Hydrothermal mineral replacement in the apatite-rhabdophane-monazite system: Experiments, reaction mechanisms and geological implications

Abstract

Apatite, rhabdophane and monazite are actinide- and rare-earth element (REE)-bearing phosphate minerals with diverse geoscientific applications. However, their mineral-fluid reaction mechanisms below 200 °C are understudied. Insufficient understanding as to how these minerals behave during hydrothermal alteration impedes useful interpretations of REE-U-Th mobilisation in regolith profiles, diagenetic environments and low-temperature hydrothermal systems. This work experimentally investigates the replacement of apatite by rhabdophane in a Ce-doped acidic fluid at 30 °C, and of rhabdophane by monazite in REE-barren acidic fluids at 180 °C. Rhabdophane replaced apatite via the coupled dissolution-precipitation mechanism, forming nanoscale prisms clustered into spherulitic aggregates. Interstitial voids that formed between rhabdophane and apatite indicate how rhabdophane precipitation was the rate-limiting step. Void widths varied in response to apatite's anisotropic dissolution; rapid dissolution parallel to the c-axis formed the widest voids (50–125 μm) and thickest rhabdophane layers (20–50 μm), while slow dissolution perpendicular to the c-axis formed narrower voids (< 1 μm) and thinner layers (< 5 μm). At 180 °C, monazite also replaced rhabdophane via the dissolution-precipitation mechanism. Replacement rates increased with increasing phosphate concentrations, implying that monazite precipitation was the rate-limiting step. However, microscale rhabdophane aggregates were pseudomorphically preserved. This is attributed to the shared orientation of rhabdophane prisms (not pseudomorphically preserved) and their intergranular boundaries which, as microreactors, guided monazite precipitation. Both replacement reactions were accompanied by a loss of U to solution, which is attributed to the stabilisation of uranyl-phosphate complexes under acidic conditions. Results indicate that: 1) anisotropic dissolution can govern the extent of rate coupling between dissolution and precipitation during mineral replacement; 2) the pseudomorphic replacement of mineral aggregates can occur when precipitation is the rate-limiting step; 3) rhabdophane is a feasible (and perhaps necessary) metastable precursor to authigenic monazite precipitation in low temperature hydrothermal systems; 4) highly porous aggregates of both rhabdophane and monazite generate insufficient EPMA totals, such that they cannot be differentiated by EPMA alone, and; 5) phosphate complexes can mobilise U under certain hydrothermal conditions, with implications for geochronology, nuclear waste management and the formation of REE deposits.