Vol. 337 No. 8 (2026)
DOI https://doi.org/10.18799/24131830/2026/8/5112
Volatile components in dioptase (Altyn-Tyube, Kazakhstan) and coexisting calcite according to pyrolysis-free gas chromatography-mass spectrometry data
Relevance. The need to obtain factual data on the composition of volatiles in mineral formation processes in oxidation zones of copper ore deposits. The new data obtained can be used to adjust the holistic model of hypergene secondary ore formation. Aim. To determine the composition of volatile components preserved in structural channels and inclusions in dioptase and in inclusions of coexisting calcite. Object. Altyn-Tyube deposit (Karaganda region, Kazakhstan). Methods. The forms of occurrence of molecules of volatile components in the silicate framework were determined by the method of Raman spectroscopy. The bulk composition of the fluid was analyzed by the method of non-pyrolysis gas chromatography-mass spectrometry with impact destruction of the sample. Results and conclusions. In the composition of the volatiles extracted from dioptase, 277 individual components were found, and from calcite 269. Based on these data, it was shown that the volatiles in dioptase and the calcite coexisting with it represent a complex multicomponent mineral-forming system. The dominant fluid component in them is water, its content in dioptase is 78.3, and in calcite 55.1 rel. %. Carbon dioxide, hydrocarbons, S-, N- and halogen-containing compounds were found in dioptase. The share of carbon dioxide exceeds 13, and hydrocarbons and their derivatives 7 rel. %. The spectrum of detected organic compounds includes oxygen-free aliphatic and cyclic hydrocarbons (paraffins, olefins, cyclic alkanes (naphthenes) and alkenes, arenes, polycyclic aromatic hydrocarbons), oxygenated hydrocarbons (alcohols, ethers, furans, dioxins, dioxanes, aldehydes, ketones, carboxylic acids). Sulfonated compounds in the gas mixture from dioptase are represented by oxide (O2S, 0.448 rel. %), sulfides (hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, dimethyl disulfide), thiols (methyl mercaptan), thiophenes and 2-mercapto-2-phenylacetic acid (C8H8O2S). The composition of nitrogenated compounds includes molecular nitrogen (N2, 0.205 rel. %), ammonia, isocyanates (CHNO and C2H3NO), nitriles (C2H3N, C3H5N, C7H5N), amines (C3H5N), 1,4-, 1,3-, 1,2-diazines, pyrrole, amides (C2H5NO-C12H25NO), pyridines (C5H5N-C6H7N), 2-methylpyrazine, pyrazole, 2,5-pyrrolidinedione, caprolactam and 4‑methylaminophenol. Among the volatiles of dioptase and calcite, the same halogenated compound 1-chlorobutane (C4H9Cl) was recorded. It was established that the aqueous solutions that formed the dioptase-calcite mineralization at the Altyn-Tyube deposit had a similar species diversity of gas phases, but with a difference in concentrations between them.
For citation: Bulbak T.A., Tomilenko A.A., Zatolokina K.I., Shaparenko E.O. Volatile components in dioptase (Altyn-Tyube, Kazakhstan) and coexisting calcite according to pyrolysis-free gas chromatography-mass spectrometry data. Bulletin of the Tomsk Polytechnic University. Geo Assets Engineering, 2026, vol. 337, no. 8, pp. 140–152. DOI: http://doi.org/10.18799/24131830/2026/8/5112
Keywords:
dioptase, calcite, Altyn-Tyube, volatile components, inclusions, hydrocarbons, gas chromatography-mass spectrometry, GC-MS
References:
1. Qin F., Wu X., Qin S., Zhang D., Prakapenka V.B., Jacobsen S.D. Pressure-induced dehydration of dioptase: A single-crystal X-ray diffraction and Raman spectroscopy study. Comptes Rendus Geoscience, 2019, vol. 351, no. 2–3, pp. 121–128.
2. Kvon S.S., Nesterova V.I., Omarova A.Ye., Kulikov V.Y., Chsherbakova Ye.P. Study of the mineral composition of promising copper ores of the Republic of Kazakhstan. Complex Use of Mineral Resources, 2023, vol. 2, no. 325, pp. 87–93.
3. Wu S., He M., Yang M., Peng B., Shi Y., Sun K. Near-infrared spectroscopic study of secondary minerals in the oxidation zones of copper-bearing deposits. Crystals, 2024, vol. 14, no. 9, pp. 791.
4. Shafizadeh G., Atapour H. Petrography, mineral chemistry, and geochemistry of calc-silicate skarn mineralization at Kuh-e-Gabri, Rafsanjan, Kerman, Southeastern Iran: a possible potential of industrial andradite–wollastonite–quartz resource. Resource Geology, 2025, vol. 75, no. 1, pp. e70001. DOI: https://doi.org/10.1111/rge.70001
5. Breuer K.H., Eysel W. Structural and chemical varieties of dioptase, Cu6[Si6O18]6H2O. I. Thermal properties. Zeitschrift für Kristallographie, 1988, vol. 184, no. 1–2, pp. 1–11.
6. Breuer K.H., Eysel W., Mueller R. Structural and chemical varieties of dioptase, Cu6[Si6O18]6H2O. II. Structural properties. Zeitschrift für Kristallographie, 1989, vol. 187, no. 1–2, pp. 15–23.
7. Goryainov S.V. Dehydration-induced changes in the vibrational states of dioptase Cu6Si6O18•6H2O. Journal of Structural Chemistry, 1996, vol. 37, pp. 58–64.
8. Frost R.L., Xi Y. Thermogravimetric analysis of the copper silicate mineral dioptase Cu6[Si6O18]6H2O. Journal of Thermal Analysis and Calorimetry, 2013, vol. 112, pp. 615–619.
9. Liu Y., Li X., Song H., Qian C., Qin F., Wu X. In-situ high pressure infrared absorption spectroscopy study of dioptase. Acta Mineralogica Sinica, 2025. DOI: 10.3724/j.1000-4734.2025.45.016
10. Loiri M. Wonderful stones. 250 minerals: history, properties and hidden features. Moscow, Eksmo Publ., 2025. 384 p. (In Russ.)
11. Ohta H., Okubo S., Souda N., Tomoo M., Sakurai T., Yoshida T., Ohmichi E., Fujisawa M., Tanaka H., Kato R. Development and applications of high-frequency ESR up to 55 T. Applied Magnetic Resonance, 2009, vol. 35, no. 3, pp. 399–410.
12. Nomura T., Hauspurg A., Gorbunov D.I., Miyata A., Schulze E., Zvyagin S.A., Tsurkan V., Matsuda Y.H., Kohama Y., Zherlitsyn S. Ultrasound measurement technique for the single-turn-coil magnets. Rev. Sci. Instrum., 2021, vol. 92, no. 6, pp. 063902.
13. Selvin P.C., Watanabe S., Ayala-Arenas J.S. Thermoluminescence and electron paramagnetic resonance (EPR) studies of mineral chrysocolla (dioptase). Radiation Physics and Chemistry, 2001, vol. 61, pp. 531–533.
14. Zatolokina K.I., Tomilenko A.A., Bul’bak T.A. Fluid components in cordierite from the rocks of epidote-amphibole facies of the Muzkol Metamorphic Complex, Tajikistan: pyrolysis-free GC-MS Data. Minerals, 2023, vol. 13, no. 3, p. 323.
15. Bul’bak T.А., Tomilenko А.А., Gibsher N.А., Sazonov А.M., Shaparenko E.O., Ryabukha M.А., Khomenko M.O., Sil’yanov S.A., Nekrasova N.A. Hydrocarbons in fluid inclusions from native gold, pyrite, and quartz of the Sovetskoe Deposit (Yenisei Ridge, Russia) according to pyrolysis-free gas chromatography-mass spectrometry data. Russian Geology and Geophysics, 2020, vol. 61, no. 11, pp. 1260–1282.
16. Shaparenko E., Gibsher N., Khomenko M., Tomilenko A., Sazonov A., Bul’bak T., Silyanov S., Petrova M., Ryabukha M. Parameters for the formation of the Dobroe Gold Deposit (Yenisei Ridge, Russia): evidence from fluid inclusions and S–C isotopes. Minerals, 2023, vol. 13, no. 1, p. 11.
17. Shaparenko E., Bul’bak T., Tomilenko A., Sazonov A., Petrova M., Silyanov S., Gibsher N., Khomenko M. The composition of volatiles in quartz and pyrite from the Konduyak Gold Deposit (Yenisei Ridge, Russia). Minerals, 2025, vol. 15, no. 3, p. 278.
18. Bukin V.I., Nozik Yu.Z., Fykin L.E., Makarov E.S. Neutron diffraction study of hydrogen bonds in the structure of dioptase Cu6[Si6O18]6H2O. Geochemistry, 1976, no. 9, pp. 1328–1332. (In Russ.)
19. Ribbe P.H., Gibbs G.V., Hamil M.M. A refinement of the structure of dioptase, Cu6[Si6O18]6H2O. American Mineralogist, 1977, vol. 62, pp. 807–811.
20. Belov N.V., Maksimov B.A., Nozik Yu.Z., Muradyan L.A. Refinement of the crystal structure of dioptase Cu6[Si6O18]6H2O by X-ray and neutron diffraction methods. Reports of the USSR Academy of Sciences, 1978, vol. 239, no. 4, pp. 842–845. (In Russ.)
21. Belokoneva E.L., Gubina Yu.K., Forsyth J.B., Brown P.J. The charge-density distribution, its multipole refinement and the antiferromagnetic structure of dioptase, Cu6[Si6O18]6H2O. Phys. Chem. Minerals, 2002, vol. 29, pp. 430–438.
22. Gros C., Lemmens P., Choi K.-Y., Güntherodt G., Baenitz M., Otto H.H. Quantum phase transition in the dioptase magnetic lattice. Europhys. Lett., 2002, vol. 60, no. 2, pp. 276–280.
23. Chukhrov F.V. Oxidation zone of sulfide deposits in the steppe part of Kazakhstan. Moscow, USSR Academy of Sciences Publ., 1950. 169 p. (In Russ.)
24. Wilson W.E. Altyn-Tyube, Karaganda Region, Kazakhstan: the type locality for dioptase. The Mineralogical Record, 2023, vol. 54, no. 2, pp. 209–253.
25. Tomilenko A.A., Chepurov A.I., Sonin V.M., Bul’bak T.A., Zhimulev E.I., Chepurov A.A., Timina T.Yu., Pokhilenko N.P. The synthesis of methane and heavier hydrocarbons in the system graphite-iron-serpentine at 2 and 4 GPa and 1200°C. High Temperatures-High Pressures, 2015, vol. 44, no. 6, pp. 451–465.
26. Sobolev N.V., Logvinova A.M., Tomilenko A.A., Wirth R., Bul'bak T.A., Luk'yanova L.I., Fedorova E.N., Reutsky V.N., Efimova E.S. Mineral and fluid inclusions in diamonds from the Urals placers, Russia: Evidence for solid molecular N2 and hydrocarbons in fluid inclusions. Geochimica et Cosmochimica Acta, 2019, vol. 266, pp. 197–219.
27. Smith J.V., Schreyer W. Location of argon and water in cordierite. Mineral. Mag., 1962, vol. 33, pp. 226–236.
28. Zhdanova N.V., Khalif A.L. Drying of hydrocarbon gases. Moscow, Khimiya Publ., 1984. 192 p. (In Russ.)
29. Toussaint J. Thermal (differential-thermal analysis) study of the natural hydrated copper silicates. Ann. Soc. Geol. Belg., 1957, vol. 80, pp. 287–295.
30. Rozinova E.L., Muratov I.G. DTA and differential thermogravimetric analysis diffraction patterns of some copper minerals. Zap. Vses. Mineral. O-va., 1976, vol. 105, no. 3, pp. 232–236.
31. Kiseleva I.A., Ogorodova L.P., Melchakova L.V., Bisengalieva M.R. Thermodynamic properties of copper silicate: dioptase: Cu6Si6O186H2O. The Journal of Chemical Thermodynamics, 1993, vol. 25, no. 5, pp. 621–630.
