Geochemistry – Geology and Geochemistry of Combustible Minerals

Posted on May 2026May 2026 by GGCMJournal

ON THE QUESTION OF THE INFLUENCE OF MIGRATING FLUIDS ON THE FORMATION CONDITIONS OF VEIN MINERALS OF THE UKRAINIAN CARPATHIANS

Home > Archive > No. 2 (202) 2026 > 98–110

Geology & Geochemistry of Combustible Minerals No. 2 (202) 2026, 98–110

ISSN 0869-0774 (Print), ISSN 2786-8621 (Online)

https://doi.org/10.15407/ggcm2026.202.098

Dina HOLOVCHENKO
State institution “Scientific Center of Mining Geology, Geoecology and infrastructure development of National Academy of Sciences of Ukraine”, Kyiv, Ukraine

e-mail: dinka666999@gmail.com, https://orcid.org/0009-0004-6206-6651

Abstract

Research on fluid migration, particularly hydrocarbon fluids, in various geological structures of Ukraine is one of the leading directions for determining their influence on the development and genesis of mineral deposits. The formation of vein mineral complexes is one of the indicators of post-formational processes of fluid transfer of matter and mechanisms of fracture healing in sedimentary rocks, and it is characteristic of the terrigenous flysch deposits of the Dukla and Krosno structural-facial units of the Ukrainian Carpathians. The formation of mineral veins represented by calcite and quartz, including the “Marmarosh diamonds” type, in the deposits of the region’s flysch formation during the Oligocene-Miocene period was influenced by regional fluid-dynamic processes. The formation of several generations of secondary inclusions in “Marmarosh diamonds” indicates that the transverse Rakhiv-Tysia deep fault, within the zone of influence of which the studied veins are located, developed under conditions of periodic stress release, resulting in the formation of fault dislocations. Considering the cyclical (stage-by-stage) process of filling fault dislocations with mineral matter, quartz crystals formed during the final stages of the vein structure development within the zone of influence of the Rakhiv-Tysia transverse deep fault. The results obtained allow for the determination of specific local and regional mineral formation trends characteristic of the Krosno and Dukla structural-tectonic zones. The data obtained from complex precision studies should be applied as a prospecting criterion for hydrocarbon accumulations within the region.

Full Text

Keywords

vein minerals, fluid inclusions, hydrocarbons, Krosno zone, Dukla nappe, Rakhiv-Tysia deep fault, Ukrainian Carpathians

Referenses

Bratus, M. D., & Lomov, S. B. (1996). Umovy mineraloutvorennia ta izotopna pryroda komponentiv fliuidiv u zhylakh sered osadochnykh porid Skladchastykh Karpat. Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(94–95), 85–95. [in Ukrainian]

Deer, W. A., Howie, R. A., & Zussman, J. (1966). An introduction to the rock-forming minerals (1st ed.). Harlow, UK: Longman Scientific and Technical Publishing.

Dudok, I. V. (1996). Hazovyi sklad vkliuchen u zhylnykh mineralakh z flishu Ukrainskykh Karpat. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(96–97), 98–104. [in Ukrainian]

Dudok, I. V., & Vovniuk, S. V. (2000). Heokhimiia izotopiv vuhletsiu i kysniu u zhylnykh utvorenniakh flishu Ukrainskykh Karpat. Heolohiia i heokhimiia horiuchykh kopalyn, 4, 30–37. [in Ukrainian]

Hnylko, O. M. (2012). Tektonichne raionuvannia Karpat u svitli tereinovoi tektoniky. Stattia 2. Flishovi Karpaty – davnia akretsiina pryzma. Heodynamika, 1(12), 67–78. https://doi.org/10.23939/jgd2012.01.067 [in Ukrainian]

Hnylko, O., Hnylko, S., Heneralova, L., Murovskaya, A., Bohdanova, M., Dvorzhak, O., & Navarivska, K. (2025). Junction area between the Western and Eastern Outer Carpathians (Ukraine) as the contact of two accretionary prisms: geological structure, sedimentary features and stratigraphy based on foraminifera. Geological Quarterly, 69(3), 29. https://doi.org/10.7306/gq.1802

Holovchenko, D. (2003). Typomorfni osoblyvosti kaltsytu z zhylnykh utvoren olihotsenovoho flishu Krosnenskoi zony Ukrainskykh Karpat. In Tezy dopovidei do VIII naukovoi konferentsii molodykh vchenykh ta spetsialistiv Instytutu heolohii i heokhimii horiuchykh kopalyn NAN Ukrainy ta NAK “Naftohaz Ukrainy” (pp. 47–50). Lviv. [in Ukrainian]

Holovchenko, D. M. (2004). Do pytannia pro mozhlyvist zastosuvannia deiakykh termobaroheokhimichnykh metodiv dlia vyrishennia problem poshukovoi heokhimii (na prykladi termobaroheokhimichnykh doslidzhen zhylnykh utvoren z flishovykh vidkladiv Krosnenskoi ta Duklianskoi strukturno-tektonichnykh odynyts Ukrainskykh Karpat). Poshukova ta ekolohichna heokhimiia, 4, 69–72. [in Ukrainian]

Holovchenko, D. M., & Kshanovska, T. O. (2004). Mineralnyi sklad ta poshyrennia karbonatnykh utvoren krosnenskoi svity Ukrainskykh Karpat. Mineralohichnyi zbirnyk, 54(2), 230–234. [in Ukrainian]

Holovchenko, D. M., Marusiak, V. P., & Popivniak, I. V. (2003). Marmaroski “diamanty” z karbonatnykh zhyl sela Kvasy (Rakhivskyi rudnyi raion, Zakarpattia). In Suchasni problemy heolohichnoi nauky: zbirnyk naukovykh prats Instytutu heolohichnykh nauk NAN Ukrainy (s. 202–204). Kyiv. [in Ukrainian]

Holovchenko, D., & Popivniak, I. (2009). Osoblyvosti mineralnoho skladu hidrotermalnykh zhyl u piskovykakh z okolyts s. Kvasy (Rakhivskyi rudnyi raion, Zakarpattia). Mineralohichnyi zbirnyk, 59(2), 143–148. [in Ukrainian]

Hopko, L. M., Datsiuk, Yu. R., Popivniak, I. V., Tsikhon, S. I., & Holovchenko, D. M. (2004). Doslidzhennia vuhletsmistiachykh teryhennykh porid luhivskoi svity (Rakhivskyi raion, Zakarpattia). Mineralohichnyi zbirnyk, 54(1), 137–142. [in Ukrainian]

Ivaniuta, M. M. (Ed.). (1998). Atlas rodovyshch nafty i hazu Ukrainy (Vol. 1–6). Lviv: Tsentr Yevropy. [in Ukrainian]

Kaliuzhnyi, V. A., & Sakhno, B. E. (1998). Perspektyvy prohnozuvannia korysnykh kopalyn za typomorfnymy oznakamy fliuidnykh vkliuchen vuhlevodniv ta vuhlets-dioksydu (Zakarpatskyi prohyn, Skladchasti Karpaty. Ukraina). Heolohiia i heokhimiia horiuchykh kopalyn, 3(104), 133–147. [in Ukrainian]

Kolodii, V. V. (Ed.). (2004). Karpatska naftohazonosna provintsiia. Lviv; Kyiv: Ukrainskyi vydavnychyi tsentr. [in Ukrainian]

Kruhlov, S. S., Arsirii, Yu. O., Velikanov, V. Ya., Znamenska, T. O., Lysak, A. M., Lukin, O. Yu., Shashkevych, I. K., Popadiuk, I. V., Radzivill, A. Ya., & Kholodnykh, A. B. (2007). Tektonichna karta Ukrainy. Masshtab 1 : 1 000 000. Poiasniuvalna zapyska (Part 1). Kyiv: UkrDHRI. [in Ukrainian]

Matkovskyi, O. I. (Ed.). (2003). Mineraly Ukrainskykh Karpat. Boraty, arsenaty, fosfaty, molibdaty, sulfaty, karbonaty, orhanichni mineraly i mineraloidy. Lviv: Vydavnychyi tsentr LNU imeni Ivana Franka. [in Ukrainian]

Matkovskyi, O. I. (Ed.). (2011). Mineraly Ukrainskykh Karpat. Sylikaty. Lviv: LNU imeni Ivana Franka. [in Ukrainian]

Matkovskyi, O. I. (Ed.). (2014). Mineraly Ukrainskykh Karpat. Protsesy mineraloutvorennia. Lviv: LNU imeni Ivana Franka. [in Ukrainian]

Matkovskyi, O., Naumko, I., Pavlun, M., & Slyvko, Ye. (2021). Termobaroheokhimiia v Ukraini. Lviv. [in Ukrainian]

Matskiv, B. V., Pukach, B. D., Vorobkanych, V. M., Pastukhanova, S. V., & Hnylko, O. M. (2009). Derzhavna heolohichna karta Ukrainy masshtabu 1 : 200 000, arkushi M 34 XXXVI (Khust), L 34 VI (Baia-Mare), M 35 XXXI (Nadvirna), L 35 I (Visheu-De-Sus). Karpatska seriia. Poiasniuvalna zapyska. Kyiv: UkrDHRI. [in Ukrainian]

Naumko, I. M. (2006). Fliuidnyi rezhym mineralohenezu porodno-rudnykh kompleksiv Ukrainy (za vkliuchenniamy u mineralakh typovykh parahenezysiv) [Extended abstract of Doctorʼs thesis, Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine]. Lviv. [in Ukrainian]

Naumko, I., Zankovych, H., Kokhan, O., Kuzemko, Ya., Sakhno, B., & Serkiz, R. (2022). Nerudni mineraly prozhylkovo-vkraplenoi mineralizatsii u vidkladakh Krosnenskoi zony Ukrainskykh Karpat (raion novoho Beskydskoho zaliznychnoho tuneliu). Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(187–188), 103–114. https://doi.org/10.15407/ggcm2022.01-02.103 [in Ukrainian]

Naumko, I. M., Zankovych, H. O., Kuzemko, Ya. D., Diakiv, V. O., & Sakhno, B. E. (2017). Vuhlevodnevi hazy fliuidnykh vkliuchen u “marmaroskykh diamantakh” z zhyl u vidkladakh flishovoi formatsii raionu novoho Beskydskoho tuneliu (Krosnenska zona Ukrainskykh Karpat). Dopovidi NAN Ukrainy, 10, 70–77. https://doi.org/10.15407/dopovidi2017.10.070 [in Ukrainian]

Shlapinskyi, V. (2022). Deiaki pytannia tektoniky Ukrainskykh Karpat. Pratsi Naukovoho tovarystva imeni Shevchenka. Heolohichnyi zbirnyk, 30, 100–118. [in Ukrainian]

Svoren, Y. M., & Naumko, I. M. (2005). Termobarometriia i heokhimiia haziv prozhylkovo-vkraplenoi mineralizatsii u vidkladakh naftohazonosnykh oblastei i metalohenichnykh provintsii – pryrodnyi fenomen litosfery Zemli. Dopovidi NAN Ukrainy, 2, 109–113. [in Ukrainian]

Tretiak, K. R., Maksymchuk, V. Yu., Kutas, R. I., Rokytianskyi, I. I., Hnylko, O. M., Kendzera, O. V., Pronyshyn, R. S., Klymkovych, T. A., Kuznietsova, V. H., Marchenko, D. O., Smirnova, O. M., Serant, O. V., Babak, V. I., Vovk, A. I., Romaniuk, V. V., & Tereshyn, A. V. (2015). Suchasna heodynamika i heofizychni polia Karpat ta sumizhnykh terytorii. Lviv: Vydavnytstvo Lvivskoi politekhniky. [in Ukrainian]

Vovk, O. P., Naumko, I. M., & Zankovych, H. O. (2025). Psevdosymetriia krystaliv kvartsu ta yii mineraloho-henetychne znachennia. Mineralohichnyi zhurnal, 47(1), 33–44. https://doi.org/10.15407/mineraljournal.47.01.033 [in Ukrainian]

Vovk, O., Naumko, I., Zankovych, H., & Kuzemko, Ya. (2022). Comparison of morphology of guartz crystals – “Marmarosh diamonds” – from Paleogene Flysch sequences of Krosno (Silesian) Zone, Dukla Zone in Ukrainian Carpathians, and Intra-Carpathian sequences of Western Carpathians. Mineralia Slovaca, 54(2), 163–174. https://doi.org/10.56623/ms.2022.54.2.3

Zankovych, H. O. (2016). Heokhimiia fliuidiv prozhylkovo-vkraplenoi mineralizatsii perspektyvno naftohazonosnykh kompleksiv pivnichno-zakhidnoi chastyny Krosnenskoi zony Ukrainskykh Karpat [Extended abstract of Candidateʼs thesis, Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine]. Lviv. [in Ukrainian]

Received: April 24, 2026
Accepted: May 11, 2026
Published: May 29, 2026

Posted on May 2026May 2026 by GGCMJournal

INFLUENCE OF THE CHEMICAL COMPOSITION OF MARINE AND CONTINENTAL WATERS ON THE FORMATION OF CLAY MINERALS OF EVAPORITIC FORMATIONS (ON THE EXAMPLE OF THE CARPATHIAN FOREDEEP AND THE SALT RANGE FORMATION (PAKISTAN)): A REVIEW

Home > Archive > No. 2 (202) 2026 > 76–97

Geology & Geochemistry of Combustible Minerals No. 2 (202) 2026, 76–97

ISSN 0869-0774 (Print), ISSN 2786-8621 (Online)

https://doi.org/10.15407/ggcm2026.202.076

Yaroslava YAREMCHUK^a, Sofiya HRYNIV^b, Nadiia HORODECHNA^c, Liudmyla BILYK^d
Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine, Lviv, Ukraine

^ae-mail: slava.yaremchuk@gmail.com, https://orcid.org/0009-0008-3952-6356
^bhttps://orcid.org/0000-0001-9721-1290
^chttps://orcid.org/0009-0003-8389-5953
^dhttps://orcid.org/0009-0007-8692-3437

Abstract

The influence of the chemical composition of marine and continental waters on the formation and transformation of clay minerals is examined using the Miocene evaporites of the Carpathian Foredeep and the Upper Neoproterozoic-Lower Cambrian evaporites of the Salt Range Formation (Pakistan) as case studies. Evidence for continental-water inflow in the Miocene evaporitic deposits of the Carpathian region is recorded in all facies based on geochemical indicators and, in the gypsum–anhydrite and halite facies, also by clay mineral assemblages atypical for these settings.

The principal controls on clay-mineral transformation under hypersaline conditions are identified, with brine concentration in both the evaporitic basin and buried deposits being the dominant factor, while interaction with organic matter against a background of volcanic activity represents the second most important control. Clay minerals from both the Badenian rock salt and the Upper Neoproterozoic-Lower Cambrian marls of the Salt Range Formation interacted with epigenetic organic matter: in the Carpathian region, regional thrusting created migration pathways for bitumens into Miocene evaporites, whereas the Sawal marl succession likewise contains bituminous layers and is regarded as a petroleum source rock.

Genetic affinities and differences among clay-mineral assemblages formed at successive stages of brine concentration in the Upper Neoproterozoic-Lower Cambrian evaporitic basin of the Salt Range Formation are demonstrated. The presence of identical intermediate transformation products indicates that the same controlling factors operated in the Biliyanwala salt succession as in the Sawal marl succession, whereas the absence of defective structures and the higher crystallinity of clay minerals in the salt unit confirm the decisive role of brine concentration in governing transformation processes.

Full Text

Keywords

clay minerals, aggradational and degradational transformation, interaction with organic matter, evaporitic deposits, supergene zone, Salt Range, marls

Referenses

Ahmad, W., & Alam, S. (2007). Organic geochemistry and source rock characteristics of Salt Range Formation, Potwar Basin, Pakistan. Journal of Hydrocarbon Research, 17, 37–59.

Bąbel, M. (2004). Badenian evaporite basin of the northern Carpathian Foredeep as a drawdown salina basin. Acta Geologica Polonica, 54(3), 317–337.

Bąbel, M., & Schreiber, B. C. (2014). Geochemistry of Evaporites and Evolution of Seawater. In H. D. Holland & K. K. Turekian (Eds.), Treatise on Geochemistry (2nd ed., Vol. 9, pp. 483–560). Oxford: Elsevier. https://doi.org/10.1016/B978-0-08-095975-7.00718-X

Bilonizhka, P. M. (1992a). Hlynysti mineraly – indykatory umov solenahromadzhennia. Heolohiia i heokhimiia horiuchykh kopalyn, 78(1), 95–102. [in Ukrainian]

Bilonizhka, P. M. (1992b). Transformatsiini peretvorennia teryhennykh hlynystykh mineraliv pid chas halohenezu. Mineralohichnyi zbirnyk, 45(2), 51–56. [in Ukrainian]

Bilonizhka, P., Iaremchuk, Ia., Hryniv, S., & Vovnyuk, S. (2012). Clay minerals of Miocene evaporites of the Carpathian Region, Ukraine. Biuletyn Państwowego Instytutu Geologicznego, 449, 137–146.

Bodine, M. W. (1985). Trioctahedral clay mineral assemblages in Paleozoic marine evaporite rocks. In Sixth International Symposium on Salt (Vol. 1, pp. 267–284).

Calvo, J. P., Blanc-Valleron, M. M., Rodríguez-Aranda, J. P., Rouchy, J. M., & Sanz, M. E. (1995). Authigenic clay minerals in continental evaporitic environments. In M. Thiry & R. Simon-Coinçon (Eds.), Palaeoweathering, Palaeosurfaces and Related Continental Deposits (pp. 129–151). Oxford. https://doi.org/10.1002/9781444304190.ch5

Cendón, D. I., Peryt, T. M., Ayora, C., Pueyo, J. J., & Taberner, C. (2004). The importance of recycling processes in the Middle Miocene Badenian evaporite basin (Carpathian foredeep): palaeoenvironmental implications. Palaeogeography, Palaeoclimatology, Palaeoecology, 212(1–2), 141–158. https://doi.org/10.1016/j.palaeo.2004.05.021

Claret, F., Bauer, A., Schäfer, T., Griffault, L., & Lanson, B. (2002). Experimental investigation of the interaction of clays with high pH solutions: A case study from the Callovo-Oxfordian formation, Meuse-Haute Marne underground laboratory (France). Clays and Clay Minerals, 50(5), 633–646. https://doi.org/10.1346/000986002320679369

Claret, F., Sakharov, B. A., Drits, V. A., Velde, B., Meunier, A., Griffault, L., & Lanson, B. (2004). Clay minerals in the Meuse-Haute Marne underground laboratory (France): Possible influence of organic matter on clay mineral evolution. Clays and Clay Minerals, 52(5), 515–532. https://doi.org/10.1346/CCMN.2004.0520501

Dopieralska, J., Belka, Z., Zieliński, M., Górka, M., Poberezhskyy, A., Stupka, O., Walczak, A., & Wysocka, A. (2024). Neodymium and strontium isotopes track the origin of parent brines of primary gypsum deposits (Miocene, Fore-Carpathian Basin). Chemical Geology, 648, 121963. https://doi.org/10.1016/j.chemgeo.2024.121963

Dunoyer de Segonzac, G. (1970). The transformation of clay minerals during diagenesis and low-grade metamorphism: A review. Sedimentology, 15(3–4), 281–346. https://doi.org/10.1111/j.1365-3091.1970.tb02190.x

Eberl, D. D., Farmer, V. C., & Barrer, R. M. (1984). Clay Mineral Formation and Transformation in Rocks and Soils [and Discussion]. Philosophical Transactions of the Royal Society of London, Series A: Mathematical and Physical Sciences, 311(1517), 241–257. https://doi.org/10.1098/rsta.1984.0026

Flecker, R., & Ellam, R. M. (2006). Identifying Late Miocene episodes of connection and isolation in the Mediterranean-Paratethyan realm using Sr isotopes. Sedimentary Geology, 188–189, 189–203. https://doi.org/10.1016/j.sedgeo.2006.03.005

Galán, E. (2006). Genesis of Clay Minerals. In F. Bergaya, B. K. G. Theng & G. Lagaly (Eds.), Developments in Clay Science: Vol. 1. Handbook of Clay Science (Ch. 14, pp. 1129–1162). Amsterdam: Elsevier. https://doi.org/10.1016/S1572-4352(05)01042-1

Garcia-Veigas, J., Cendón, D. I., Gibert, L., Lowenstein, T. K., & Artiaga, D. (2018). Geochemical indicators in Western Mediterranean Messinian evaporites: Implications for the salinity crisis. Marine Geology, 403, 197–214. https://doi.org/10.1016/j.margeo.2018.06.005

Grim, R. E. (1969). Clay Mineralogy. McGraw-Hill Book Company.

Halamai, A. R. (2003). Vmist bromu u haliti badenskykh solenosnykh vidkladiv Karpatskoho rehionu yak pokaznyk yikh henezysu i umov formuvannia. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4, 102–111. [in Ukrainian]

Hodell, D. A., Mueller, P. A., & Garrido, J. R. (1991). Variations in the strontium isotopic composition of seawater during the Neogene. Geology, 19(1), 24–27. https://doi.org/10.1130/0091-7613(1991)019<0024:VITSIC>2.3.CO;2

Hryniv, S., Parafiniuk, J., & Peryt, T. M. (2007). Sulphur isotopic composition of K-Mg sulphates of the Miocene evaporites of the Carpathian Foredeep, Ukraine. Geological Society, London, Special Publications, 285, 211–219. https://doi.org/10.1144/SP285.15

Hryniv, S., Yaremchuk, Ya., & Radkovets, N. (2023). Vplyv vod morskoho i kontynentalnoho pokhodzhennia na protsesy transformatsii hlynystykh mineraliv evaporytovykh vidkladiv (na prykladi Kalush-Holynskoho rodovyshcha Peredkarpatskoho prohynu). Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(191–192), 122–134. https://doi.org/10.15407/ggcm2023.191-192.122 [in Ukrainian]

Hryniv, S. P., Yaremchuk, Ya. V., & Vovniuk, S. V. (2022). Tsyklichni zminy asotsiatsii hlynystykh mineraliv evaporytovykh vidkladiv fanerozoiu yak vidobrazhennia evoliutsii khimichnoho skladu okeanichnoi vody. In Vid mineralohii i heohnozii do heokhimii, petrolohii, heolohii ta heofizyky: fundamentalni i prykladni trendy XXI stolittia: materialy naukovoi konferentsii “MinGeoIntegration XXI” (Kyiv, 28–30 veresnia 2022 r.) (pp. 33–37). Kyiv. [in Ukrainian]

Iaremchuk, Ia., Tariq, M., Hryniv, S., Vovnyuk, S., & Meng, F. (2017). Clay minerals from rock salt of Salt Range Formation (Late Neoproterozoic–Early Cambrian, Pakistan). Carbonates and Evaporites, 32(1), 63–74. https://doi.org/10.1007/s13146-016-0294-5

Kasprzyk, A., Pueyo, J. J., Hałas, S., & Fuenlabrada, J. M. (2007). Sulphur, oxygen and strontium isotope composition of Middle Miocene (Badenian) calcium sulphates from the Carpathian Foredeep, Poland: palaeoenvironmental implications. Geological Quarterly, 51(3), 285–294.

Kazmi, A. H., & Jan, M. Q. (1997). Geology and Tectonics of Pakistan. Graphic Publishers.

Khan, I., Zhong, N., Luo, Q., Ai, J., Yao, L., & Luo, P. (2020). Maceral composition and origin of organic matter input in Neoproterozoic–Lower Cambrian organic-rich shales of Salt Range Formation, upper Indus Basin, Pakistan. International Journal of Coal Geology, 217, 103319. https://doi.org/10.1016/j.coal.2019.103319

Kovalevych, V. M., Marshall, T., Peryt, T. M., Petrychenko, O. Y., & Zhukova, S. A. (2006). Chemical composition of seawater in Neoproterozoic: Results of fluid inclusion study of halite from Salt Range (Pakistan) and Amadeus Basin (Australia). Precambrian Research, 144(1–2), 39–51. https://doi.org/10.1016/j.precamres.2005.10.004

Lagaly, G., Ogawa, M., & Dékány, I. (2006). Clay mineral organic interactions. In F. Bergaya, B. K. G. Theng & G. Lagaly (Eds.), Developments in Clay Science: Vol. 1. Handbook of Clay Science (Ch. 7.3, pp. 309–377). Elsevier. https://doi.org/10.1016/S1572-4352(05)01010-X

Lanson, B., Beaufort, D., Berger, G., Bauer, A., Cassagnabère, A., & Meunier, A. (2002). Authigenic kaolin and illitic minerals during burial diagenesis of sandstones: a review. Clay Minerals, 37(1), 1–22. https://doi.org/10.1180/0009855023710014

Lanson, B., Sakharov, B. A., Claret, F., & Drits, V. A. (2009). Diagenetic smectite-to-illite transition in clay-rich sediments: A reappraisal of X-ray diffraction results using the multi-specimen method. American Journal of Science, 309(6), 476–516. https://doi.org/10.2475/06.2009.03

Lippmann, F., & Savaşçin, M. Y. (1969). Mineralogische Untersuchungen an Lösungsrückständen eines württembergischen Keupergipsvorkommens. Tschermaks mineralogische und petrographische Mitteilungen, 13, 165–190. https://doi.org/10.1007/BF01088021

Lucas, J. (1962). La transformation des minéraux argileux dans la sédimentation. Etudes sur les argiles du Trias. Mém. Serv. Carte géol. Alsace-Lorraine, Strasbourg, France. Vol. 23.

McArthur, J. M., Howarth, R. J., & Bailey, T. R. (2001). Strontium isotope stratigraphy: LOWESS Version 3: Best fit to the marine Sr-isotope curve for 0–509 Ma and accompanying look-up table for deriving numerical age. The Journal of Geology, 109(2), 155–170. https://doi.org/10.1086/319243

McCaffrey, M. A., Lazar, B., & Holland, H. D. (1987). The evaporation path of seawater and the coprecipitation of Br^– and K⁺ with halite. Journal of Sedimentary Petrology, 57(5), 928–937. https://doi.org/10.1306/212F8CAB-2B24-11D7-8648000102C1865D

Millot, G. (1970). Geology of Clays: Weathering, Sedimentology, Geochemistry. New York; Berlin: Springer. https://doi.org/10.1007/978-3-662-41609-9

Millot, G., Lucas, J., & Paquet, H. (1966). Evolution géochimique par dégradation et agradation des minéraux argileux dans l’hydrosphère. Geologische Rundschau, 55, 1–20. https://doi.org/10.1007/BF01982951

Moore, D. M., & Reynolds, R. C. (1997). X-Ray diffraction and the identification and analysis of clay minerals. Oxford University Press.

Oliiovych, O., Yaremchuk, Ya., & Hryniv, S. (2004). Hlyny halohennykh vidkladiv i kory zvitriuvannia Kalush-Holynskoho rodovyshcha kaliinykh solei (miotsen, Peredkarpattia). Mineralohichnyi zbirnyk, 54(2), 214–223. [in Ukrainian]

Peryt, T. M. (1996). Sedimentology of Badenian (middle Miocene) gypsum in eastern Galicia, Podolia аnd Bukovina (West Ukraine). Sedimentology, 43(3), 571–588. https://doi.org/10.1046/j.1365-3091.1996.d01-26.x

Peryt, T. M., & Hryniv, S. (2001). On strontium isotope composition of Miocene potash evaporites in the Ukrainian Carpathian Foredeep. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(156–157), 81–95.

Peryt, T. M., Hryniv, S. P., & Anczkiewicz, R. (2010). Strontium isotope composition of Badenian (Middle Miocene) Ca-sulfate deposits in West Ukraine: a preliminary study. Geological Quarterly, 54(4), 465–476.

Peryt, T. M., Poberezhskyi, A. V., & Yasonovskyi, M. (1995). Fatsii badenskykh hipsiv Prydnistrovia. Heolohiia i heokhimiia horiuchykh kopalyn, 1–2, 16–27. [in Ukrainian]

Peryt, T. M., Poberezhskyi, A. V., Yasonovskyi, M., Petrychenko, O. Y., & Peryt, D. (2004). Koreliatsiia badenskykh sulfatnykh vidkladiv Naddnistrovia. Heolohiia i heokhimiia horiuchykh kopalyn, 1, 56–69. [in Ukrainian]

Petrichenko, O. I. (1988). Fiziko–khimicheskie usloviia osadkoobrazovaniia v drevnikh solerodnykh basseinakh. Kiev: Naukova dumka. [in Russian]

Pozo, M., & Calvo, J. P. (2018). An overview of authigenic magnesian clays. Minerals, 8(11), 520. https://doi.org/10.3390/min8110520

Rosenberg, P. E. (2002). The nature, formation, and stability of end-member illite: A hypothesis. American Mineralogist, 87(1), 103–107. https://doi.org/10.2138/am-2002-0111

Rowe, M. C., & Brewer, B. J. (2018). AMORPH: A statistical program for characterizing amorphous materials by X-ray diffraction. Computers & Geosciences, 120, 21–31. https://doi.org/10.1016/j.cageo.2018.07.004

Rudko, H. I., & Petryshyn, V. Yu. (2017). Soliani resursy Peredkarpattia ta perspektyvy yikh vykorystannia. Kyiv; Chernivtsi: Bukrek. [in Ukrainian]

Shah, S. M. I. (1977). Stratigraphy of Pakistan (Geological Survey of Pakistan Memoir, Vol. 12).

Smith, A. G. (2012). A review of the Ediacaran to Early Cambrian (“Infra-Cambrian”) evaporates and associated sediments of the Middle East. Geological Society, London, Special Publications, 366, 229–250. https://doi.org/10.1144/SP366.12

Sokolova, T. N. (1982).Autigennoe silikatnoe mineraloobrazovanie raznykh stadii osoloneniia. Moskva: Nauka. [in Russian]

Sonnenfeld, P. (1984). Brines and Evaporites. Orlando: Academic Press.

Wójtowicz, A., Hryniv, S. P., Peryt, T. M., Bubniak, A., Bubniak, I., & Bilonizhka, P. M. (2003). K/Ar dating of the Miocene potash salts of the Carpathian Foredeep (West Ukraine): application to dating of tectonic events. Geologica Carpathica, 54(4), 243–249.

Yaremchuk, Ya. V. (2010). Hlynysti mineraly evaporytiv fanerozoiu ta yikhnia zalezhnist vid stadii zghushchennia rozsoliv i khimichnoho typu okeanichnoi vody. Zbirnyk naukovykh prats Instytutu heolohichnykh nauk NAN Ukrainy, 3, 138–146. https://doi.org/10.30836/igs.2522-9753.2010.147301 [in Ukrainian]

Yaremchuk, Ya. (2012). Zalezhnist asotsiatsii hlynystykh mineraliv u neohenovykh evaporytakh Karpatskoho rehionu vid kontsentratsii rozsoliv solerodnykh baseiniv. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(160–161), 119–130. [in Ukrainian]

Yaremchuk, Ya., & Halamai, A. (2009). Mineralnyi sklad vodonerozchynnoho zalyshku badenskoi kamianoi soli Ukrainskoho Peredkarpattia (dilianka Hrynivka). Heolohiia i heokhimiia horiuchykh kopalyn, 1(146), 79–90. [in Ukrainian]

Yaremchuk, Ya. V., & Hryniv, S. P. (2008). Mineralnyi sklad hlyn kamianoi soli miotsenovykh evaporytiv Karpatskoho rehionu Ukrainy. Zbirnyk naukovykh prats Instytutu heolohichnykh nauk NAN Ukrainy, 1, 209–215. [in Ukrainian]

Yaremchuk, Y., Hryniv, S., & Meng, F. (2025). The peculiarities of the clay minerals of Sahwal Marl Member of the Salt Range Formation, Pakistan. In Modern science: trends, challenges, solutions: Proceedings of IV International scientific and practical conference (November 13–15, 2025) (pp. 320–328). Liverpool: Cognum Publishing House. https://sci-conf.com.ua/iv-mizhnarodna-naukovo-praktichna-konferentsiya-modern-science-trends-challenges-solutions-13-15-11-2025-liverpul-velikobritaniya-arhiv/

Yaremchuk, Y., Hryniv, S., & Peryt, T. (2025). Controls on the transformation of clay minerals in the Miocene evaporite deposits of the Ukrainian Carpathian Foredeep. Minerals, 15(4), 395. https://doi.org/10.3390/min15040395

Yaremchuk, Y., Hryniv, S., Peryt, T., Vovnyuk, S., & Meng, F. (2020). Controls on associations of clay minerals in Phanerozoic evaporite formations: An overview. Minerals, 10(11), 974. https://doi.org/10.3390/min10110974

Yaremchuk, Ya., Menh, F., Hryniv, S., Vovniuk, S., & Horodechna, N. (2025). Asotsiatsii hlynystykh mineraliv verkhnoneoproterozoisko-nyzhnokembriiskykh merheliv formatsii Solianyi kriazh, Pakystan. Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(197–198), 91–110. https://doi.org/10.15407/ggcm2025.197-198.091 [in Ukrainian]

Yaremchuk, Ya. V., & Poberezhskyi, A. V. (2009). Mineralnyi sklad hlyn badenskykh hipsiv Naddnistrovia. Mineralohichnyi zbirnyk, 59(1), 116–127. [in Ukrainian]

Yaremchuk, Ya., Vovniuk, S., Hryniv, S., Tarik, M., Menh, F., Bilyk, L., & Kochubei, V. (2017). Umovy utvorennia hlynystykh mineraliv verkhnoneoproterozoisko-nyzhnokembriiskoi kamianoi soli formatsii Solianyi kriazh, Pakystan. Mineralohichnyi zbirnyk, 2(67), 72–90. [in Ukrainian]

Yaremchuk, Y. V., Vovnyuk, S. V., & Hryniv, S. P. (2020). The peculiarities of high-magnesium clay minerals occurrence in Phanerozoic evaporite formation. Geodynamics, 1(28), 52–61. https://doi.org/10.23939/jgd2020.01.052

Received: February 09, 2026
Accepted: February 25, 2026
Published: May 29, 2026

Posted on May 2026May 2026 by GGCMJournal

INFLUENCE OF THE PORE STRUCTURE OF FOSSIL ORGANIC MATTER ON METHANOGENESIS IN FREE-CHAIN RADICAL REACTIONS

Home > Archive > No. 2 (202) 2026 > 62–75

Geology & Geochemistry of Combustible Minerals No. 2 (202) 2026, 62–75

ISSN 0869-0774 (Print), ISSN 2786-8621 (Online)

https://doi.org/10.15407/ggcm2026.202.062

Myroslava YAKOVENKO^a, Yurii KHOKHA^b, Oleksandr LYUBCHAK^c
Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine, Lviv, Ukraine

^ae-mail: myroslavakoshil@ukr.net, https://orcid.org/0000-0001-8967-0489
^be-mail: khoha_yury@ukr.net, https://orcid.org/0000-0002-8997-9766
^ce-mail: oleksandr.lyubchak@gmail.com, https://orcid.org/0000-0002-0700-6929

Abstract

The paper considers the role of pore structure in the formation of local thermobaric conditions that may support methane generation in fossil organic matter through chain free-radical reactions. The gas–organic matter system is treated as a heterogeneous dispersed medium in which nano-, micro- and mesopores cannot be described only by bulk pressure and temperature. A dimensionless pore-pressure coefficient π = P_p/P_∞ is used, where P_p is the pore pressure and P_∞ is the geostatic pressure. The value π = 1 corresponds to equality between pore and geostatic pressures, whereas π < 1 indicates a pore-pressure deficit; therefore, 1 − π can be interpreted as a relative measure of rarefaction. Model data are analysed for pore diameters of 0.5, 1, 2, 5, 10, 20, 50, 100 and 1000 nm within the depth range 0–10 km. Additional trends are discussed for peat and brown coal, medium-rank coal and anthracite under heat flows of 40 and 100 mW/m². The results show that pore size is the main factor controlling the deviation of pore pressure from geostatic pressure. In pores of 0.5–2 nm, π remains far below unity even at a depth of 10 km, whereas pores of 100–1000 nm approach a quasi-equilibrium state. A higher heat flow slightly lowers π in small pores and can promote the formation of free radicals, but this effect is secondary to the geometric restriction imposed by pore size and shape. The evolution from peat and brown coal to anthracite is therefore interpreted not only as a change in sorption capacity and transport properties, but also as a change in the abundance of local pore domains favourable to the mechanical destruction of organic matter, radical stabilization, and methane generation. The proposed interpretation links pore-scale pressure heterogeneity with the kinetics of homolytic reactions and provides a basis for further quantitative modelling of methane formation in a three-phase coal matrix.

Full Text

Keywords

coal, peat, anthracite, porosity, methane, pore pressure, rarefaction, free radicals, geostatic pressure, heat flow

Referenses

Boelter, D. H. (1969). Physical properties of peats as related to degree of decomposition. Soil Science Society of America Journal, 33(4), 606–609. https://doi.org/10.2136/sssaj1969.03615995003300040033x

Bulat, A. F., Zviagilskii, E. L., Lukinov, V. V., Perepelitca, V. G., Pimonenko, L. I., & Shevelev, G. A. (2008). Ugleporodnyi massiv Donbassa kak geterogennaia sreda. Kiev: Naukova dumka. [in Russian]

Clarkson, C. R., & Bustin, R. M. (1996). Variation in micropore capacity and size distribution with composition in bituminous coal of the Western Canadian Sedimentary Basin: Implications for coalbed methane potential. Fuel, 75(13), 1483–1498. https://doi.org/10.1016/0016-2361(96)00142-1

Clarkson, C. R., & Bustin, R. M. (1999a). The effect of pore structure and gas pressure upon the transport properties of coal: A laboratory and modeling study. 1. Isotherms and pore volume distributions. Fuel, 78(11), 1333–1344. https://doi.org/10.1016/S0016-2361(99)00055-1

Clarkson, C. R., & Bustin, R. M. (1999b). The effect of pore structure and gas pressure upon the transport properties of coal: A laboratory and modeling study. 2. Adsorption rate modeling. Fuel, 78(11), 1345–1362. https://doi.org/10.1016/S0016-2361(99)00056-3

Dziewonski, A. M., & Anderson, D. L. (1981). Preliminary reference Earth model. Physics of the Earth and Planetary Interiors, 25(4), 297–356. https://doi.org/10.1016/0031-9201(81)90046-7

Ettinger, I. L. (1988). Neobiatnye zapasy i nepredskazuemye katastrofy: Tverdye rastvory gazov v nedrakh Zemli. Moskva: Nauka. [in Russian]

Gan, H., Nandi, S. P., & Walker, P. L. (1972). Nature of the porosity in American coals. Fuel, 51(4), 272–277. https://doi.org/10.1016/0016-2361(72)90003-8

Hasterok, D., & Chapman, D. S. (2011). Heat production and geotherms for the continental lithosphere. Earth and Planetary Science Letters, 307(1–2), 59–70. https://doi.org/10.1016/j.epsl.2011.04.034

Khokha, Yu. V., Liubchak, O. V., & Yakovenko, M. B. (2019). Enerhiia Hibbsa utvorennia komponentiv pryrodnoho hazu v osadovykh tovshchakh. Heolohiia i heokhimiia horiuchykh kopalyn, 2(179), 37–46. https://doi.org/10.15407/ggcm2019.02.037 [in Ukrainian]

Khramov, V., & Liubchak, O. (2009). Mekhanizm heneratsii metanu v porovomu prostori vuhillia. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(148–149), 44–54. [in Ukrainian]

Kleimeier, C., Rezanezhad, F., Van Cappellen, P., & Lennartz, B. (2017). Influence of pore structure on solute transport in degraded and undegraded fen peat soils. Mires and Peat, 19, 18. https://doi.org/10.19189/MaP.2017.OMB.282

Klym, M. M., & Yakibchuk, P. M. (2003). Molekuliarna fizyka. Lviv: Lvivskyi natsionalnyi universytet imeni Ivana Franka. [in Ukrainian]

Li, Y., Liu, W., Song, D., Ren, Z., Wang, H., & Guo, X. (2023). Full-scale pore characteristics in coal and their influence on the adsorption capacity of coalbed methane. Environmental Science and Pollution Research, 30, 72187–72206. https://doi.org/10.1007/s11356-023-27298-2

Liu, D., Qiu, F., Liu, N., Cai, Y., Guo, Y., Zhao, B., & Qiu, Y. (2022). Pore structure characterization and its significance for gas adsorption in coals: A comprehensive review. Unconventional Resources, 2, 139–157. https://doi.org/10.1016/j.uncres.2022.10.002

McCarter, C. P. R., Rezanezhad, F., Quinton, W. L., Gharedaghloo, B., Lennartz, B., Price, J., Connon, R., & Van Cappellen, P. (2020). Pore-scale controls on hydrological and geochemical processes in peat: Implications on interacting processes. Earth-Science Reviews, 207, 103227. https://doi.org/10.1016/j.earscirev.2020.103227

Nie, B., Liu, X., Yang, L., Meng, J., & Li, X. (2015). Pore structure characterization of different rank coals using gas adsorption and scanning electron microscopy. Fuel, 158, 908–917. https://doi.org/10.1016/j.fuel.2015.06.050

Pan, J., Wang, K., Hou, Q., Niu, Q., Wang, H., & Ji, Z. (2016). Micro-pores and fractures of coals analysed by field emission scanning electron microscopy and fractal theory. Fuel, 164, 277–285. https://doi.org/10.1016/j.fuel.2015.10.011

Rezanezhad, F., Price, J. S., & Craig, J. R. (2012). The effects of dual porosity on transport and retardation in peat: A laboratory experiment. Canadian Journal of Soil Science, 92(5), 723–732. https://doi.org/10.4141/cjss2011-050

Rezanezhad, F., Price, J. S., Quinton, W. L., Lennartz, B., Milojevic, T., & Van Cappellen, P. (2016). Structure of peat soils and implications for water storage, flow and solute transport: A review update for geochemists. Chemical Geology, 429, 75–84. https://doi.org/10.1016/j.chemgeo.2016.03.010

Rezanezhad, F., Quinton, W. L., Price, J. S., Elrick, D., Elliot, T. R., & Heck, R. J. (2009). Examining the effect of pore size distribution and shape on flow through unsaturated peat using computed tomography. Hydrology and Earth System Sciences, 13, 1993–2002. https://doi.org/10.5194/hess-13-1993-2009

Sing, K. S. W., Everett, D. H., Haul, R. A. W., Moscou, L., Pierotti, R. A., Rouquerol, J., & Siemieniewska, T. (1985). Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure and Applied Chemistry, 57(4), 603–619. https://doi.org/10.1351/pac198557040603

Zou, G., She, J., Peng, S., Yin, Q., Liu, H., & Che, Y. (2020). Two-dimensional SEM image-based analysis of coal porosity and its pore structure. International Journal of Coal Science & Technology, 7, 350–361. https://doi.org/10.1007/s40789-020-00301-8

Received: April 21, 2026
Accepted: May 08, 2026
Published: May 29, 2026

Posted on April 2026April 2026 by GGCMJournal

ESTIMATION OF THE METHANE-GENERATING CAPACITY OF FOSSIL ORGANIC MATTER

Home > Archive > No. 1 (201) 2026 > 51–62

Geology & Geochemistry of Combustible Minerals No. 1 (201) 2026, 51–62

ISSN 0869-0774 (Print), ISSN 2786-8621 (Online)

https://doi.org/10.15407/ggcm2026.201.051

Yurii KHOKHA^a, Oleksandr LYUBCHAK^b, Myroslava YAKOVENKO^c
Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine, Lviv, Ukraine

^ae-mail: khoha_yury@ukr.net, https://orcid.org/0000-0002-8997-9766
^be-mail: oleksandr.lyubchak@gmail.com, https://orcid.org/0000-0002-0700-6929
^ce-mail: myroslavakoshil@ukr.net, https://orcid.org/0000-0001-8967-0489

Abstract

The methane-generative capacity of fossil organic matter (FOM) controls both the resource potential of sedimentary successions (natural gas) and the environmental implications of CH₄ generation and migration. While equilibrium thermodynamic models provide an upper bound for methane yield, methane generation in geological settings is predominantly kinetic-controlled, and comprehensive equilibrium/kinetic reconstructions often require detailed structural inputs that are unavailable in routine practice.

Aim. To develop a minimal-parameter, chemically consistent framework for quantifying methane generation from FOM in the “solid organic matrix–fluid” system using measurable quantities and a kinetics-centered descriptor applicable under limited structural information.

Approach and methods. Methane formation is treated as a radical-controlled demethanation process, formalized by the rate expression d[CH₄]/dt = k[CH₃][H]. Here [CH₃] denotes the amount of structural methyl fragments (–CH₃) bound within the macromolecular matrix (kerogen/coal/peat), whereas [H] represents the pool of chemically bound donor hydrogen, excluding –OH and –COOH hydrogen in the baseline formulation. Conditions under which protonic (heterolytic) stages may become significant (high polarity, pore water, strong acidity/alkalinity, Lewis-acid catalysis, oxidants, transition metals, mineral surfaces, irradiation) are outlined, and it is shown that explicitly accounting for such pathways would substantially complicate the kinetic equation set. An analytical solution is discussed together with a practical reduction to an exponential law, [CH₄] = [CH₄]₀+ [CH₃]₀ (1 − e^−t/τ), where the characteristic time τ is defined from the initial slope of the methane accumulation curve CH₄(t) and can be estimated graphically via the tangent at t = 0. The paper specifies an experimental–analytical workflow to determine [CH₄]₀ by gas chromatography and to quantify the –CH₃ reservoir using direct structural methods: FTIR spectroscopy (integration of –CH₃/–CH₂ bands with spectral approximation and peak separation of overlapping features) and quantitative solid-state ¹³C MAS NMR (integration of methyl carbon at 0–22 ppm, with explicit separation of methoxyl O–CH₃ at 55–60 ppm when peat/soils are considered). Product-oriented techniques (pyrolysis GC/GC-MS and Rock-Eval) are discussed as complementary controls of CH₄ release during thermal decomposition.

Key results and interpretation. The proposed framework reduces methane-generative capacity to two experimentally anchored descriptors: the structural reservoir of methyl fragments and the kinetic parameter τ, interpreted as an integral measure of reactive-site accessibility and the overall rate of radical transformations in a given matrix. Using τ enables laboratory characterization within shortened observation windows, by passing the impracticality of directly determining k on geological time scales, and provides a consistent basis for comparing samples of different origin and maturity. The applicability domain is delineated, emphasizing external factors capable of shifting mechanisms and kinetics (O₂, water, mineral/metal catalysis, oxidants, irradiation), and the necessity to discriminate aliphatic –CH₃ from methoxyl O–CH₃ in oxygen-rich matrices is highlighted.

Conclusion and significance. The study delivers an analytically transparent and experimentally verifiable route to quantify methane-generative capacity of FOM as the coupled outcome of a measurable –CH₃ structural reserve and the characteristic time τ. The approach is suitable for comparative assessments across kerogen, coal, peat and soil organic matrices and provides a methodological foundation for further predictive modelling.

Full Text

Keywords

organic matter, kerogen, methane, methane generation, kinetics, FTIR, ¹³C MAS NMR, programmed pyrolysis

Referenses

Behar, F., Beaumont, V., & Penteado, H. L. de B. (2001). Rock-Eval 6 technology: performances and developments. Oil & Gas Science and Technology, 56(2), 111–134. https://doi.org/10.2516/ogst:2001013

Galimov, E. M. (1988). Sources and mechanisms of formation of gaseous hydrocarbons in sedimentary rocks. Chemical Geology, 71(1–3), 77–95. https://doi.org/10.1016/0009-2541(88)90107-6

Henry, A. A., & Lewan, M. D. (1999). Comparison of kinetic-model predictions of deep gas generation (No. 99-326). U.S. Department of the Interior, U.S. Geological Survey. https://doi.org/10.3133/ofr99326

Ibarra, J. V., Muñoz, E., & Moliner, R. (1996). FTIR study of the evolution of coal structure during the coalification process. Organic Geochemistry, 24(6–7), 725–735. https://doi.org/10.1016/0146-6380(96)00063-0

Johnson, R. L., & Schmidt-Rohr, K. (2014). Quantitative solid-state ¹³C NMR with signal enhancement by multiple cross polarization. Journal of Magnetic Resonance, 239, 44–49. https://doi.org/10.1016/j.jmr.2013.11.009

Kenney, J. F., Kutcherov, V. A., Bendeliani, N. A., & Alekseev, V. A. (2002). The evolution of multicomponent systems at high pressures: VI. The thermodynamic stability of the hydrogen–carbon system: The genesis of hydrocarbons and the origin of petroleum. Proceedings of the National Academy of Sciences, 99(17), 10976–10981. https://doi.org/10.1073/pnas.172376899

Khokha, Yu., Liubchak, O., & Yakovenko, M. (2019). Termodynamika transformatsii kerohenu II typu. Heolohiia i heokhimiia horiuchykh kopalyn, 3(180), 25–40. https://doi.org/10.15407/ggcm2019.03.025 [in Ukrainian]

Khokha, Yu. V., Pavliuk, M. I., Yakovenko, M. B., & Liubchak, O. V. (2020). Termodynamichna rekonstruktsiia rezhymiv evoliutsii orhanichnoi rechovyny Dniprovsko-Donetskoi zapadyny. Zbirnyk naukovykh prats Instytutu heolohichnykh nauk NAN Ukrainy, 13, 3–13. https://doi.org/10.30836/igs.2522-9753.2020.215156 [in Ukrainian]

Khokha, Yu. V., Yakovenko, M. B., & Lyubchak, O. V. (2020). Entropy maximization method in thermodynamic modelling of organic matter evolution at geodynamic regime changing. Geodynamics, 2(29), 79–88. https://doi.org/10.23939/jgd2020.02.079

Khramov, V., & Liubchak, O. (2009). Mekhanizm heneratsii metanu v porovomu prostori vuhillia. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(148–149), 44–54. [in Ukrainian]

Kuwatsuka, S., Tsutsuki, K., & Kumada, K. (1978). Chemical studies on soil humic acids: 1. Elementary composition of humic acids. Soil Science and Plant Nutrition, 24(3), 337–347. https://doi.org/10.1080/00380768.1978.10433113

Lai, D., Zhan, J. H., Tian, Y., Gao, S., & Xu, G. (2017). Mechanism of kerogen pyrolysis in terms of chemical structure transformation. Fuel, 199, 504–511. https://doi.org/10.1016/j.fuel.2017.03.013

Sweeney, J. J., & Burnham, A. K. (1990). Evaluation of a simple model of vitrinite reflectance based on chemical kinetics. AAPG Bulletin, 74(10), 1559–1570. https://doi.org/10.1306/0C9B251F-1710-11D7-8645000102C1865D

Tissot, B. P., & Welte, D. H. (2013). Petroleum formation and occurrence. Springer Science & Business Media.

Verhelska, N. V. (2016). Teoretychni osnovy perervno-neperervnoho formuvannia vuhilno-vuhlevodnevykh formatsii [Extended abstract of Doctorʼs thesis, Institute of Geological Sciences of the National Academy of Sciences of Ukraine]. Kyiv. [in Ukrainian]

Wei, L., Yin, J., Li, J., Zhang, K., Li, C., & Cheng, X. (2022). Mechanism and controlling factors on methane yields catalytically generated from low-mature source rocks at low temperatures (60–140 °C) in laboratory and sedimentary basins. Frontiers in Earth Science, 10, 889302. https://doi.org/10.3389/feart.2022.889302

Zherebetska, L., Khokha, Yu., Liubchak, O., & Khramov, V. (2011). Mekhanizm heneratsii metanu z orhanichnoi chastyny vuhillia. Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(154–155), 56–57. [in Ukrainian]

Received: January 25, 2026
Accepted: February 20, 2026
Published: April 21, 2026

Posted on April 2026April 2026 by GGCMJournal

GEOCHEMISTRY OF HALOGENESIS AND POST-SEDIMENTARY MINERALOGENESIS OF SELECTED EVAPORITE BASINS IN CHINA AND TURKEY IN RELATION TO THE FORMATION OF MINERAL RESOURCE COMPLEXES

Home > Archive > No. 1 (201) 2026 > 63–89

Geology & Geochemistry of Combustible Minerals No. 1 (201) 2026, 63–89

ISSN 0869-0774 (Print), ISSN 2786-8621 (Online)

https://doi.org/10.15407/ggcm2026.201.063

Anatoliy GALAMAY^a, Daria SYDOR^b, Sofiia MAKSYMUK^c, Oksana OLIIOVYCH-HLADKA^d
Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine, Lviv, Ukraine

^ae-mail: galamaytolik@ukr.net, https://orcid.org/0000-0003-4864-6401
^bhttps://orcid.org/0009-0007-5704-3748
^chttps://orcid.org/0009-0004-6301-9988
^dhttps://orcid.org/0009-0005-7678-1725

Abstract

Comprehensive studies of Messinian salt-bearing deposits of the Tuz Gölü Basin (Turkey) and Pleistocene deposits of the Qaidam Basin (China) have established the physicochemical causes of changes in brine composition in salt-forming basins and reconstructed the crystallization conditions of halite, glauberite, and polyhalite. These results contribute to the theoretical framework of salt mineralogenesis in applied evaporite studies and serve as geochemical criteria for predicting salt deposits. Particular attention to the identification of evaporite genesis was given to the preliminary investigation of the origin of fluid inclusions in halite.

According to the results of brine studies of fluid inclusions in halite from the Tuz Gölü Basin, the sources of salts in the basin were both continental and marine waters. A decrease in potassium concentration in basin brines is related to their interaction with organic matter and clay of continental origin. Since the concentration of sedimentary brines and their potassium content remained low throughout salt accumulation, this indicates a lack of potential for the occurrence of potash-bearing units within the salt sequence. The removal of sulfate ions and part of sodium from the brines at certain stages of basin evolution was caused by the formation of glauberite during periods of halted halite deposition. Repeated significant increases in sulfate ion concentrations in basin brines, followed by abrupt decreases, indicate favourable conditions for the occurrence of glauberite-bearing units within the depositional sequence.

According to the study of salt-bearing deposits of the Qaidam Basin, the principal mechanism of polyhalite formation was the salting-out of gypsum, which was transformed into polyhalite during the sedimentary stage. The sources of calcium in the sulfate-type salt-forming basin were continental fresh waters as well as pore and intercrystalline brines of chemogenic–terrigenous sediments. It was determined that the temperature regime of bottom brines during sedimentogenesis played a key role in the transformation of gypsum into polyhalite. Relics of potassium–magnesium minerals in the studied samples and elevated magnesium contents in the brines of secondary fluid inclusions indicate that part of the polyhalite may have formed through the replacement of sylvite and carnallite in the deposits due to calcium input from solutions associated with nearby oil accumulations. The established physicochemical conditions of polyhalite formation in the basin expand the theoretical understanding of polyhalite mineralization in fundamental and applied studies and represent geochemical criteria for predicting its deposits.

Detailed investigation of chemical paleooceanography, the features of salt mineral formation with specific chemical compositions in basins, and the discrimination between marine and continental salt-forming basins makes a significant contribution to understanding the genetic nature of evaporite-related mineral resources and to improving their future exploration and prediction.

Full Text

Keywords

fluid inclusions, halite, glauberite, polyhalite, sources of salts

Referenses

Akgün, F., Kayseri-Özer, M. S., Tekin, E., Varol, B., Şen, Ş., Herece, E., Gündoğan, İ., Sözeri, K., & Us, M. S. (2021). Late Eocene to Late Miocene palaeoecological and palaeoenvironmental dynamics of the Ereğli–Ulukışla Basin (Southern Central Anatolia). Geological Journal, 56(2), 673–703. https://doi.org/10.1002/gj.4021

Andeskie, A. S., & Benison, K. C. (2020). Using sedimentology to address the marine or continental origin of the Permian Hutchinson Salt Member of Kansas. Sedimentology, 67(2), 882–896. https://doi.org/10.1111/sed.12665

Ayora, C., Garcia-Veigas, J., & Pueyo, J. J. (1994). The chemical and hydrological evolution of an ancient potash-forming evaporite basin as constrained by mineral sequence, fluid inclusion composition, and numerical simulation. Geochimica et Cosmochimica Acta, 58(16), 3379–3394. https://doi.org/10.1016/0016-7037(94)90093-0

Benison, K. C., & Goldstein, R. H. (1999). Permian paleoclimate data from fluid inclusions in halite. Chemical Geology, 154(1–4), 113–132. https://doi.org/10.1016/S0009-2541(98)00127-2

Charykova, M. V., Kurilenko, V. V., & Charykov, N. A. (1992). Temperatures of formation of certain salts in sulfate-type brines. Journal of Applied Chemistry of the USSR, 65(6), 1037–1040.

Demir, E., & Varol, E. (2022). Origin and palaeodepositional environment of evaporites in the Bala sub-basin, Central Anatolia, Türkiye. International Geology Review, 65(11), 1900–1922. https://doi.org/10.1080/00206814.2022.2114021

Doebelin, N., & Kleeberg, R. (2015). Profex: a graphical user interface for the Rietveld refinement program BGMN. Journal of Applied Crystallography, 48, 1573–1580. https://doi.org/10.1107/S1600576715014685

Dumon, M., & Van Ranst, E. (2016). PyXRD v0.6.7: a free and open-source program to quantify disordered phyllosilicates using multi-specimen X-ray diffraction profile fitting. Geoscientific Model Development, 9, 41–57. https://doi.org/10.5194/gmd-9-41-2016

Ercan, H. Ü., Karakaya, M. Ç., Bozdağ, A., Karakaya, N., & Delikan, A. (2019). Origin and evolution of halite based on stable isotopes (δ³⁷Cl, δ⁸¹Br, δ¹¹B and δ⁷Li) and trace elements in Tuz Gölü Basin, Turkey. Applied Geochemistry, 105, 17–30. https://doi.org/10.1016/j.apgeochem.2019.04.008

Galamay, A. R., Karakaya, M. Ç., Bukowski, K., Karakaya, N., & Jaremchuk, Y. (2023). Geochemistry of brine and paleoclimate reconstruction during sedimentation of Messinian salt in the Tuz Gölü Basin (Türkiye): Insights from the study of fluid inclusions. Minerals, 13(2), 171. https://doi.org/10.3390/min13020171

Galamay, A. R., Meng, F., & Bukowski, K. (2014). Sulphur isotopes in anhydrite from Badenian (Middle Miocene) salts of the Hrynivka area (Ukrainian Carpathian Foredeep). Geological Quarterly, 58(3), 439–448. https://doi.org/10.7306/gq.1159

Garcia-Veigas, J., Orti, F., Rosell, L., Ayora, C., Rouchy, J.-M., & Lugli, S. (1995). The Messinian salt of the Mediterranean: geochemical study of the salt from the Central Sicily Basin and comparison with the Lorca Basin (Spain). Bulletin de la Societé géologique de France, 166(6), 699–710.

Görür, N., & Derman, A. S. (1978). Stratigraphic and tectonic analysis of the Tuz Gölü-Haymana Basin (Turkish Petroleum Corporation Report 1514). TPAO. Ankara, Turkey.

Görür, N., Okay, F. Y., Seymen, I., & Şengör, A. M. C. (1984). Paleotectonic evolution of the Tuzgölü basin complex, Central Turkey: Sedimentary record of a Neo-Tethyan closure. Geological Society, London, Special Publications, 17, 467–482. https://doi.org/10.1144/GSL.SP.1984.017.01.34

Gündoğan, I., & Helvaci, С. (1996). Geology, hydrochemistry, mineralogy and economic potential of the Bolluk lake (Cihanbeyli-Konya) and the adjacent area. Turkish Journal of Earth Sciences, 5(2), 91–104. https://doi.org/10.55730/1300-0985.1741

Halamai, A. R. (2012a). Vplyv kontynentalnykh vod na sklad morskykh rozsoliv tsentralnoi chastyny badenskoho solerodnoho baseinu Ukrainskoho Peredkarpattia. Mineralohichnyi zbirnyk, 62(2), 228–235. [in Ukrainian]

Halamai, A. (2012b). Umovy utvorennia halitu v badenskomu Zakarpatskomu solerodnomu baseini (za doslidzhenniamy vkliuchen). Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(160–161), 82–101. [in Ukrainian]

Halamai, A., Poberezhskyi, A., Hryniv, S., Vovniuk, S., Sydor, D., Yaremchuk, Ya., Maksymuk, S., Oliiovych-Hladka, O., & Bilyk, L. (2021). Heokhimichni osoblyvosti evaporytovykh formatsii Yevrazii u konteksti evoliutsii khimichnoho skladu morskoi vody protiahom fanerozoiu. Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(183–184), 110–129. https://doi.org/10.15407/ggcm2021.01-02.110 [in Ukrainian]

Halamai, A. R., Sydor, D. V., & Oliiovych-Hladka, O. V. (2021). Dosvid praktychnoho vykorystannia ultramikrokhimichnoho metodu doslidzhennia khimichnoho skladu rozsoliv fliuidnykh vkliuchen u haliti. In Heolohichna nauka v nezalezhnii Ukraini: zbirnyk tez naukovoi konferentsii, prysviachenoi 30-tii richnytsi Nezalezhnosti Ukrainy (8–9 veresnia 2021 r.) (pp. 26–28). Kyiv. [in Ukrainian]

Halamai, A., Zinchuk, I., & Sydor, D. (2023). Termometrychni doslidzhennia fliuidnykh vkliuchen u badenskomu haliti karpatskoho rehionu v konteksti vstanovlennia hlybyny solerodnoho baseinu. Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(189–190), 54–65. https://doi.org/10.15407/ggcm2023.189-190.054 [in Ukrainian]

Hua, Z., Liu, C., Zhang, Y., & Dai, T. (2015). Characteristics and hydrogen–oxygen isotopic compositions of halite fluid inclusions in the Thakhek area, Laos, and the way of salt material supplie. Acta Geologica Sinica, 11, 2134–2140.

Karakaya, M. C., Bozdağ, A., Ercan, H. Ü., & Karakaya, N. (2020). The origin of Miocene evaporites in the Tuz Gölü basin (Central Anatolia, Turkey): Implications from strontium, sulfur and oxygen isotopic compositions of the Ca-Sulfate minerals. Applied Geochemistry, 120, 104682. https://doi.org/10.1016/j.apgeochem.2020.104682

Karakaya, M. Ç., Bozdağ, A., Ercan, H. Ü., Karakaya, N., & Delikan, A. (2019). Origin of Miocene halite from Tuz Gölü basin in Central Anatolia, Turkey: Evidences from the pure halite and fluid inclusion geochemistry. Journal of Geochemical Exploration, 202. https://doi.org/10.1016/j.gexplo.2019.03.004

Karakaya, M. Ç., Bozdağ, A., & Karakaya, N. (2021). Elemental and C, O and Mg isotope geochemistry of middle-late Miocene carbonates from the Tuz Gölü Basin (Central Anatolia, Turkey): Evidence for Mediterranean incursions. Journal of Asian Earth Sciences, 221, 104946. https://doi.org/10.1016/j.jseaes.2021.104946

Kashkarov, O. D. (1956). Sadka solei v solyanykh ozerakh. Trudy VNIIG, 32, 3–33. [in Russian]

Kovalevich, V. M. (1990). Galogenez i khimicheskaia evoliutciia okeana v fanerozoe. Kiev: Naukova dumka. [in Russian]

Kovalevych, V. M., Jarmołowicz-Szulc, K., Peryt, T. M., & Poberegski, A. V. (1997). Messinian chevron halite from the Red Sea (DSDP Sites 225 and 227): fluid inclusion study. N. Jb. Mineral. Mh., 10, 433–450. https://doi.org/10.1127/njmm/1997/1997/433

Li, C., Li, В., & Li, Z. (1990). Census report of the potash deposit in Kunteyi, Lenghu Town, Qinghai Province. Delingha. The Qinghai Qiandam comprehensive geological survey unit. [in Chinese]

Li, J., Li, W., Miao, W., Tang, Q., Li, Y., Yuan, X., Hai, Q., Du, Y., & Zhang, X. (2022). Reconstruction of polyhalite ore-formed temperature from Late Middle Pleistocene brine temperature research in Kunteyi Playa, Western China. Geofluids, 255886. https://doi.org/10.1155/2022/6255886

Li, M., Fang, X., Galy, A., Wang, H., Song, X., & Wang, X. (2020). Hydrated sulfate minerals (bloedite and polyhalite): formation and paleoenvironmental implications. Carbonates and Evaporites, 35, 126. https://doi.org/10.1007/s13146-020-00660-y

Liu, C., Ma, L., Jiao, P., Sun, X., & Chen, Y. (2010). Chemical sedimentary sequence of Lop Nur salt lake in Xinjiang and its controlling factors. Mineral. Deposits, 29(4), 625–630.

Lowenstein, T. K., Li, J., & Brown, C. B. (1998). Paleotemperatures from fluid inclusions in halite: method verification and a 100,000 year paleotemperature record, Death Valley, CA. Chemical Geology, 150(3–4), 223–245. https://doi.org/10.1016/S0009-2541(98)00061-8

Lowenstein, T. K., Timofeeff, M. N., Brennan, S. T., Hardie, L. A., & Demicco, R. V. (2001). Oscillations in Phanerozoic seawater chemistry: evidence from fluid inclusions. Science, 294(5544), 1086–1088. https://doi.org/10.1126/science.1064280

McCaffrey, M. A., Lazar, B., & Holland, H. D. (1987). The evaporation path of seawater and the coprecipitation of Br⁻ and K⁺ with halite. Journal of Sedimentary Research, 57(5), 928–937. https://doi.org/10.1306/212F8CAB-2B24-11D7-8648000102C1865D

Morachevskii, Iu. V., & Petrova, E. M. (1965). Metody analiza rassolov i solei. Moskva; Leningrad: Khimiia. [in Russian]

Palmer, M. R., Helvací, C., & Fallick, A. E. (2004). Sulphur, sulphate oxygen and strontium isotope composition of Cenozoic Turkish evaporites. Chemical Geology, 209(3–4), 341–356. https://doi.org/10.1016/j.chemgeo.2004.06.027

Pavlyshyn, V. I., Diakiv, V. O., Tsar, Kh. M., & Kytsmur, I. I. (2012). Ontohenichni zakonomirnosti krystalizatsii mirabilit-tenardytovykh ahrehativ z ropy kaliinykh rodovyshch Peredkarpattia. Mineralohichnyi zhurnal, 2(34), 17–25. [in Ukrainian]

Petrichenko, O. I. (1988). Fiziko-khimicheskie usloviia osadkoobrazovaniia v drevnikh solerodnykh basseinakh. Kiev: Naukova dumka. [in Russian]

Petrychenko, O. Y. (1973). Metody doslidzhennia vkliuchen u mineralakh halohennykh porid. Kyiv: Naukova dumka. [in Ukrainian]

Şafak, Ü., Kelling, G., Gökçen, N. S., & Gürbüz, K. (2005). The mid-Cenozoic succession and evolution of the Mut basin, southern Turkey, and its regional significance. Sedimentary Geology, 173(1–4), 121–150. https://doi.org/10.1016/j.sedgeo.2004.03.012

Timofeeﬀ, M. N., Lowenstein, T. K., Martins da Silva, M. A., & Harris, N. B. (2006). Secular variation in the major-ion chemistry of seawater: Evidence from ﬂuid inclusions in Cretaceous halites. Geochimica et Cosmochimica Acta, 70(8), 1977–1994. https://doi.org/10.1016/j.gca.2006.01.020

Vakhrameeva, V. A. (1956). K mineralogii i petrografii solianykh otlozhenii zaliva Karabogaz-Gol. Trudy VNIIG, 32, 67–86. [in Russian]

Valiashko, M. G. (1962). Zakonomernosti formirovaniia mestorozhdenii solei. Moskva: Moskovskii universitet. [in Russian]

Valiashko, M. G., & Pelsh, G. K. (1952). Metamorfizatciia nasyshchennykh sulfatnykh rastvorov bikarbonatom kaltciia. Trudy VNIIG, 23, 177–200. [in Russian]

Wang, M., Yang, Z., Liu, C., Xie, Z., Jiao, P., & Li, C. (1997). Potash deposits and their exploitation prospects of saline lakes of the north Qaidam Basin. Beijing: Geological Publishing House. [in Chinese]

Wei, X., Shao, C., Wang, M., Zhao, D., Cai, K., Jiang, J., He, G. & Hu, W. (1993). Material constituents, depositional features and formation conditions of potassium-rich Salt Lakes in western Qaidam Basin. Beijing: Geological Publishing House.

Xu, Y., Cao, Y., & Liu, C. (2021). Whether the Middle Eocene salt-forming brine in the Kuqa Basin reached the potash-forming stage: Quantitative evidence from halite fluid inclusions. Geofluids, 5574772. https://doi.org/10.1155/2021/5574772

Zhang, X., Fan, Q., Li, Q., Du, Y., Qin, Z., Wei, H., & Shan, F. (2019). The source, distribution, and sedimentary pattern of K-rich brines in the Qaidam Basin, Western China. Minerals, 9(11), 655. https://doi.org/10.3390/min9110655

Zhang, Y., & Xuan, Z. (1996). Economic evaluation of potassium and magnesium solid deposit in Kunteyi and Mahai Salt Lake of Qinghai Province. Journal of Salt Lake Science, 4(1), 36–45. [in Chinese]

Zhou, J., Gong, D., & Li, M. (2015). The characteristic of evaporite, migration of salt basins and its tectonic control in Triassic Sichuan Basin. Acta Geologica Sinica, 11, 1945–1952.

Zimmermann, H. (2000). Tertiary seawater chemistry – implications from primary fluid inclusions in marine halite. American Journal of Science, 300(10), 723–767. https://doi.org/10.2475/ajs.300.10.723

Zinchuk, I. M. (2003). Heokhimiia mineraloutvoriuiuchykh rozchyniv zoloto-polimetalevykh rudoproiaviv Tsentralnoho Donbasu (za vkliuchenniamy u mineralakh) [Extended abstract of Candidateʼs thesis, Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine]. Lviv. [in Ukrainian]

Received: January 21, 2026
Accepted: February 23, 2026
Published: April 21, 2026

Posted on December 2025February 2026 by GGCMJournal

GEOCHEMICAL FEATURES OF THE DISTRIBUTION OF MOBILE FORMS OF Pb, Cd, As, and Hg IN PEATLANDS OF THE LVIV REGION

Home > Archive > No. 3–4 (199–200) 2025 > 25–43

Geology & Geochemistry of Combustible Minerals No. 3–4 (199–200) 2025, 25–43

https://doi.org/10.15407/ggcm2025.199-200.025

Myroslav PAVLYUK¹, Myroslava YAKOVENKO², Yurii KHOKHA³, Olga SERDІUKOVA⁴
^{1, 2, 3}Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, Ukraine, e-mail: ¹pavlyuk.myroslav@gmail.com; ²myroslavakoshil@ukr.net; ³khoha_yury@ukr.net
⁴V. N. Karazin Kharkiv National University, Kharkiv, Ukraine, e-mail: serd.64@ukr.net

Abstract

The aim of the work was to quantitatively characterize the spatial‑stratigraphic variability of mobile forms of lead (Pb), cadmium (Cd), arsenic (As) and mercury (Hg) in peatlands of the Lviv Region and to identify the main physicochemical factors of their accumulation.

Materials and methods. 26 samples from six peatlands (Bilohorshcha, Honchary, Hamaliivka, Artyshchiv, Polonychna, Sknylivok) were studied along profiles 0–140 cm at 20 cm intervals. Mobile forms of Pb, Cd, As were determined by ICP AES after extraction with 0.2 M HCl, whereas Hg was measured by direct thermal decomposition-amalgamation AAS (NIC MA 3 Solo) without prior wet extraction. pH, ash content (Ash), moisture content (W), and organic matter content were measured. Statistical processing included descriptive statistics, geoaccumulation index (GI), Spearman correlations, hierarchical clustering (Ward) and PCA with varimax rotation.

Results. The studied peat deposits of the Lviv Region are characterized by a high proportion of organic matter (median = 83.95 %), variable ash content (9.69–37.08 %) and an acidic-to-weakly neutral environment (pH = 4.40–7.69). Mobile forms of Pb, Cd, As and Hg show high spatial stratigraphic variability and lognormal distributions; coefficients of variation are ≈ 236–263–136 % for Pb, Cd and Hg, respectively, while As has moderately high variability (≈ 82 %). According to the averaged concentration coefficients normalized to the median, the geochemical spectrum is: Cd (3.57) > Pb (3.02) > Hg (1.28) > As (1.20). Comparison with lithospheric and soil reference levels indicates persistent enrichment in Cd, whereas Hg is generally at background to subbackground levels (I_geo ≤ 0), with Pb and As mostly not exceeding background except for local anomalies. The vertical structure is mosaic: Hg shows modest near-surface increases with no stable deep maxima and no significant geoaccumulation (I_geo < 0); Pb frequently peaks near the surface but exhibits a deep maximum in the Honchary profile (60–80 cm); Cd forms contrasting intraprofile anomalies (Honchary, 60–80 cm), and As combines near-surface increases with a deep peak (Hamaliivka, 120–140 cm), indicating the role of redox gradients and mineral admixture. Multivariate analyses (correlation, clustering, PCA) before and after ash normalization consistently reveal a stable cationic Pb–Cd block, organic control of As, and moisture-redox-acid-base control on Hg, separating the roles of organic and mineral phases in forming profile anomalies and providing a basis for further monitoring.

Full Text

Keywords

peat, geochemistry, mobile forms, lead, cadmium, arsenic, mercury, Lviv Region

Referenses

Borówka, R. K., Sławińska, J., Okupny, D., Osóch, P., & Tomkowiak, J. (2022). Mercury in the sediments of selected peatlands in Małopolska region. Acta Geographica Lodziensia, 112, 61–76. https://doi.org/10.26485/AGL/2022/112/5

Bowen H. J. M. (1979). Environment Chemistry of the Elements. London; New York; Toronto; Sydney; San Francisco: Academic Press.

Fiałkiewicz-Kozieł, B., Smieja-Król, B., & Palowski, B. (2011). Heavy metal accumulation in two peat bogs from southern Poland. Studia Quaternaria, 28, 17–24.

Instytut gruntoznavstva ta ahrokhimii imeni O. N. Sokolovskoho Ukrainskoi akademii ahrarnykh nauk. (2006). Yakist gruntu. Vyznachennia rukhomykh spoluk fosforu i kaliiu za metodom Kirsanova v modyfikatsii NNTs IHA (DSTU 4405:2005). Kyiv: Derzhspozhyvstandart Ukrainy. [in Ukrainian]

Instytut gruntoznavstva ta ahrokhimii imeni O. N. Sokolovskoho Ukrainskoi akademii ahrarnykh nauk. (2008). Melioranty gruntu ta seredovyshcha rostu. Hotuvannia prob do khimichnoho ta fizychnoho analizu, vyznachennia vmistu sukhoi rechovyny, vmistu volohy ta laboratorno ushchilnenoi nasypnoi shchilnosti (DSTU EN 13040:2005). Kyiv. [in Ukrainian]

Instytut silskohospodarskoi mikrobiolohii ta ahropromyslovoho vyrobnytstva NAAN (2016). Torf i produkty yoho pereroblennia dlia silskoho hospodarstva. Metody vyznachennia obminnoi y aktyvnoi kyslotnosti (DSTU 7882:2015). Kyiv. [in Ukrainian]

Jensen, A. (1997). Historical deposition rates of Cd, Cu, Pb, and Zn in Norway and Sweden estimated by 210Pb dating and measurement of trace elements in cores of peat bogs. Water, Air, and Soil Pollution, 95(1), 205–220. https://doi.org/10.1007/BF02406166

Kempter, H., & Frenzel, B. (1999). The local nature of anthropogenic emission sources on the elemental content of nearby ombrotrophic peat bogs, Vulkaneifel, Germany. Science of the Total Environment, 241(1–3), 117–128. https://doi.org/10.1016/S0048-9697(99)00331-9

Klos, V. R., Birke, M., Zhovynskyi, E. Ya., Akinfiiev, H. O., Amashukeli, Yu. A., & Klamens, R. (2012). Rehionalni heokhimichni doslidzhennia gruntiv Ukrainy v ramkakh mizhnarodnoho proektu z heokhimichnoho kartuvannia silskohospodarskykh ta pasovyshchnykh zemel Yevropy (GEMAS). Poshukova ta ekolohichna heokhimiia, 1(12), 51–66. [in Ukrainian]

Miszczak, E., Stefaniak, S., Michczyński, A., Steinnes, E., & Twardowska, I. (2020). A novel approach to peatlands as archives of total cumulative spatial pollution loads from atmospheric deposition of airborne elements complementary to EMEP data: priority pollutants (Pb, Cd, Hg). Science of the Total Environment, 705, 135776. https://doi.org/10.1016/j.scitotenv.2019.135776

Nieminen, T. M., Ukonmaanaho, L., & Shotyk, W. (2002). Enrichment of Cu, Ni, Zn, Pb and As in an ombrotrophic peat bog near a Cu–Ni smelter in Southwest Finland. Science of the Total Environment, 292(1–2), 81–89. https://doi.org/10.1016/S0048-9697(02)00028-1

Tekhnichnyi komitet standartyzatsii “Gruntoznavstvo” (TK 142) ta Natsionalnyi naukovyi tsentr “Instytut gruntoznavstva ta ahrokhimii im. O. N. Sokolovskoho” (2015). Yakist gruntu. Vyznachennia zolnosti torfu i torfovoho gruntu (DSTU 7942:2015). Kyiv. [in Ukrainian]

Ukonmaanaho, L., Nieminen, T. M., Rausch, N., & Shotyk, W. (2004). Heavy Metal and Arsenic Profiles in Ombrogenous Peat Cores from Four Differently Loaded Areas in Finland. Water, Air, & Soil Pollution, 158, 277–294. https://doi.org/10.1023/B:WATE.0000044860.70055.32

Vile, M. A., Wieder, R. K., & Novák, M. (1999). Mobility of Pb in Sphagnum-derived peat. Biogeochemistry, 45(1), 35–52. https://doi.org/10.1007/BF00992872

Voitkevich, G. V., Miroshnikov, A. E., Povarennykh, A. S., & Prokhorov, V. G. (1970). Kratkii spravochnik po geokhimii. Moskva: Nedra. [in Russian]

Posted on June 2025September 2025 by GGCMJournal

DETERMINATION AND DISTRIBUTION of Na, K, Li, Ca, and Ba MOBILE FORMS IN PEAT OF THE LVIV REGION BY FLAME SPECTROPHOTOMETRY

Home > Archive > No. 1–2 (197–198) 2025 > 75–90

Geology & Geochemistry of Combustible Minerals No. 1–2 (197–198) 2025, 75–90

https://doi.org/10.15407/ggcm2025.197-198.075

Myroslava YAKOVENKO¹, Yurii KHOKHA²
Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, Ukraine, e-mail: ¹myroslavakoshil@ukr.net; ²khoha_yury@ukr.net

Abstract

The article presents the results of determining the quantitative content and geochemical features of the distribution (including depth distribution), accumulation, migration, and origin of Na, K, Li, Ca, and Ba mobile forms in peat from selected representative deposits and areas of the Lviv Region (Bilogorshcha, Honchary, Hamaliivka, Artyshchiv, Polonychna, Sknylivok), and identifying the main factors affecting the unevenness of their concentration. The analyses were performed using the flame spectrophotometry method with two low-temperature flame spectrophotometers: FP910 (PG Instruments) and FF-200 (Cole-Parmer, Jenway). This method is distinguished by its simplicity, speed, expressivity, high sensitivity, reliability, and relatively low equipment cost.

Mathematical and statistical processing of the quantitative characteristics of the distribution of Ca, Ba, Na, K, and Li mobile forms content in the studied peatlands of the Lviv Region was carried out using MS Excel 2019 and Statistica 12 software packages. Employing correlation (calculation and construction of correlation matrices and profiles), cluster, and factor (principal component method) analyses, the degree of dependence between variables and typomorphic geochemical associations of mobile forms of chemical elements in the researched environment were established. The values of the limits of local background fluctuations and the level of element content deviations were determined; the values of the concentration coefficients relative to the background (median) content were calculated.

The vertical distribution of Ca, Ba, Na, K, and Li mobile forms along the peat deposit profiles showed that the content of K and Na decreases with depth for all researched deposits, as well as Ca, Ba, and Li (except Honchary deposit). It was established that the vertical distribution of the studied elementsʼ mobile forms in peat deposits is characterized by maxima in the upper peat horizon and contact layers with mineral soil (0–40 cm), which is mainly due to biological accumulation and aeolian input. An exception is the uneven distribution of Ca, Ba, and Li in the Honchary peat deposit, where a significant enrichment with freshwater mollusk shells is observed, particularly at a depth of 80–120 cm.

Full Text

Keywords

peat, mobile forms, elemental analysis, flame spectrophotometry

Referenses

Alekseenko, V. A. (1990). Geokhimiia landshafta i okruzhaiushchei sredy. Moskva: Nedra. [in Russian]

Alekseenko, V. A. (2000). Ekologicheskaia geokhimiia. Moskva: Logos. [in Russian]

Andrejko, M. J., Fiene, F., & Cohen, A. D. (1983). Comparison of ashing techniques for determination of the inorganic content of peats. In P. M. Jarrett (Ed.), Testing of Peats and Organic Soils (pp. 5–20). Philadelphia: ASTM International. https://doi.org/10.1520/STP37331S

Bowen, H. J. M. (1979). Environment Chemistry of the Elements. London; New-York; Toronto; Sydney; San Francisco: Academic Press.

Lishtvan, I. I., Bazin, E. T., Gamaiunov, N. I., & Terentev, A. A. (1989). Fizika i khimiia torfa. Moskva: Nedra. [in Russian]

Lucas, R. E. (1982). Organic soils (Histosols) formation, distribution, physical and chemical properties and management for crop production (No 435, pp. 3–77) [Research Report]. Michigan State University.

Malyshev, V., Hab, A., Shakhnin, D. (2018). Analitychna khimiia ta instrumentalni metody analizu. Universytet “Ukraina”. [in Ukrainian]

Rydelek, P. (2013). Origin and composition of mineral constituents of fen peats from Eastern Poland. Journal of Plant Nutrition, 36(6), 911–928. https://doi.org/10.1080/01904167.2013.770525

Siddique, M. A. B., Alam, M. K., Islam, S., Diganta, M. T. M., Akbor, M. A., Bithi, U. H., Chowdhury, A. I., & Ullah, A. A. (2020). Apportionment of some chemical elements in soils around the coal mining area in northern Bangladesh and associated health risk assessment. Environmental Nanotechnology, Monitoring & Management, 14, Article 100366. https://doi.org/10.1016/j.enmm.2020.100366

Spaska, O. A., Bilokopytov, Yu. V., & Yatchyshyn, Y. Y. (2024). Analitychna khimiia ta instrumentalni metody khimichnoho analizu. Kyiv: Vydavnytstvo Natsionalnoho aviatsiinoho universytetu “NAU-druk”. [in Ukrainian]

Qin, S., Zhao, C., Li, Y., & Zhang, Y. (2015). Review of coal as a promising source of lithium. International Journal of Oil, Gas and Coal Technology, 9(2), 215–229. https://doi.org/10.1504/IJOGCT.2015.067490

Voitkevich, G. V., Miroshnikov, A. E., Povarennykh, A. S., Prokhorov, V. G. (1970). Kratkii spravochnik po geokhimii. Moskva: Nedra. [in Russian]

Yakovenko, M., Khokha, Yu., & Liubchak, O. (2022). Heokhimichni osoblyvosti nakopychennia i mihratsii vazhkykh metaliv u torfakh Lvivskoi oblasti. Visnyk Kharkivskoho natsionalnoho universytetu imeni V. N. Karazina, ceriia “Heolohiia. Heohrafiia. Ekolohiia”, 56, 105–121. https://doi.org/10.26565/2410-7360-2022-56-07 [in Ukrainian]

Posted on June 2025September 2025 by GGCMJournal

THE CHEMICAL COMPOSITION OF FLUID INCLUSIONS BRINE IN HALITE OF EVAPORITE DEPOSITS IN WENKOU DEPRESSION (PRC) IN THE CONTEXT OF SALT MINERALOGENESIS

Home > Archive > No. 1–2 (197–198) 2025 > 57–74

Geology & Geochemistry of Combustible Minerals No. 1–2 (197–198) 2025, 57–74

https://doi.org/10.15407/ggcm2025.197-198.057

Anatoliy GALAMAY¹, Fanwei MENG², Daria SYDOR¹
¹Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, Ukraine, e-mail: galamaytolik@ukr.net
²China University of Mining and Technology (CUMT), Xuzhou, Jiangsu Province, China, e-mail: fwmeng@isl.ac.cn

Abstract

The chemical composition of brines of fluid inclusions of different genesis has established the peculiarities of mineralogenesis of the Wenkou Depression of the Dawenkou Basin. The content of K⁺, Mg²⁺ and SO₄²⁻ in sedimentary brines ranged from 27.6 to 32.9, 41.5 to 32.7, and 66.6 to 33.3 g/l, respectively. The obtained data on the chemical composition of sedimentary brines and the values of δ³⁴S (+10.9…+35.7 ‰) and δ¹⁸O (+14.7…+19.4 ‰) of anhydrite do not exclude the influence of marine transgressions on the continental halogenation of the Dawenkou Basin. The main source of sulfate in the Basin was ancient evaporites in the Yi-Meng Mountains of Shandong Province, which were eroded by surface waters. At the post-sedimentation stage, the salt strata were heated to temperatures of about 45 and 63 ℃. Halite recrystallization occurred at elevated pressure, which was tens of times higher than normal atmospheric pressure.

Weakly mineralized waters enriched in Ca(HCO₃)₂, which entered the basin, led to the precipitation of gypsum or glauberite. Taking into account the high potassium content in the brines, which is close to the beginning of sylvite deposition, one can expect polyhalite (due to newly formed gypsum) mineralization to be found in the sediments.

The chemical composition of post-sedimentation brines is characterized by a wide fluctuation in the content of the main ions. In the salt-bearing stratum, brines of various compositions circulated: a) with a sharply increased (relative to the sedimentary) content of potassium, magnesium and sulfate; b) with an increased content of potassium, magnesium and a reduced content of sulfate; c) with a reduced content of potassium and an increased content of magnesium and sulfate; d) with a significantly reduced concentration of all ions.

In the XZK-101 well under investigation, no other salt minerals were found except halite, mirabilite, and glauberite. However, according to the data from the study of the chemical composition of brine inclusions in halite, in the immediate vicinity of its location in the Wenkou Depression, one should expect the detection of kieserite, langbeinite, and other salt minerals in salt deposits. The formation of langbeinite was facilitated by elevated temperatures and pressure. The brines found with an abnormally high magnesium content are apparently residual brines (reaction products) during the formation of langbeinite due to unstable sedimentary hexahydrite and sylvite.

According to the obtained data on the chemical composition of brines of inclusions in halite, the boundaries of both the halite and potassic facies on the existing facies maps of the basin are subject to revision.

Full Text

Keywords

fluid inclusions, halite, brines, homogenization temperature, salt strata

Referenses

Acros, D., & Ayora, C. (1997). The use of fluіd іnclusіons іn halіte as envіronmental thermometer: an experіmental study. In M. C. Boiron & J. Pironon (Eds.), XIV ECROFІ: proceedings of the XIVth European Current Research on Fluid Inclusions, Nancy, France, July 1–4, 1997 (pp. 10–11). CNRS-CREGU.

Benison, K. C. (2019). How to search for life in Martian chemical sediments and their fluid and solid inclusions using petrographic and spectroscopic methods. Frontiers in Environmental Science, 7, 108. https://doi.org/10.3389/fenvs.2019.00108

Claypool, G. E., Holser, W. T., Kaplan, І. R., Sakaі, H., & Zak, І. (1980). The age curves of sulfur and oxygen іsotopes іn marіne sulfate and theіr mutual іnterpretatіon. Chemical Geology, 28, 199–260. https://doi.org/10.1016/0009-2541(80)90047-9

Eugster, H. P., Harvіe, C. E., & Weare, J. H. (1980). Mіneral equіlіbrіa іn a sіx-component seawater system, Na-K-Mg-Ca-SO₄-Cl-H₂O, at 25 °C. Geochimica et Cosmochimica Acta, 44(9), 1335–1347. https://doi.org/10.1016/0016-7037(80)90093-9

Galamay, A. R., Bukowski, K., Sydor, D. V., & Meng, F. (2020). The ultramicrochemical analyses (UMCA) of fluid inclusions in halite and experimental research to improve the accuracy of measurement. Minerals, 10(9), 823. https://doi.org/10.3390/min10090823

Galamay, A. R., Karakaya, M. Ç., Bukowski, K., Karakaya, N., & Yaremchuk, Y. (2023). Geochemistry of brine and paleoclimate reconstruction during sedimentation of Messinian salt in the Tuz Gölü Basin (Türkiye): Insights from the study of fluid inclusions. Minerals, 13(2), 171. https://doi.org/10.3390/min13020171

Galamay, A. R., Meng, F., Bukowski, K., Ni, P., Shanina, S. N., & Ignatovich, O. O. (2016). The sulphur and oxygen isotopic composition of anhydrite from the Upper Pechora Basin (Russia): new data in the context of the evolution of the sulphur isotopic record of Permian evaporites. Geological Quarterly, 60(4), 990–999. https://doi.org/10.7306/gq.1309

Gibson, M. E., & Benison, K. C. (2023). It’s a trap!: Modern and ancient halite as Lagerstätten. Journal of Sedimentary Research, 93(9), 642–655. https://doi.org/10.2110/jsr.2022.110

Halamai, A. R., Maksymuk, S. V., & Sydor, D. V. (2021). Heokhimichni osoblyvosti vplyvu naftohazovykh pokladiv na pokryvaiuchi soli Karpatskoi naftohazonosnoi provintsii. In Nadrokorystuvannia v Ukraini. Perspektyvy investuvannia: Mizhnarodna naukovo-praktychna konferentsiia (1–5 lystopada 2021 r.) (pp. 100–105). Lviv. [in Ukrainian]

Halamai, A. R., Sadovyi, Yu. V., Meng, F., & Sydor, D. (2024). Fizyko-khimichni umovy formuvannia polihalitu pivnichno-zakhidnoi chastyny baseinu Kaidam, KNR. Mineralohichnyi zbirnyk, 74, 94–108. https://doi.org/10.30970/min.74.08 [in Ukrainian]

Halas, S., & Szaran, J. (1999). Low-temperature thermal decomposition of sulfates to SO₂for on-line ³⁴S/³²S analysis. Analytical Chemistry, 71(15), 3254–3257. https://doi.org/10.1021/ac9900174

Khodkova, S. V. (1968). Langbeinit Peredkarpatia i ego paragenezisy. Litologiia i poleznye iskopaemye, 6, 73–85. [in Russian]

Kovalevich, V. M. (1973). Fiziko-khimicheskie usloviia formirovaniia solei Stebnikskogo kaliinogo mestorozhdeniia. Kiev: Naukova dumka. [in Russian]

Li, M. H. (1986). Paleoecological analysis of the early Tertiary oil-bearing sedimentary formation in the Dongpu depression, North China Diwa Region. Geotectonica Metallogenia, 10, 159–168. [in Chinese with English abstract]

Liu, M. W., Song, W. Q., Xu, J. Q., Zhang, Y. J., & Xu, L. J. (2003). Geological characteristics of Cambrian gypsum deposit in Longquan of Yiyuan County. Geology of Shandong, 19(1), 39–42. [in Chinese with English abstract]

Lowenstein, T. K., Li, J. & Brown, C. B. (1998). Paleotemperatures from fluid inclusions in halite: method verification and a 100,000 year paleotemperature record, Death Valley, CA. Chemical Geology, 150(3–4), 223–245. https://doi.org/10.1016/S0009-2541(98)00061-8

Meng, F., Galamay, A. R., Ni, P., Ahsan, N., & Rehman, S. U. (2020). Composition of middle-late Eocene salt lakes in the Jintan Basin of eastern China: Evidence of marine transgressions. Marine and Petroleum Geology, 122, Article 104644. https://doi.org/10.1016/j.marpetgeo.2020.104644

Meng, F., Galamay, A. R., Ni, P., Yang, C.-H., Li, Y. P., & Zhuo, Q. G. (2014). The major composition of a middle-late Eocene salt lake in the Yunying depression of Jianghan Basin of Middle China based on analyses of fluid inclusions in halite. Journal of Asian Earth Sciences, 85, 97–105. https://doi.org/10.1016/j.jseaes.2014.01.024

Paytan, A., Kastner, M., Campbell, D., & Thiemens, M. H. (1998). Sulfur isotopic composition of Cenozoic seawater sulfate. Science, 282(5393), 1459–1462. https://doi.org/10.1126/science.282.5393.1459

Petrychenko, O. Y. (1973). Metody doslidzhennia vkliuchen u mineralakh halohennykh porid. Kyiv: Naukova dumka. [in Ukrainian]

Ren, L. Y., Lin, G. F., Zhao, Z. Q., & Wang, X. W. (2000). Early Tertiary marine transgression in Dongpu depression. Acta Palaeontologica Sin., 39, 553–557. [in Chinese with English abstract]

Song, S. W. (2010). Rock salt mining and securite study of Tai’an Dawenkou Basin. Geology of Chemical Minierals, 32(3), 177–185. [in Chinese with English abstract]

Stankevich, E. F., Batalin, Iu. V., & Chaikin, V. G. (1991). Ob otlichiiakh morskikh i kontinentalnykh galogennykh otlozhenii. In Problemy morskogo i kontinentalnogo galogeneza (pp. 23–30). Novosibirsk: Nauka. [in Russian]

Valiashko, M. G. (1962). Zakonomernosti formirovaniia mestorozhdenii solei. Moskva: MGU. [in Russian]

Wang, Z. J., Li, Q., & Li, Z. C. (2003). Potentiality evaluation of gypsum resource in Dawenkou Basin in Tai’an City and suggestion on ore need predication and exploration. Land and Resources in Shangdong Province, 19(5), 23–25. [in Chinese with English abstract]

Wu, T., & Ren, L. Y. (2004). The tertiary seaway and new reservoir probe in Dongpu depression as well as its surrounded basins. Acta Palaeontologica Sin., 43, 147–154. [in Chinese with English abstract]

Xiao, B. J., Liu, A. T., Zhang, Y. Y., & Dong, W. H. (2010). Geological characteristics of Xiaotun Gypsum deposits in Zhangfanxiang of Zaozhuang City in Shandong Province. Land and Resources in Shangdong Province, 26(5), 12–15. [in Chinese with English abstract]

Xu, Y., Cao, Y., Liu, C., Zhang, H., & Nie, X. (2020). The history of transgressions during the Late Paleocene-Early Eocene in the Kuqa Depression, Tarim Basin: Constraints from C-O-S-Sr isotopic geochemistry. Minerals, 10(9), 834. https://doi.org/10.3390/min10090834

Yao, W., Wortmann, U. G., & Paytan, A. (2019). Sulfur isotopes – Use for stratigraphy during times of rapid perturbations. In M. Montenari (Ed.), Stratigraphy & Timescales: Vol. 4. Case Studies in Isotope Stratigraphy (Ch. 1, pp. 1–33). https://doi.org/10.1016/bs.sats.2019.08.004

Zhang, D., Huang, X. Y., & Li, C. J. (2013). Sources of riverine sulfate in Yellow River and its tributaries determined by sulfur and oxygen isotopes. Advances In Water Science, 24(3), 418–426. [in Chinese with English abstract]

Zhu, M. (2015). Study on the origin of salt deposit in Dawenkou Basin in Shandong Province. Land and Resources in Shangdong Province, 31(1), 27–30. [in Chinese with English abstract]

Posted on December 2024December 2024 by GGCMJournal

USE OF CHEMOMETRIC METHODS AND REGRESSION MODELS IN PROCESSING NIR SPECTRA OF PEAT FOR QUANTITATIVE DETERMINATION OF ITS CHEMICAL AND TECHNOLOGICAL INDICATORS

Home > Archive > No. 3–4 (195–196) 2024 > 100–125

Geology & Geochemistry of Combustible Minerals No. 3–4 (195–196) 2024, 100–125

https://doi.org/10.15407/ggcm2024.195-196.100

Yurii KHOKHA¹, Myroslava YAKOVENKO²
Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, Ukraine, e-mail: ¹khoha_yury@ukr.net; ²myroslavakoshil@ukr.net

Abstract

The article discusses theoretical and practical aspects of the use of near infrared (NIR) spectroscopy combined with chemometrics for express analysis of peat. Near infrared spectroscopy provides a significant amount of information about complex organic systems, including irregular polymers such as peat. Compared to classical analytical methods, NIR spectrometry allows analysis without complex sample preparation with analysis time measured in minutes. Since the results represent the intensity of radiation reflection in the overtone range of fundamental frequencies, their processing requires the use of special mathematical and statistical methods. The use of the Chemoface software package modules (PLS method) for quantitative analysis of the technical and chemical properties of peat based on NIR spectroscopy data has demonstrated the possibility of obtaining calibration models that allow for the quick and reliable analysis of this raw material, including in field conditions. The conducted studies have shown that using a spectrometer that analyzes reflected (absorbed) radiation in the near-infrared spectrum and based on the averaged spectral characteristics of the reflected (absorbed) radiation and using chemometric software, it is possible to calculate the chemical and technological characteristics of peat. The analysis procedure consists of the following stages: selection of a sample representing the entire batch of raw materials; irradiation of the sample with radiation containing a significant proportion of energy in the near-infrared spectrum; analysis with a detector of reflected (absorbed) radiation and construction of an integral spectral characteristic of the sample; compilation of a calibration model using chemometric software; processing of the obtained spectrum using chemometric software with subsequent calculation of the qualitative and quantitative characteristics of the raw materials. The proposed method (express analysis) for rapid determination of qualitative and quantitative characteristics of fossil carbon raw materials of organic origin, namely lowland and highland peat of various degrees of decomposition, can be used to establish its compliance with current norms, standards and technical conditions for moisture content, ash (inorganic) residue content and acidity (pH).

Full Text

Keywords

near-infrared reflectance (NIR) spectroscopy, peat analysis, predictive models, multivariate analysis, Partial Least Squares Regression (PLS), pre-treatments effect

Referenses

Andrés, J. M., & Bona, M. T. (2005). Analysis of coal by diffuse reflectance near-infrared spectroscopy. Analytica chimica acta, 535(1–2), 123–132. https://doi.org/10.1016/j.aca.2004.12.007

Geladi, P., MacDougall, D., & Martens, H. (1985). Linearization and scatter-correction for near-infrared reflectance spectra of meat. Applied spectroscopy, 39(3), 491–500. https://doi.org/10.1366/0003702854248656

Instytut gruntoznavstva ta ahrokhimii imeni O. N. Sokolovskoho Ukrainskoi akademii ahrarnykh nauk. (2008). Melioranty gruntu ta seredovyshcha rostu. Hotuvannia prob do khimichnoho ta fizychnoho analizu, vyznachennia vmistu sukhoi rechovyny, vmistu volohy ta laboratorno ushchilnenoi nasypnoi shchilnosti (EN 13040:1999, IDT) (DSTU EN 13040:2005). [in Ukrainian]

Instytut silskohospodarskoi mikrobiolohii ta ahropromyslovoho vyrobnytstva NAAN. (2016). Torf i produkty yoho pereroblennia dlia silskoho hospodarstva. Metody vyznachennia obminnoi y aktyvnoi kyslotnosti (DSTU 7882:2015). [in Ukrainian]

McClure, W. F. (1994). Near-infrared spectroscopy: The giant is running strong. Analytical chemistry, 66(1), 42A–53A. https://doi.org/10.1021/ac00073a730

Mostert, M. M., Ayoko, G. A., & Kokot, S. (2010). Application of chemometrics to analysis of soil pollutants. TrAC Trends in Analytical Chemistry, 29(5), 430–445. https://doi.org/10.1016/j.trac.2010.02.009

Nunes, C. A., Freitas, M. P., Pinheiro, A. C. M., & Bastos, S. C. (2012). Chemoface: a novel free user-friendly interface for chemometrics. Journal of the Brazilian Chemical Society, 23(11), 2003–2010. https://doi.org/10.1590/S0103-50532012005000073

Suprunovych, S. V., Kormosh, Zh. O., & Slyvka, N. Yu. (2022). Statystychni ta khemometrychni metody v khimii: navchalnyi posibnyk dlia studentiv vyshchykh navchalnykh zakladiv. Lutsk: VNU imeni Lesi Ukrainky. [in Ukrainian]

Tekhnichnyi komitet standartyzatsii “Gruntoznavstvo”. (2016). Yakist gruntu. Vyznachennia zolnosti torfu i torfovoho gruntu (DSTU 7942:2015). [in Ukrainian]

Yakovenko, M., & Khokha, Yu. (2024). Vykorystannia metodiv infrachervonoi spektroskopii dlia doslidzhennia torfu (rodovyshche Honchary, Lvivska oblast). Heolohiia i heokhimiia horiuchykh kopalyn, 1–2(193–194), 113–129. https://doi.org/10.15407/ggcm2024.193-194.113 [in Ukrainian]

Posted on July 2024October 2024 by GGCMJournal

INNOVATIVE STUDY COMPLEX OF COMPLEXLY STRUCTURED HYDROCARBON RESERVOIR ROCKS, BASED ON PETROPHYSICAL AND GEOCHEMICAL PARAMETERS (on the example of the Boryslav-Pokuttia zone of the Pre-Carpathian depression)

Home > Archive > No. 1–2 (193–194) 2024 > 130–140

Geology & Geochemistry of Combustible Minerals No. 1–2 (193–194) 2024, 130–140

https://doi.org/10.15407/ggcm2024.193-194.130

Roman-Danyil KUCHER, Oksana SENIV
Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, Ukraine, e-mail: igggk@mail.lviv.ua

Abstract

The article examines methods of studying the capacity-filtration properties of reservoir rocks of hydrocarbon deposits and transformation processes and the state of kerogen depletion within the Boryslav-Pokuttia zone of the Pre-Сarpathian depression.

The complex stressed state of rocks, which arises because of the action of geodynamic stresses, and the processes of catagenetic changes cause the development of secondary pore-crack and crack-cavernous reservoirs. Crack formation is caused by deformation and depends on the mechanical properties of rocks. The development of traps, pore-crack and crack-cavernous reservoirs is associated with rock loosening zones, which tend to tectonic disturbances and to places of intrusion of fluids from great depths into the sedimentary layer. At the same time, two multidirectional processes – thermal degradation and consolidation under the influence of pressure – cause changes that occur in the structure of kerogen during its evolution.

Based on the results of the analysis of the actual and theoretical material, the optimal methodical set of studies of the most important characteristics of the reservoirs and the processes of kerogen evolution for the considered zone is substantiated. An analysis of the geological and petrophysical characteristics of the Oligocene deposits of the Inner Zone of the Pre-Carpathian Trough was carried out and database were formed.

It has been established that pore-crack and crack reservoirs have a complex structure, and their distribution and capacity are controlled by two factors of different nature – lithological-facies and structural-deformation. It was found that thermodynamic modelling models – maximization of entropy and constants of independent chemical reactions – provide reliable results of the distribution of elements between the components of complex heterogeneous and homogeneous geochemical systems. It is shown that the chosen method of calculating the Gibbs energy of individual components of geochemical systems has sufficient accuracy for use in the above models.

Full Text

Keywords

Boryslav-Pokuttia zone, complicated reservoir rocks, petrophysical and geochemical parameters

Referenses

Bell, I. H., Wronski, J., Quoilin, S., & Lemort, V. (2014). Pure and Pseudo-pure Fluid Thermophysical Property Evaluation and the Open-Source Thermophysical Property Library CoolProp. Industrial & Engineering Chemistry Research, 53(6), 2498–2508. https://doi.org/10.1021/ie4033999

Blecic, J., Harrington, J., & Bowman, M. O. (2016). TEA: A code calculating thermochemical equilibrium abundances. The Astrophysical Journal Supplement Series, 225(1). https://doi.org/10.3847/0067-0049/225/1/4

Chekalyuk, E. B. (1971). Termodinamicheskiye osnovy teorii mineralnogo proiskhozhdeniya nefti. Kiev: Naukova dumka. [in Russian]

Glushko, V. P. (1972). Termodinamicheskiye svoystva individualnykh veshchestv. Moskva: Nauka. [in Russian]

Khokha, Yu. V. (2014). Termodynamika hlybynnykh vuhlevodniv u prohnozuvanni rehionalnoi naftohazonosnosti. Kyiv: Naukova dumka. [in Ukrainian]

Khokha, Yu. V., Liubchak, O. V., & Yakovenko, M. B. (2019). Enerhiia Hibbsa utvorennia komponentiv pryrodnoho hazu v osadovykh tovshchakh. Heolohiia i heokhimiia horiuchykh kopalyn, 2(179), 37–46. https://doi.org/10.15407/ggcm2019.02.037 [in Ukrainian]

Koukkari, P. (2014). Introduction to constrained Gibbs energy methods in process and materials research. VTT Technical Research Centre of Finland. VTT Technology No. 160. https://publications.vtt.fi/pdf/technology/2014/T160.pdf

van Krevelen, D. W., & Chermin, H. A. G. (1951). Estimation of the free enthalpy (Gibbs free energy) of formation of organic compounds from group contributions. Chemical Engineering Science, 1(2), 66–80. https://doi.org/10.1016/0009-2509(51)85002-4

Krupskyi, Yu. Z., Kurovets, I. M., Senkovskyi, Yu. M., Mykhailov, V. A., Chepil, P. M., Dryhant, D. M., Shlapinskyi, V. Ye., Koltun, Yu. V., Chepil, V. P., Kurovets, S. S., & Bodlak, V. P. (2014). Netradytsiini dzherela vuhlevodniv Ukrainy: Vol. 2. Zakhidnyi naftohazonosnyi rehion. Kyiv: Nika-Tsentr. [in Ukrainian]

Kucher, R.-D. A., & Seniv, O. R. (2024). Obgruntuvannia optymalnoho metodychnoho kompleksu doslidzhen yemnisno-filtratsiinykh vlastyvostei kolektoriv ta protsesiv transformatsii kerohenu Boryslavsko-Pokutskoi zony Peredkarpatskoho prohynu. In Suchasni problemy nauk pro Zemliu: materialy XIII Vseukrainskoi konferentsii-shkoly (Kyiv, 10–12 kvitnia 2024 r.) (pp. 22–24). Kyiv. [in Ukrainian]

Kurovets, I., Hrytsyk, I., Prykhodko, O., Chepusenko, P., Kucher, Z., Mykhalchuk, S., Melnychuk, S., Lysak, Yu., & Petelko, L. (2021). Petrofizychni modeli vidkladiv menilitovoi svity olihotsenovoho flishu Karpat i Peredkarpatskoho prohynu. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(185–186), 33–43. https://doi.org/10.15407/ggcm2021.03-04.033 [in Ukrainian]

Kurovets, I., Hrytsyk, I., Zubko, O., Prykhodko, O., & Kucher, R.-D. (2023). Aparaturno-metodychnyi kompleks doslidzhen petrofizychnykh vlastyvostei trishchynuvatykh porid-kolektoriv vuhlevodniv. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(191–192), 37−44. https://doi.org/10.15407/ggcm2023.191-192.037 [in Ukrainian]

Kurovets, I. M., Prytulka, H. Y., Sheremeta, O. V., Zubko, O. S., Osadchyi, V. H., Hrytsyk, I. I., Prykhodko, O. A., Kosianenko, H. P., Chepusenko, P. S., Shyra, A. I., Kucher, Z. I., & Oliinyk, K. A. (2006). Petrofizychni modeli skladnopobudovanykh kolektoriv vuhlevodniv. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4, 119–139. [in Ukrainian]

Kurovets, I., Zubko, O., Hrytsyk, I., Prykhodko, O., & Kucher, R.-D. (2023). Osoblyvosti formuvannia yemnisno-filtratsiinykh vlastyvostei porid-kolektoriv Vnutrishnoi zony Peredkarpatskoho prohynu. In Heofizyka i heodynamika: prohnozuvannia ta monitorynh heolohichnoho seredovyshcha: zbirnyk materialiv XI Mizhnarodnoi naukovoi konferentsii (Lviv, 10−12 zhovtnia 2023 r.) (pp. 109−112). Lviv. [in Ukrainian]

Pavliuk, M., Naumko, I., Lazaruk, Ya., Khokha, Yu., Krupskyi, Yu., Savchak, O., Rizun, B., Medvediev, A., Shlapinskyi, V., Kolodii, I., Liubchak, O., Yakovenko, M., Ternavskyi, M., Hryvniak, H., Triska, N., Seniv, O., & Huzarska, L. (2022). Rezerv naftohazovydobutku Zakhidnoho rehionu Ukrainy (Digital ed.). Lviv. http://iggcm.org.ua/wp-content/uploads/2015/10/РЕЗЕРВ-НАФТОГАЗОВИДОБУТКУ-ЗАХІДНОГО-РЕГІОНУ-УКРАЇНИ.pdf [in Ukrainian]

Sanford, G., & McBride, B. J. (1994). Computer Program for Calculation of Complex Chemical Equilibrium Compositions and Applications. NASA reference publication, 1311.

Stull, D. R., Westrum Jr., E. F., & Sinke, G. C. (1969). The Chemical Thermodynamics of Organic Compounds. NewYork: J. Wiley and Sons, Inc.

Tribus, M. (1961). Thermostatics and thermodynamics: an introduction to energy, information and states of matter, with engineering applications. Princeton: D. Van Nostrand Company Inc.