The experimental alteration of monazite to allanite, REE-epidote, fluorapatite, and/or fluorapatite-britholite was investigated at 450 to 610 MPa and 450 to 500 °C. Experiments involved monazite + albite ± K-feldspar + muscovite ± biotite + SiO₂ + CaF₂ and variety of fluids including H₂O, (KCl + H₂O), (NaCl + H₂O), (CaCl₂ + H₂O), (Na₂Si₂O₅ + H₂O), 1 M HCl, 2 M NaOH, 2 M KOH, 1 M Ca(OH)₂, 2 M Ca(OH)₂, and (CaCO₃ + H₂O). The reaction products, or lack thereof, clearly show that the stability relations between monazite, fluorapatite, and allanite or REE-epidote are more dependent on the fluid composition and the ratio of silicate minerals than on the P-T conditions. A high Ca content in the fluid promotes monazite dissolution and the formation of fluorapatite and allanite or REE-epidote. Lowering the Ca content and raising the Na content in the fluid decreases the solubility of monazite but promotes the formation of allanite. Replacing Na with K in the same fluid causes fluorapatite, with a britholite component, to form from the monazite. However, allanite and REE-epidote are not formed. Monazite is stable in the presence of NaCl brines. In KCl brine, monazite shows a very limited reaction to fluorapatite. When the fluid is (Na₂Si₂O₅ + H₂O), strong dissolution of monazite occurs resulting in the mobilization of REEs, and actinides to form fluorapatite-britholite and turkestanite. These experimental results are consistent with natural observations of the partial to total replacement of monazite by fluorapatite, REE-epidote, and allanite in fluid-aided reactions involving the anorthite component in plagioclase at mid- to high-grade metamorphic conditions. In contrast, an alkali-bearing environment with excess Na prevents the growth of allanite and eventually promotes the precipitation of secondary monazite. The results from this study provide implications for geochronology and for deducing fluid compositions in metamorphic rocks.

The relative stabilities of phases within the two systems monazite-(Ce) – fluorapatite – allanite-(Ce) and xenotime-(Y) – (Y,HREE)-rich fluorapatite – (Y,HREE)-rich epidote have been tested experimentally as a function of pressure and temperature in systems roughly replicating granitic to pelitic composition with high and moderate bulk CaO/Na₂O ratios over a wide range of P-T conditions from 200 to 1000 MPa and 450 to 750 °C via four sets of experiments. These included (1) monazite-(Ce), labradorite, sanidine, biotite, muscovite, SiO₂, CaF₂, and 2 M Ca(OH)₂; (2) monazite-(Ce), albite, sanidine, biotite, muscovite, SiO₂, CaF₂, Na₂Si₂O₅, and H₂O; (3) xenotime-(Y), labradorite, sanidine, biotite, muscovite, garnet, SiO₂, CaF₂, and 2 M Ca(OH)₂; and (4) xenotime-(Y), albite, sanidine, biotite, muscovite, garnet, SiO₂, CaF₂, Na₂Si₂O₅, and H₂O. Monazite-(Ce) breakdown was documented in experimental sets (1) and (2). In experimental set (1), the Ca high activity (estimated bulk CaO/Na₂O ratio of 13.3) promoted the formation of REE-rich epidote, allanite-(Ce), REE-rich fluorapatite, and fluorcalciobritholite at the expense of monazite-(Ce). In contrast, a bulk CaO/Na₂O ratio of ~1.0 in runs in set (2) prevented the formation of REE-rich epidote and allanite-(Ce). The reacted monazite-(Ce) was partially replaced by REE-rich fluorapatite-fluorcalciobritholite in all runs, REE-rich steacyite in experiments at 450 °C, 200–1000 MPa, and 550 °C, 200–600 MPa, and minor cheralite in runs at 650–750 °C, 200–1000 MPa. The experimental results support previous natural observations and thermodynamic modeling of phase equilibria, which demonstrate that an increased CaO bulk content expands the stability field of allanite-(Ce) relative to monazite-(Ce) at higher temperatures indicating that the relative stabilities of monazite-(Ce) and allanite-(Ce) depend on the bulk CaO/Na₂O ratio. The experiments also provide new insights into the re-equilibration of monazite-(Ce) via fluid-aided coupled dissolution-reprecipitation, which affects the Th-U-Pb system in runs at 450 °C, 200–1000 MPa, and 550 °C, 200–600 MPa. A lack of compositional alteration in the Th, U, and Pb in monazite-(Ce) at 550 °C, 800–1000 MPa, and in experiments at 650–750 °C, 200–1000 MPa indicates the limited influence of fluid-mediated alteration on volume diffusion under high P-T conditions. Experimental sets (3) and (4) resulted in xenotime-(Y) breakdown and partial replacement by (Y,REE)-rich fluorapatite to Y-rich fluorcalciobritholite. Additionally, (Y,HREE)-rich epidote formed at the expense of xenotime-(Y) in three runs with 2 M Ca(OH)₂ fluid, at 550 °C, 800 MPa; 650 °C, 800 MPa; and 650 °C, 1000 MPa similar to the experiments involving monazite-(Ce). These results confirm that replacement of xenotime-(Y) by (Y,HREE)-rich epidote is induced by a high Ca bulk content with a high CaO/Na₂O ratio. These experiments demonstrate also that the relative stabilities of xenotime-(Y) and (Y,HREE)-rich epidote are strongly controlled by pressure.

Zircon from a microgranular enclave in the ca. 315 Ma postcollisional Karkonosze pluton (Western Sudetes, northeastern Bohemian Massif) is characterized by unusual morphologies and reequilibration textures. Blocky, clustered, and skeletal Th-U–rich zircon grains are internally corroded along discrete boundary zones, and subsequently replaced by porous microgranular aggregates of zircon and various other minerals, including thorite. The boundary zones have textures and compositions characteristic of diffusion-controlled chemical reaction fronts, including enrichment in Ca, Ba, and light rare earth elements, whereas microgranular domains are typical of zircon replacement and regrowth by coupled dissolution and precipitation. Initial zircon crystallization occurred with the mingling of mafic magma into a cooler granitic melt, whereas zircon modification is attributed to the reaction of late magmatic fluids from the host granite with the enclave. Precise dating of reequilibrated zircon as 304 ± 2 Ma indicates that fluid activity, which is also responsible for scheelite mineralization, postdates the emplacement of the main part of the pluton by several millions of years.