers (cm -1 ) Fig. 7. Fourier transform infrared spectra of pollen grains heated under the air Wavenumbers (cm -1 ) Fig. 8. Fourier transform infrared spectra of pollen grains heated under the nitrogen gas. 7

8 Fig Fig Fig. 7 Fig absorbance absorbance Fig. 9. Changes in absorbance of OH functional group of the equal number of heated pollen grains as a function of heating temperature. Fig. 10. Changes in absorbance of aliphatic CH 2 functional group of the equal number of heated pollen grains as a function of heating temperature absorbance absorbance Fig. 11. Changes in absorbance of C=O functional group of heated pollen grains as a function of heating temperature Fig. 12. Changes in absorbance of aromatic C=C functional group of the equal number of heated pollen grains as a function of heating temperature. 8

9 Tissot et al Robin and Rouxhet 1976,1978 Rouxhet et al Tissot and Welte OH 3430 cm -1 CH cm -1 C=O 1710 cm -1 C=C cm -1 CH cm -1 CH cm -1 CH 865 cm -1 Fig. 7 Fig. 8 OH 3450 cm -1 CH cm -1 C=O 1710 cm -1 C=C 1605 cm -1 Table 3 OH 290 Fig Fig. 9 CH Fig Fig. 10 A-factor Fig. 13. Changes in A-factor (= [absorbance of aliphatic CH 2 ]/[absorbance of aliphatic CH 2 + absorbance of aromatic C=C]) as a function of heating temperature. C=O Fig Fig. 11 C=C 290 Fig Fig Fig Fig. 3, Fig. 4 Fig O/C 277 Fig. 5 O/C Tissot and Welte, O/C C=O Fig. 11 C=O Tissot et al., 1974; Robin and Rouxhet, 1976, Fig. 11 C=O CO C=O 9

10 Rouxhet et al C=O 208 C=O O/C 180 Fig Tissot and Welte, 1984 C=C Tissot et al.,1974 Robin and Rouxhet, 1976; Rouxhet et al., 1979; Tissot and Welte, C=C Fig. 12 C=C OH Fig. 9 OH 5.2. Yule et al Lycopodium clavatum H/C H/C Brooks, 1980; Marshall, 1991; Yule et al., % 10% 55~65% Shaw and Yeadon, 1966; Stanley and Lichtenberg, 1974 H/ C Fig. 3 Yule et al., 2000 CH2 60 Fig. 10 CH2 Ganz et al A-factor A-factor CH2 CH2 C=C A-factor Table Fig. 13 A-factor H/C 10

11 sttai sttai RO ; Ujiié 2001 sttai Fig. 6 H/C H/C sttai H/C A-factor sttai Fig. 3, Fig.6 Fig N/C Van Krevelen, 1961; Tissot and Welte, 1984 N/C Fig. 4 N/C 2003 N/C 159 Fig. 4 Table 1 Table Table Table 2 N/C N/C N/ C Table 1 Table H/C O/C

12 C=O N/C N/C H/C A-factor sttai Brooks J. (1980) Chemical studies on the thermal products from sporopollenin and their probable geochemical significance. International Palynol. Conference 6 th, Lucknow ( ) 2, Ganz H. H., Kalkreuth W., Ganz S. N., Oener F., Pearson M. L. and Wehner H. (1990) Infrared analysis-state of art. Berliner Geowiss. Abh. (A) 120, Gutjahr C. C. M. (1966) Carbonization measurements of pollen-grains and spores and their application. Leidse Geologische Mededelingen 38, Lewan M. D. and Ruble T. E. (2002) Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis. Organic Geochemistry 33, Marshall J. A. E. (1991) Quantitative spore colour. Journal of Geological Society 148, FTIR Researches in Organic Geochemistry 13, Robin P. L. and Rouxhet P. G. (1976) Contribution des differentes functions chimiques dans les bandes d absorption infrarouge des kerogenes situees a 1710, 1630 et 3430 cm -1. Revue de l Institut Français du Pétorole 31, Robin P. L. and Rouxhet P. G. (1978) Characterization of kerogens and study of their evolution by infrared spectroscopy: carbonyl and carboxyl groups. Geochimica et Cosmochimica Acta 42, Rouxhet P. G., Villey M., and Oberlin A. (1979) Infrared study of the pyrolysis products of sporopollenin and lignite. Geochimica et Cosmochimica Acta 43, Sengupta S. (1974) The effects of temperature and pressure on Lycopodium clavatum spores. Advances in Organic Geochemistry 1973 (Tissot B. and Bienner F., eds) , Editions Technip. Shaw G. and Yeadon A. (1966) Chemical studies on the constitution of some pollen and spore membranes. Journal of Geological Society 1, Stanley R. G. and Lichtenberg E. (1974) Pollen. Springer-Verlag Berlin, 125p , FTIR IR 59, p. Tissot B. P., Durand B., Espitalié J. and Combaz A. (1974) Influence of nature and diagenesis of organic matter in formation of petroleum. American Association of Petroleum Geologists Bulletin 58,

13 Tissot B. and Welte D. H. (1984) Petroleum formation and occurrence. Springer-Verlag, Berlin, 699p , Ujiié Y. (2001) Brightness of pollen as an indicator of thermal alteration by means of a computer-driven image processor: statistical thermal alteration index (sttai) Organic Geochemistry 32, Researches in Organic Geochemistry 18, Ujiié Y., Arata Y. and Sugawara M. (2003) Heating experiments on Pinus pollen grains and its relation to petroleum genesis. Geochemical Journal 37, Van Krevelen D. W. (1961) Coal. Elsevier. Amsterdam. 514p. Yule B., Robert S., Marshall J. A. E. and Milton J. A. (1998) Quantitative spore colour measurement using colour image analysis. Organic Geochemistry 28, Yule B., Carr A. D., Marshall J. A. E. and Roberts S. (1999) Spore transmittance (%St): a quantitative method for spore colour analysis. Organic Geochemistry 30, Yule B., Roberts S. and Marshall J. A. E. (2000) The thermal evolution of sporopollenin. Organic Geochemistry 31,

Visual Evaluation of Polka-dot Patterns Yoojin LEE and Nobuko NARUSE * Granduate School of Bunka Women's University, and * Faculty of Fashion Science,

Visual Evaluation of Polka-dot Patterns Yoojin LEE and Nobuko NARUSE * Granduate School of Bunka Women's University, and * Faculty of Fashion Science, Bunka Women's University, Shibuya-ku, Tokyo 151-8523