The paper summarizes authors' earlier and newly obtained experimental data on the formation of phlogopite and chromium-bearing potassium titanates of the crichtonite, magnetoplumbite, and hollandite groups, which are indicator minerals that characterize various stages of modal metasomatism in the upper mantle. Phlogopite-forming reactions were studied in the garnet–orthopyroxene system in the presence of H2O–KCl fluid at 3 and 5 GPa and 900–1000°C as simulating phlogopite formation in garnet peridotites and pyroxenites. Experiments have demonstrated regular variations in Ca and Cr contents in the garnet and Al in the pyroxenes, as well as the composition of the newly formed phlogopite, depending on the concentration of the potassium component (KCl or K2CO3) of the fluid. Experiments on the formation of potassium titanates (yimengite, mathiasite, and priderite) in the chromite–rutile/ilmenite–K2CO3–H2O–CO2 system at 3.5 and 5 GPa and 1200°C have proved that these minerals can be formed when chromite reacts with potassic aqueous–carbonic fluid, but these reactions require additional sources of titanium. These sources may be rutile and/or ilmenite, which are usually also produced by modal metasomatism of peridotites. The experiments thus confirm that the formation of titanates marks the most advanced stages of metasomatism in mantle peridotites. The experiments have shown that the formation of potassium titanates follows the formation of phlogopite, whereas assemblages of the titanates with phlogopite are produced at higher concentrations of the potassium component of the fluid than phlogopite alone. The relationships between the titanates are also a function of the activity of the potassium component in the fluid and, probably, pressure. The relationships and trends reproduced in the experiments clearly illustrate features of mineral assemblages and variations in compositions of minerals from metasomatized peridotites in the lithospheric mantle.

The salt components of aqueous and aqueous-carbonic fluids are very important agents of metasomatism and partial melting of crustal and mantle rocks. The paper presents examples and synthesized data on mineral associations in granulite- and amphibolite-facies rocks of various composition in the middle and lower crust and in upper-mantle eclogites and peridotites that provide evidence of reactions involving salt components of fluids. These data are analyzed together with results of model experiments that reproduce some of these associations and make it possible to more accurately determine their crystallization parameters.

Reactions and partial melting of peraluminous rocks in the presence of H2O-CO2–salt fluids under parameters of granulite-facies metamorphism were modeled in experiments on interaction between orthopyroxene–cordierite–biotite–plagioclase–quartz metapelite with H2O, H2O-CO2, H2O-CO2-NaCl, and H2O-CO2-KCl fluids at 600 MPa and 850°C. Rock melting in the presence of H2O and equimolar H2O-CO2 fluids generates peraluminous (A/CNK1 > 1.1) melts whose composition corresponds to magnesian calcic or calc–alkaline S-type granitoids. The melts are associated with peritectic phases: magnesian spinel and orthopyroxene containing up to 9 wt % Al2O3. In the presence of H2O-CO2-NaCl fluid, cordierite and orthopyroxene are replaced by the association of K-Na biotite, Na-bearing gedrite, spinel, and albite. The Na2O concentrations in the biotite and gedrite are functions of the NaCl concentrations in the starting fluid. Fluids of the composition H2O-CO2-KCl induce cordierite replacement by biotite with corundum and spinel and by these phases in association with potassium feldspar at X KCl = 0.02 in the fluid. When replaced by these phases, cordierite is excluded from the melting reactions, and the overall melting of the metapelite is controlled by peritectic reactions of biotite and orthopyroxene with plagioclase and quartz. These reactions produce such minerals atypical of metapelites as Ca-Na amphibole and clinopyroxene. The compositions of melts derived in the presence of salt-bearing fluids are shifted toward the region with A/CNK < 1.1, as is typical of so-called peraluminous granites of type I. An increase in the concentrations of salts in the fluids leads to depletion of the melts in Al2O3 and CaO and enrichment in alkalis. These relations suggest that the protoliths of I-type peraluminous granites might have been metapelites that were melted when interacting with H2O-CO2-salt fluids. The compositions of the melts can evolve from those with A/CNK > 1.1 (typical of S-type granites) toward those with A/CNK = 1.0–1.1 in response to an increase in the concentrations of alkali salts in the fluids within a few mole percent. Our experiments demonstrate that the origin of new mineral assemblages in metapelite in equilibrium with H2O-CO2-salt fluids is controlled by the activities of alkaline components, while the H2O and CO2 activities play subordinate roles. This conclusion is consistent with the results obtained by simulating metapelite mineral assemblages by Gibbs free energy minimization (using the PERPE_X software), as shown in log(\({a_{{H_2}O}}\))–log(\({a_{N{a_2}O}}\)) and log(\({a_{{H_2}O}}\))–log(\({a_{{K_2}O}}\)) diagrams.