Keywords: temperature-programmed desorption mass spectrometry, biogenic calcite, egg shell, shell of molluscs, belemnite, dispersion of calcite, biocomposite


The correlation between the dynamics of thermal destruction and morphological parameters of biogenic calcites based on the TPD-MS method using eggshells of different species of poultry to develop a convenient model system for assessing the state of complex multicomponent bioceramic structures of the eggshell. For this purpose, different spectra of thermal desorption of biogenic calcites were studied: limestone, eggshell of different species of birds, mollusk shells and calcite nanoparticles. It is proved that the spectrum correlates with morphological parameters and depends on the degree of dispersion of biogenic calcites. The increase in the content of microdisperse, ultrafine and nanodisperse components in a biocomposite based on calcite leads to a significant change in the type of thermodesorption spectrum, which is manifested in the appearance of additional temperature regions of desorption (peaks) and their displacement in the region of temperature decrease. The spectrum of thermodesorption (thermogram) of chalk samples and non-incubated eggs of agricultural poultry was determined experimentally. It was found that the release of carbon dioxide CO 2 as a result of the reaction CaCO 3 (s) → CaO (s) + CO 2 (g), 178 kJ/mol begins at a temperature of 440-450°C and ends at 720-750°C. This indicates the nonlinear nature of the dependence of the partial pressure of CO 2 in the quartz cell on the temperature with two distinct peaks 550-560 and 640-660°C, and the peak in the low temperature region is significantly higher. It is proved that when maintaining for all heterogeneous samples of biogenic calcite the interval on the temperature scale 440-750°C of intensive CO 2 release, the intensity and width of individual peaks corresponding to the specified selection are extremely variable. The working hypothesis to explain this phenomenon was the assumption that the coordinates of the peaks on the temperature scale correspond to the dispersion levels of calcite crystals and their location in the biomaterial. Indeed, almost all of the studied samples give similar diffraction patterns corresponding to calcium carbonate. The next assumption was that the heterogeneity of the micro- and macrostructure of calcite-based biocomposites was responsible for expanding the temperature range of destruction and increasing the number of peaks of intensive release of chalk samples and bird eggs. In this case, the preliminary grinding of the belemnite sample should lead to a change in the type of thermogram, namely, to a narrowing of the destruction interval for fine-grained (> 5-10 μm) and to a corresponding expansion of this interval in the case of combining coarse and fine-grained calcite fractions in one sample.


1. Ahmed Shakeel, Bisetty Krishna, Ikram Saiqa, Kanchi Suvardhan (2018). Biocomposites : biomedical and environmental applications. Pan Stanford Publishing; CRC Press. p. 496.
2. Bain, M.M. , McDade, K., Burchmore, R. , Law, A., Wilson, P.W., Schmutz, M., Preisinger, R. and Dunn, I.C. (2013) Enhancing the egg's natural defence against bacterial penetration by increasing cuticle deposition. Animal Genetics, 44(6), pp. 661-668. doi: 10.1111/age.12071
3. Cesar Araujo Filho, Dmitry Yu.Murzin (2018). A structure sensitivity approach to temperature programmed desorption. Applied Catalysis A: General, vol. 550, pp. 48-56,
4. D’Alba, L. (2014). Antimicrobial properties of a nanostructured eggshell from a compostnesting bird. J. Exp Biol., vol. 217. pp.1116–1121.
5. Danylchenko, S.N., Chyvanov, V.D., Riabyshev, A.H., Novykov, S.V., Stepanenko, A.A., Kuznetsov, V.N., Myronets, E.V., Maryichuk, A.V., Yanovskaia, A.A., Bordunova, O.H., Buhai, A.N. Yssledovanye termycheskoho razlozhenyia pryrodnykh karbonatov kaltsyia metodom temperaturno-prohrammyrovannoi mass-spektrometryy [Investigation of the thermal decomposition of natural calcium carbonates by temperature-programmed mass spectrometry], Zhurnal nano- ta elektronnoi fizyky [Journal of nano- and electronic physics], vol. 8 Nomer 4(1) 2016/10/1, cc. 04031(3ss) doi: 10.21272/jnep.8(4(1)).04031. [in Ukrainian].
6. Dash, S., Kamruddin, M. and Tyagi, A. (1997). Mass spectrometry based evolved gas analysis system for thermal decomposition studies. Bulletin of Materials Science, vol. 20(3), pp. 359-375.
7. Freire, M. N., Holanda, J. N. F. (2006). Characterization of avian eggshell waste aiming its use in a ceramic wall tile paste, Cerâmica, vol.52 no.324 São Paulo, doi: 10.1590/S0366-69132006000400004.
8. Hester, P.(2017), Egg Innovations and Strategies for Improvements, San Diego, CA: Elsevier Inc., 625
9. Hincke, M.(2012). The eggshell: structure, composition and mineralization. Frontiers in Bioscience, vol. 17, pp. 1266-1280
10. James J. De Yoreo Ed (2013) Research Methods in Biomineralization Science, In: Methods in Enzymology 532,. Academic Pres. pp. 614.
11. Kazuyoshi Endo, Toshihiro Kogure, Hiromichi Nagasawa (2018). Biomineralization: From Molecular and Nanostructural Analyses to Environmental Science. Springer: Singapore, pp. 413.
12. Ketta, M. and Tumova, E. (2016) Eggshell structure, measurements, and quality-affecting factors in laying hens: a review. Czech J. Anim. Sci., vol. 61, pp. 299-309.
13. Kulik T. (2012). Use of TPD–MS and Linear Free Energy Relationships for Assessing the Reactivity of Aliphatic Carboxylic Acids on a Silica Surface. J. Phys. Chem. C, vol. 116 (1), pp. 570–580.
14. Kulik, T. V., Lipkovska, N. A., Barvinchenko, V. N., Palyanytsya, B. B., Kazakova, O. A., Dovbiy, O. A., & Pogorelyi, V. K. (2009). Interactions between bioactive ferulic acid and fumed silica by UV-vis spectroscopy, FT-IR, TPD MS investigation and quantum chemical methods. Journal of colloid and interface science, 339(1), 60–68.
15. Kuznetsov, V. N., Yanovskaia, A. A., Novykov, S. V. y dr. (2015) Yzuchenye termoaktyvyruemыkh protsessov эkstraktsyy CO2 yz karbonatnыkh apatytov s yspolzovanyem hazovoi khromatohrafyy [Study of thermally activated processes of CO2 extraction from carbonate apatites using gas chromatography], Zhurnal nano- ta elektronnoi fizyky [Journal of nano- and electronic physics]. T. 7. –№ 3. –03034-1. 03034-9 (9cc). URL: http://jnep. sumdu. edu. ua/download/numbers/2015/3/articles/jnep_20 15_V7_03034. pdf (rezhym dostupu). [in Ukrainian]
16. Laca, A., Laca, A., & Díaz, M. (2017). Eggshell waste as catalyst: A review. Journal of environmental management, 197, 351–359.
17. Mohamed, M., Yusup, S., Maitra, S. (2012). Decomposition study of calcium carbonate in cockle shell. Journal of Engineering Science and Technology, vol. 7, No. 1, pp. 1 – 10.
18. Nastasiienko N, Palianytsia B, Kartel M, Larsson M, Kulik T. (2019) Thermal Transformation of Caffeic Acid on the Nanoceria Surface Studied by Temperature Programmed Desorption Mass-Spectrometry, Thermogravimetric Analysis and FT–IR Spectroscopy. Colloids and Interfaces; 3(1):34.
19. Oates J.A.H. (1998) Lime and Limestone: Chemistry and Technology, Production and Uses. Wiley-VCH Verlag GmbH, pp. 460.
20. Partha Sarathi Guru, Sukalyan Dash (2014). Sorption on eggshell waste—A review on ultrastructure, biomineralization and other applications. Advances in Colloid and Interface Science,Volume 209, 49-67,ISSN 0001-8686. doi: 10.1016/j.cis.2013.12.013.
21. Patricia Y. Hester Ed. San Diego (2017) Egg Innovations and Strategies for Improvements, CA: Elsevier Inc., 625 p.
22. Peter W. Wilson, Ceara S. Suther, Maureen M. Bain, Wiebke Icken, Anita Jones, Fiona Quinlan-Pluck, Victor Olori, Joël Gautron, Ian C. Dunn (2017). Understanding avian egg cuticle formation in the oviduct: a study of its origin and deposition, Biology of Reproduction, Volume 97, Issue 1, Pages 39–49,
23. Pokrovskij, V. (2010). Маss spectrometry of nanosystems. Surface, vol. 2 (17), pp. 63–93.
24. Pokrovskiy, V. A. (1996). Temperature-Programmed Desorption Mass Spectrometry (TPDMS) of Dispersed Oxides. Adsorption Science & Technology, 14(5), 301–317.
25. Pokrovskyi V.A. (2010) Mass-spektrometryia nanostrukturyrovannыkh system [Mass spectrometry of nanostructured systems] Poverkhnost, vyp. [Surface, vol.]2(17), рр. 63–93. [in Ukrainian].
26. Rao, A. (2015). Biomineralization Sourcebook: Characterization of Biominerals and Biomimetic Materials, Elaine DiMasi and Laurie B. Gower (Eds), CRC Press, Taylor & Francis Group, Boca Raton, FL, 2014, 432 pages. ISBN 13:978-1-4665-1835-3. Microscopy and Microanalysis, 21(2), 534-534. doi:10.1017/S1431927614014640
27. Rongqing Zhang, Liping Xie, Zhenguang Yan (2019). Biomineralization Mechanism of the Pearl Oyster, Pinctada fucata, Springer: Singapore. pp. 737.
28. Tatsuko Hatakeyama, Hyoe Hatakeyama (2005). Thermal Properties of Green Polymers and Biocomposites, In.: Hot Topics in Thermal Analysis and Calorimetry 4, Springer: Netherlands, p. 336. doi: 10.1007/1-4020-2354-5.
29. Tetiana V. Kulik (2012). Use of TPD–MS and Linear Free Energy Relationships for Assessing the Reactivity of Aliphatic Carboxylic Acids on a Silica Surface”, J. Phys. Chem. C, 116 (1), pp. 570–580. doi: 10.1021/jp204266c.
30. Tsuboi, Y. and Koga, N. (2018). Thermal Decomposition of Biomineralized Calcium Carbonate: Correlation between the Thermal Behavior and Structural Characteristics of Avian Eggshell. ACS Sustainable Chem. Eng., vol. 6, (4), pp. 5283–5295.
31. Yoji Tsuboi and Nobuyoshi Koga (2018). Thermal Decomposition of Biomineralized Calcium Carbonate: Correlation between the Thermal Behavior and Structural Characteristics of Avian Eggshell. ACS Sustainable Chemistry & Engineering 6 (4), 5283-5295 DOI: 10.1021/acssuschemeng.7b04943
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