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Date submitted2022-03-20
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Date accepted2022-05-25
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Date published2022-07-26
Ophiolite association of Cape Fiolent (western part of the Mountainous Crimea) – the upper age constraint according to the U-Pb isotope dating of plagiorhyolites (Monakh Cliff)
The article presents the results of U-Pb isotope dating (SHRIMP-II, VSEGEI, Saint Petersburg) of zircon crystals extracted from plagiorhyolites of the Monakh Cliff in the area of Cape Fiolent in the western part of the Mountainous Crimea (southern suburb of Sevastopol). a concordant age estimate of 168.3±1.3 Ma was obtained from 20 zircon crystals. It exactly corresponds to the Bajocian/Bathonian boundary of the Middle Jurassic according to the International Chronostratigraphic Chart (February 2022 version). The available results of isotope dating of igneous rocks from the Mountainous Crimea, as well as their geochemical typification are synthesised. The plagiorhyolites of the Monakh Cliff in the area of Cape Fiolent are spatially, and most likely paragenetically, associated with the wallrock (Cape Vinogradny) and ore (Heraclea Plateau on the cognominal peninsula) massive sulphide formations, as well as pillow basalts, gabbroids, and serpentinized hyperbasites, combined into the ophiolite association of Cape Fiolent. The obtained dating is the upper age limit for the entire ophiolite association of Cape Fiolent.
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Date submitted2019-01-13
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Date accepted2019-03-04
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Date published2019-06-25
Thermodynamic model of ion-exchange process as exemplified by cerium sorption from multisalt solutions
A complex heterogeneous process of ion exchange can be defined with an isotherm-isobar equation of the chemical reaction, which describes differential affinity between the process and its effect – the law of mass action. Ion exchange includes processes accompanied by changes in the charge of ions and functional groups caused by the passing of ionic bond into covalent one. Hence isotherm equations of ion exchange for such processes must differ from conventional stoichiometric equations, but they can be obtained by classical study approaches to ion exchange equilibrium. The paper describes a new thermodynamic model, based on linearization of mass action law, modified for the ion exchange equation. The application of this model allows to define stoichiometry of ion exchange and the shape of ions adsorbed by the solid phase of ion-exchange resins, as well as to estimate equilibrium constant and Gibbs free energy of the process. Comparative analysis has been carried out for the thermodynamic model of cerium sorption in the form of anionic complex with Trilon B from a multisalt solution with ionic strength of 1 mol/kg (NaNO 3 ) under рН = 3 and temperature 298 K on a test sample of weak-base anion-exchange resin Cybber EV009. Experimental isotherm of the sorption has been obtained. Calculations of thermodynamic parameters have been performed using Langmuir, Freundlich, Dubinin – Radushkevich, Temkin and Flory – Huggins models, as well as thermodynamic model of linearized mass action law, proposed by the authors. Calculated values of the equilibrium constant and Gibbs energy – K = 9.0±0.5 and ΔrG 0 298 = –5.54±0.27 kJ/mol – characterize the sorption of EDTA cerate ions by ion-exchange resin. The shape of adsorbed ions has been defined in Stern-Helmholtz layer of CeTr, and total capacity of anion resin EV009 for EDTA cerate ions has been estimated as q ∞ = 2.0±0.1 mol/kg.