The origin of secondary heavy rare earth element enrichment in carbonatites: Constraints from the evolution of the Huanglongpu district, China
Martin SmithJindřích KynickýCheng XuWenlei SongJohn SprattTeresa E. JeffriesMartin BrtnickýAntonín KopřivaDelia Cangelosi
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Abstract:
The silico‑carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnäsite and parisite where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate hydrothermal fluids must have contributed HREE to the mineralisation. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32− in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl−) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexation may have been important for preferential HREE transport. Alongside HREE-enriched magmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.Keywords:
Carbonatite
Allanite
Rare-earth element
Metasomatism
Uraninite
Carbonatite
Gangue
Rare-earth element
Allanite
Fluorite
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Approximately >50% of global rare earth element (REE) resources are hosted by carbonatite related deposits, of which monazite is one of the most important REE minerals. Monazite dominates more than 30 carbonatite-related REE deposits around the world, including currently exploited mineralization at Bayan Obo and Mount Weld. These deposits are widely distributed across all continents, except Antarctica. Though rare, monazite occurs as the primary mineral in carbonatite, and mostly presents as a secondary mineral that has a strong association with apatite. It can partially or completely replace thin or thick overgrowth apatite, depending on the availability of REE. Other mineral phases that usually crystallize together with monazite include barite, fluorite, xenotime, sulfide, and quartz in a carbonate matrix (e.g., dolomite, calcite). This review of monazite geochemistry within carbonatite-related REE deposits aims to provide information regarding the use of monazite as a geochemical indicator to track the formation history of the REE deposits and also supply additional information for the beneficiation of monazite. The chemical compositions of monazite are highly variable, and Ce-monazite is the dominant solid solution in carbonatite related deposits. Most monazite displays steep fractionation from La to Lu, absent of either Eu or Ce anomalies in the chondrite normalized REE plot. The other significant components are huttonite and cheratite. Some rare sulfur-bearing monazite is also identified with an SO3 content up to 4 wt %. A 147Sm/144Nd ratio with an average ~0.071 for monazite within carbonatite-related ores is similar to that of their host rocks (~0.065), and is the lowest among all types of REE deposits. Sm/Nd variation of monazite from a single complex reflects the differentiation stage of magma, which decreases from early to late. Based on the differences of Nd and Sr abundances, Nd isotopic composition for monazite can be used to track the magma source, whereas Sr isotopic composition records the signatures of the fluid source. Th-(U)-Pb age determination of the secondary monazite records variable thermal or metasomatic disturbances, and careful geochronological interpretation should be brought forward combined with other lines of evidence. ThO2 is the most difficult contamination in the beneficiation of monazite, luckily, the ThO2 content of monazite within carbonatite is generally low (<2 wt %).
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Abstract The textural and chemical evolution of allanite and monazite along a well‐constrained prograde metamorphic suite in the High Himalayan Crystalline of Zanskar was investigated to determine the P–T conditions for the crystallization of these two REE accessory phases. The results of this study reveals that: (i) allanite is the stable REE accessory phase in the biotite and garnet zone and (ii) allanite disappears at the staurolite‐in isograd, simultaneously with the occurrence of the first metamorphic monazite. Both monazite and allanite occur as inclusions in staurolite, indicating that the breakdown of allanite and the formation of monazite proceeded during staurolite crystallization. Staurolite growth modelling indicates that staurolite crystallized between 580 and 610 °C, thus setting the lower temperature limit for the monazite‐forming reaction at ~600 °C. Preservation of allanite and monazite inclusions in garnet (core and rim) constrains the garnet molar composition when the first monazite was overgrown and subsequently encompassed by the garnet crystallization front. Garnet growth modelling and the intersection of isopleths reveal that the monazite closest to the garnet core was overgrown by the garnet advancing crystallization front at 590 °C, which establishes an upper temperature limit for monazite crystallization. Significantly, the substitution of allanite by monazite occurs in close spatial proximity, i.e. at similar P–T conditions, in all rock types investigated, from Al‐rich metapelites to more psammitic metasedimentary rocks. This indicates that major silicate phases, such as staurolite and garnet, do not play a significant role in the monazite‐forming reaction. Our data show that the occurrence of the first metamorphic monazite in these rocks was mainly determined by the P–T conditions, not by bulk chemical composition. In Barrovian terranes, dating prograde monazite in metapelites thus means constraining the time when these rocks reached the 600 °C isotherm.
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<p>Table S1: The chemical compositions of allanite and monazite from the Huangjiagou carbonatite. Table S2: The U-Th-Pb date of monazite and allanite from the Huangjiagou carbonatite. Table S3: The Sr-Nd isotope data of monazite and allanite from the Huangjiagou carbonatite.</p>
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Monazite, a typical light rare-earth element (LREE) mineral of S-type granitoids in the Western Carpathians, was found in the peraluminous biotite granodiorite-tonalite in the Tribeč Mountains commonly containing polymineralic inclusions. These inclusions are dominated by anhedral allanite, although allanite also occurs rarely as discrete grains not enclosed by monazite. The monazite studied here is relatively homogeneous and characterized by high Th contents with proportions of huttonite (ThSiO4) and brabantite [CaTh(PO4)2] up to 14.6 and 9.3%, respectively. The discrete allanite grains are highly aluminous with a composition consistent with the peraluminous type of host rock. However, allanite included in monazite is extremely variable in LREE, Al, Fe, and Mg contents. This variation is interpreted to result from entrapment of allanite (+ melt) in monazite before local equilibrium was attained. The change from allanite to monazite as the stable LREE-rich phase is related to an overall decrease in Ca concentration caused by the onset of plagioclase crystallization. The early precipitation of allanite was possible because of the high LREE concentrations in the melt. The crystallization temperature of allanite must have been higher than monazite saturation (>856-845 °C and 798-790 °C for two analyzed samples). The Zr saturation temperature based on zircon solubility and REE thermometry based on monazite solubility reflect an increase in temperature from the edge to the center of the pluton, which coincides with an increase in the huttonite content in monazite. The primary LREE assemblage is accompanied by small grains of late huttonite(?) replacing monazite and brabantite replacing allanite.
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Monazite ages from carbonatites and high-grade assemblages exposed along a significant lineament within the Southern Granulite Terrane of India termed the Kambam fault were obtained in thin section (in situ) using an ion microprobe. X-ray maps for Ce and Th were acquired in larger monazites to decipher the significance of the ages of individual spots within grains. The Kambam carbonatite contains large (millimeter-sized) apatite rimmed by ~10 μm thick bands of monazite. Monazite commonly appears as a lower-Th, late-stage mineral in carbonatites, and bands surrounding apatite are interpreted as products of metasomatism, rather than exsolution. The age of a Kambam carbonatite monazite band is 715 ± 42 Ma (Th-Pb, ± 1σ), but monazite filling cracks within the apatite is ~300 m.y. younger (405 ± 5 Ma). The younger monazite grains are in contact with quartz, a mineral thought to be an indicator of subsolidus alteration in carbonatites. The age of the monazite rim is similar to ages of several carbonatites located 50-400 km further north, and chemical analyses show that this sample displays chemical trends similar to the other complexes (e.g., Y/Ho, Ce/Pb, REE, and HFSE patterns). The mid-Neoproterozoic event is recorded in garnet-bearing assemblages ~20 km west of the Kambam fault (733 ± 15 Ma) and garnet-bearing enclaves within Southern Granulite Terrane charnockites (701 ± 26 Ma; 786 ± 84 Ma). The results show that monazite can crystallize during metasomatism and be useful in deciphering fluid processes occurring at deeper crustal levels. The Kambam fault, which records over 300 million years of monazite growth, should be considered a major boundary in reconstructions of Gondwana.
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Abstract Carbonatite hosts the most important rare earth resources in the world, but the precise timing, ore-forming history, and mechanism of rare earth mineralization in carbonatite systems are still in debate. Here, we report a rare corona texture of monazite-allanite-fluorapatite from the Huangjiagou carbonatite in the Lesser Qinling of central China, and demonstrate that the U-Th-Pb dating, trace elements, and Sr-Nd isotopes of these minerals in the corona are useful tools to unravel multiple-stage events for rare earth element (REE) mineralization and mobilization. The first mineralization event took place at ca. 219 Ma as revealed by the monazite U-Pb age, the same as regional carbonatite forming ages, but the Th-Pb age has been disturbed, which shows a negative correlation with Th contents. The second mineralization event occurred at ca. 128 Ma, as revealed by in situ U-Pb dating of allanite, coeval with the intrusions of neighboring I-type granite. The initial Sr-Nd isotope ratios of allanite show a downtrend from the center to the rim of monazite-allanite-apatite coronas to approach the ratios of neighboring granite, indicating an increasing effect by the metasomatism of magmatic-hydrothermal fluids during the growth of these REE-mineral coronas. Therefore, a two-episode REE mineralization was recognized with the replacement of ca. 219 Ma monazite by ca. 128 Ma allanite-apatite coronas on the function of magmatic-hydrothermal fluid metasomatism, and this process accompanies the disturbance of Th/Pb geochronology in monazite. Allanite as the product of monazite dissolution can represent the later-stage REE mineralization tracing the REE reworking processes under the hydrothermal conditions in carbonatite systems. Our study highlights the implication of monazite-allanite-fluorapatite coronas on the REE remobilization and mineralization in carbonatite systems.
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Carbonatite
Allanite
Pegmatite
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The experimental alteration of monazite to allanite, REE-epidote, fluorapatite, and/or fluorapatitebritholite 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.
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