Formation of richterite in the enstatite–diopside system in the presence of the K2CO3–Na2CO3–CO2–H2O fluid in application to the processes of mantle metasomatism

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Abstract

The paper presents results of studying the formation reaction of K–Na-richterite in the enstatite + diopside association with the participation of the K2CO3–Na2CO3–CO2–H2O fluid at 3 GPa and 1000°C, simulating the formation of this mineral in peridotites of the upper mantle. Richterite formation depends on the (H2O + CO2) / (K2CO3 + Na2CO3) and K2CO3 / Na2CO3 ratios in the starting material. A high concentration of alkaline components in the fluid leads to the decomposition of clinopyroxene, the formation of olivine, as well as a change in the component composition of pyroxene and amphibole. Fluids with a high concentration of the potassium component are responsible for the formation of K-richterite, similar in composition to that formed in metasomatized peridotites of the upper mantle. In some cases, such a fluid leads to the decomposition of amphibole and stabilization of the alkaline melt. With an increase in the activity of the sodium component, the fluid contains richterite, which is similar in composition to richterite from lamproites. The obtained patterns can be used to assess the activities of fluid components and the conditions for the formation of K-richterite. To replenish the data bank of Raman spectra of minerals, the largest and most homogeneous amphibole crystals of different compositions were studied.

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About the authors

E. V. Limanov

D.S. Korzhinskii Institute of Experimental Mineralogy RAS

Author for correspondence.
Email: limanov.ev@iem.ac.ru
Russian Federation, Academician Osipyan st., 4, Chernogolovka, 142432

V. G. Butvina

D.S. Korzhinskii Institute of Experimental Mineralogy RAS

Email: limanov.ev@iem.ac.ru
Russian Federation, Academician Osipyan st., 4, Chernogolovka, 142432

O. G. Safonov

D.S. Korzhinskii Institute of Experimental Mineralogy RAS; Lomonosov Moscow State University

Email: limanov.ev@iem.ac.ru

Faculty of Geology MSU

Russian Federation, Academician Osipyan st., 4, Chernogolovka, 142432; Leninskie Gory, 1, Moscow, 119991

A. V. Spivak

D.S. Korzhinskii Institute of Experimental Mineralogy RAS

Email: limanov.ev@iem.ac.ru
Russian Federation, Academician Osipyan st., 4, Chernogolovka, 142432

K. V. Van

D.S. Korzhinskii Institute of Experimental Mineralogy RAS

Email: limanov.ev@iem.ac.ru
Russian Federation, Academician Osipyan st., 4, Chernogolovka, 142432

S. S. Vorobey

Vernadsky Institute of Geochemistry and Analytical Chemistry RAS

Email: limanov.ev@iem.ac.ru
Russian Federation, Kosygina st., 19, Moscow, 119991

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2. Fig. 1. Photographs of samples in reflected electrons: (a) I-10; (b) I-30; (c) II-40; (d) II-30. Legend: Ol – olivine, Cpx – clinopyroxene, Opx – orthopyroxene, Amph – amphibole, L – melt quench products. Black areas are the result of aggregate chipping during polishing. The “spottiness” of amphibole and olivine is due to the presence of inclusions of both pyroxenes. Aggregates of needle-shaped crystals are probably silicate melt quench products.

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3. Fig. 2. Photographs of samples in reflected electrons: (a) II-50; (b) III-10; (c) III-60; (d) III-50. The zonal distribution of phases in the last sample is associated with the temperature gradient in the cell used in the NL-40 apparatus. Legend: see Fig. 1.

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4. Fig. 3. Graphs of mineral composition changes depending on fluid composition in system I: (a) Ca f.u. in Cpx (Cpx* is relict clinopyroxene preserved as inclusions in other phases); (b) Ca f.u. in Opx; (c) comparison of synthesized K-richterites with natural analogues: black circles, gray squares, and black triangles are richterites from lamproites (Wagner, Velde, 1986), (Kaur, Mitchell, 2015), and (Downes et al., 2006), respectively, white circles and white squares are K-richterites from metasomatized peridotites (Jones et al., 1982) and (Erlank, 1973), respectively, gray square with a cross is richterite from dianite of the Murun complex; Grey diamonds – K-richterites from MARID (Waters et al., 1989), grey triangles – from PKP peridotites (Waters et al., 1989), light grey field – amphiboles of system I, grey field – system II, dark grey field – system III; (d) comparison of amphiboles with analogues from the work of Zimmerman et al. (1997): black circles – the present study 1000°C, 3 GPa, grey – 800°C, 250 MPa, white – 700°C, 250 MPa. The black dotted line reflects the linear regression for our data, the grey line – for amphiboles at 800°C and 250 MPa (Zimmerman et al., 1997).

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5. Fig. 4. Comparison of changes in amphibole composition depending on K/Na and (K2CO3 + Na2CO3) / (CO2 + H2O) ratios in the fluid: (a) system I (K/Na = 50 : 50); (b) II (K < Na); (c) III (K > Na). White dots – Ca, gray – K, black – Na.

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6. Fig. 5. Comparison of the obtained Raman spectra of amphiboles (III-60 and II-40) with synthetic K-richterite (Della Ventura et al., 2021), natural K-richterite (Dumanska-Słowik et al., 2022), and natural richterite (R050414) from the library https://rruff.info.

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