Carbonatitic magma fractionation and contamination generate rare earth element enrichment and mineralization in the Maoniuping giant REE deposit, SW China

Carbonatite intrusions host the world’s most important light rare earth element (LREE) deposits, and their formation generally requires extraordinary fertile sources, magmatic evolution, and hydrothermal events. However, carbonatitic magma evolution, particularly the role of fractional crystallization and contamination from silicate rocks in REE enrichment, remains enigmatic. The Maoniuping world-class REE deposit in southwestern China, is an ideal target to decipher magmatic evolution and related REE enrichment as it shows continuous textual evolution from medium- to coarse-grained calcite carbonatite (carbonatite I) at depth, to progressively pegmatoidal calcite carbonatite (carbonatite II) at shallow levels. In both types of calcite carbonatites, four generations of calcite can be classified according to petrographic and geochemical characteristics. Early-crystalizing calcite (Cal-I and Cal-II) are found in carbonatite I and exhibit equigranular and a polygonal mosaic textures, while late calcites (Cal-III and Cal-IV) in carbonatite II are large-size oikocrysts (>0.5 mm in length) with strain-induced undulatory extinction and bent twinning lamellae. All these generations of calcite yield similar, near-chondritic, Y/Ho ratios (26.6−28.1) and are inferred to be of magmatic origin. Remarkably, gradual enrichment of MgO, FeO and MnO from Cal-I to Cal-IV is coupled with a significant increase in REE contents (~800 to 2000 ppm), with LREE-rich and gentle-to-steep chondrite-normalized REE patterns ((La/Yb)N = 3.1–26.8 and (La/Sm)N = 0.9–3.9, respectively). Such significant REE enrichment is ascribed to protracted magma fractional crystallization with initial low degree of fractional crystallization (fraction of melt remining (F) = ~0.95) evolving to late stage (F = 0.5–0.6) by formation of abundant calcite cumulates. Differential LREE and HREE behavior during magma evolution largely depend on separation of phlogopite, amphibole, and clinopyroxene from the carbonatitic melt, which is indicated by progressively elevated (La/Yb)N ratios ranging from 3.1 to 26.8. The four generations of calcite have significantly different C and Sr isotopic compositions with δ13CV-PDB decreasing from –3.28 to –9.97 ‰ and 87Sr/86Sr increasing from 0.70613 to 0.70670. According to spatial relations and petrographic observations, the relative enrichment of δ13C and depletion in 87Sr/86Sr ratios of Cal-I and Cal-II show primary isotopic characteristics inherited from initial carbonatitic magma. By contrast, the variable Sr and C isotopic compositions of Cal-III and Cal-IV are interpreted as the results of contamination by components derived from silicate wall rocks and loss of CO2 by decarbonation reactions. To model such contamination processes, Raleigh volatilization and Monte Carlo simulation have been invoked and the model results reveal that carbonatitic melt-wall rock interaction requires 40% radiogenic Sr contamination from silicate rocks and 35% CO2 degassing from carbonatitic melt. Moreover, positive correlations between decreasing δ13C values and increasing REE contents, together with bastnäsite-(Ce) precipitation, indicate further REE accumulation during the contamination processes. In summary, alongside REE-rich magma sources, the extent of fractional crystallization and contamination during carbonatitic magma evolution are inferred to be important mechanisms in terms of REE enrichment and mineralization in carbonatite-related REE deposits worldwide.