Accessory REE minerals occur in a small metamorphic magnetite ore deposit at Bacuch, Veporic Superunit, central Slovakia. We distinguish two populations of monazite. Monazite I forms subhedral to euhedral crystals associated with magnetite. It contains ≤12 wt.% ThO2, ≤2.7% UO2, ≤0.85% SO3, with low Ca and Sr contents. Compared to the common monazite-(Ce) I, monazite-(Nd) I (≤26.1% Nd2O3) occasionally occurs with an atomic ratio Nd:Ce up to 1.17. Monazite II is present as irregular aggregates with hingganite in younger hydrothermal quartz – albite – chlorite veinlets, or as rim zones on monazite I. Monazite II is depleted in Th and U and has an unusually high content of S (≤11.3% SO3, 0.31 apfu S) and Sr (≤8.7% SrO, 0.18 apfu Sr). This composition indicates a (Ca,Sr)S(REE,Y)−1P−1 substitution as a dominant mechanism of Sr and S entry into the monazite structure. Some monazite II crystals display an elevated Eu content (≤1.2% Eu2O3). Xenotime-(Y) forms subhedral crystals, in association with monazite-(Ce) I, magnetite, pyrite transformed to goethite (?) and quartz. Gadolinite-group minerals at Bacuch are represented by hingganite with an atomic value of X □/ X (□ + Fe) in the range 0.51–0.72. Neodymium is locally the most abundant REE (17.8–18.7% Nd, ~0.56 apfu ), and an Nd-dominant member of the gadolinite group was identified. The composition of hingganite-(Y) was also determined. The principal mechanism of substitution in hingganite is Fe2+O2□−1(OH)−2. Primary monazite I and xenotime are most likely products of regional metamorphism, together with magnetite mineralization. On the contrary, Sr- and S-rich monazite II and hingganite originated during a younger (Alpine) metamorphic-hydrothermal overprint in a fluid-rich regime.
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.
Experimentally metasomatised monazite was studied in terms of preservation of U-Pb and Th-Pb ages during alkali-bearing fluid-induced alteration over a broad range of temperature conditions 250–750 °C. Starting materials for experiments included Burnet monazite (Concordia age 1100.5 ± 11.6 Ma, 2σ), albite, K-feldspar, biotite, muscovite, SiO2, CaF2, Na2Si2O5 and H2O. Monazite from experiments at 250–550 °C is partially replaced by secondary REE-rich fluorapatite [(Ca,LREE,Si,Na)5(PO4)3F], fluorcalciobritholite [(Ca,REE)5(SiO4,PO4)3F] and REE-rich steacyite [K1−x(Na,Ca)2(Th,U)Si8O20], and developed patchy zoning, whereas partial replacement by fluorcalciobritholite and cheralite [CaTh(PO4)2] occurred at 650 and 750 °C, with no signs of compositional alteration based on EPMA data and BSE imaging. Raman microspectroscopy results show narrowing of the ν1(PO4) stretching band in unaltered domains, which indicates advancing annealing of the monazite structure with increasing temperature, and narrow ν1(PO4) band with low FWHM values in altered domains. TEM investigations revealed that unaltered domains of monazite from experiments at 250–550 °C have mottled diffraction contrast, similar to the starting Burnet monazite, which indicates low to moderate degree of metamictization. On the contrary, the altered domains of monazite (patchy zones) show no mottled contrast, suggesting an ordered crystalline structure. TEM imaging demonstrated low degree of metamictization in monazite from the experiment at 650 °C; fluid-aided alteration along the cleavage planes resulted in the development of nanoporosity or partial replacement by fluorcalciobritholite and cheralite. Monazite from the experiment at 750 °C has crystalline structure with no signs of metamictization and shows significant development of nanoporosity and formation of secondary cheralite nanocrystals across the grain. For comparison, TEM and Raman evaluation of xenotime from similar experiments at 350 and 650 °C revealed that both starting xenotime and xenotime from experimental products are crystalline with no signs of radiation damage or fluid-induced alteration affecting internal domains on submicron scale, which could result in compositional alteration of the xenotime. The unaltered domains of monazite from runs at 250–550 °C yielded U-Pb and Th-Pb dates similar to the age of Burnet monazite, whereas altered domains yielded discordant dates due to various degree of Pb-loss (up to 99.4%). Linear regressions on the Concordia diagrams show lower intercept ages from −266 ± 160 Ma (run 350 °C, 200 MPa) to −1 ± 48 Ma (450 °C, 800 MPa), which reflect the "true age" of experimental alteration. The monazite from runs at 650 and 750 °C yielded data indicating initial disturbance of the U-Th-Pb system, ranging from 8.4% Pb-gain to 18.6% Pb-loss. Linear regressions with lower intercepts of −53 ± 420 Ma and −55 ± 610 Ma roughly correspond to the timing of the experiments. Furthermore, LA-ICPMS results demonstrate discrepancy between Th-Pb and U-Pb dates suggesting higher mobility of 208Pb than that of 207Pb and 206Pb. To summarize, TEM and Raman data indicate increasing annealing of the radiation damaged monazite with increasing temperature. Alteration processes induced by alkali-bearing fluid can result in recrystallization of monazite and various degrees of the age disturbance at temperatures 250–550 °C, whereas isotopic U-Th-Pb microanalysis provide an opportunity to constrain the age of the metasomatic processes as the lower intercept in the Concordia diagram. The particular importance of this study lies in submicron alteration of monazite at 650–750 °C induced by alkali-bearing fluid and/or melt, which remains unnoticed using common electron microscopy BSE imaging. Such alteration, however, induces substantial disturbance of U-Pb and Th-Pb ages, which can cause misinterpretations in reconstructions of geological processes.
