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The carbonatite dike swarm and vein stockwork at the center of the Paleogene Bear Lodge alkaline complex (BLAC), Wyoming, USA, is host to diverse REE mineral assemblages that are largely a result of subsolidus modification and REE redistribution. Pseudomorphic replacement of primary burbankite by an assemblage of ancylite, strontianite, and barite is the result of interaction with late-stage hydrothermal fluids that added Sr, Ba, S, F, and REE, analogous to the replacement processes described for some carbonatite complexes of Russia's Kola Peninsula. Carbon and oxygen stable isotope ratios indicate that the primary carbonatite mineralogy experienced degassing/pneumatolysis and alteration by fluids of variable temperature, CO2/H2O ratios, and/or meteoric water content. Isotopic differences of matrix calcite between Group 1 carbonatites (avg. δ13C = −7.3‰; δ18O = 9.1‰) and Group 2 carbonatites (avg. δ13C = −9.9‰; δ18O = 10.2‰) are consistent with loss of CO2 during degassing. The open-system alteration of burbankite caused a pronounced positive δ18O-shift in bulk ancylite pseudomorphs (δ18O: 14.3–25.7‰) relative to matrix calcite (δ18O: 8.7–11.2‰). Oxygen isotope compositions of biotite (δ18O: 4.5–5.9‰) and K-feldspar (δ18O: 7.3–7.9‰) in unoxidized carbonatite are typical of primary magmatic silicates and suggest that fluids responsible for the burbankite-to-ancylite conversion remained predominantly magmatic (carbohydrothermal). Concomitant increases toward the surface in 13C and 18O, oxidation, matrix carbonate dissolution, and the replacement of REE carbonates (ancylite, carbocernaite, and burbankite) by Ca-REE fluorocarbonates (bastnasite, parisite, synchysite) suggest interaction with late-stage, low temperature (

The silico-carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartzbearing, 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), bastnasite-(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). Bastnasite and parisite where replaced by synchysite-(Ce) and rontgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution re carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphateminerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE.Mass balance considerations indicate hydrothermal HREE to themineralisation. The evolution of the in may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferentialHREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexationmay have been important for preferential HREE transport. AlongsideHREE-enrichedmagmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.flects the evolution from magmaticfluids must have contributedfluorcarbonate mineral assemblage requires an increaseaCa2+ and aCO3 2− in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite−) may account

Hydrothermal rare earth element (REE) precipitation in carbonatite is generally attributed to increase in pH or decrease in temperature when REE-bearing acidic fluids interact with carbonates. Here, we document microtextures comprising intergrowth of bastnasite, hydroxyl-parisite, rontgenite, synchysite, and pyrochlore, with calcite that pseudomorphically replaces patches of hematite with cellular boxwork-type structure, in calciocarbonatites from the Kamthai alkaline complex in western India. The nature of the REE mineralization grades from proximal bastnasite-dominated to distal hydroxyl-parisite dominated in the boxworks. The microtextural relations and trace element chemistry of hematite, magnetite and calcite, and C-O isotope composition of carbonate are suggestive of extensive low-temperature hydrothermal alteration of the carbonatites. The hematite boxwork structure and the REE mineral-calcite intergrowths often have squarish outlines and are interpreted to have pseudomorphed primary magnetite during fluid-rock interaction. We propose a new mechanism of REE precipitation in magnetite-rich carbonatites involving influx of acidic hydrothermal fluids, which scavenged the REE and other trace elements from magmatic carbonates and apatite. These acidic fluids were responsible for the protonation of magnetite and leaching out of Fe2+, converting them to hematite through a non-redox transformation. The reaction results in 32% volume reduction for every mole of magnetite consumed, generating significant rock porosity, which further aided and abetted fluid-rock reaction and hydrothermal alteration. More importantly, it consumed proton, which increased the fluid pH triggering precipitation of bastnӓsite-group minerals (including bastnӓsite, parasite, rontgenite, synchysite). Close to the magnetite-hematite reaction front, fluor-dominated bastnӓsite-group minerals (mainly bastnӓsite) appear, while away from such fronts, mineralization was enriched in hydroxyl-bastnӓsite group minerals (mainly parisite) as a consequence of decreasing activity of F‐ and/or increasing activity of OH‐ with the progress of magnetite-to-hematite transformation.

The Morro dos Seis Lagos niobium rare earth element, Ti-bearing lateritic deposit (Amazonas, Brazil) is derived from a primary siderite carbonatite. The complex is the only example of a Nb deposit in which Nb-rich rutile is the main Nb ore mineral. Apart from the laterites, at the current level of exposure the complex consists only of siderite carbonatite; silicate rocks are absent. Three types of siderite carbonatite are recognized: (1) a brecciated and oxidized core siderite carbonatite consisting of up to 95 vol% siderite together with: hematite; pyrochlore; Nb-brookite; Ti-maghemite; and thorobastnasite; (2) a REE- and P-rich variety of the core siderite carbonatite consisting of siderite (up to 95 vol%), hematite, minor pyrochlore, monazite and bastnasite; (3) a border hydrothermal siderite carbonatite with ~70 vol% siderite, barite (~15 vol%), gorceixite (~7 vol%) and minor rhabdophane and pyrochlore. The country rock gneiss in which the carbonatite was emplaced was affected by potassic fenitization, with the formation of phlogopite and orthoclase together with monazite, fluorapatite and bastnasite. The siderite carbonatites exhibit a wide variation of δ13C (−5.39‰ to −1.40‰), accompanied by a significant variation in δ18O (17.13‰ to 31.33‰), especially in the REE-rich core siderite carbonatite, and are explained as due to the presence of both H2O and CO2 in the magma. The core siderite carbonatite is the richest in Fe (48.64–70.85 wt% Fe2O3) and the poorest in Ca (up 0.82 wt% CaO) example of a siderite carbonatite yet recognized The ferrocarbonatite has significant contents of Mn, Ba, Th, Pb and LREE, and a very high Nb (up to 7667 ppm) content due to the presence of Nb-brookite. The substitution 3Ti4+ = Fe2+ + 2Nb5+ recognized in Nb-rich brookite explains enrichment of Nb in the core siderite carbonatite and indicates formation in a reducing environment. The high Nb/Ta ratio (1408–11,459) of the carbonatite is compatible with residual liquids derived by fractional crystallization. The 87Sr/86Sr (0.70411–0.70573) and 144Nd/143Nd (0.512663–0.512715) isotopic data suggest the carbonatite is mantle-derived with essentially no crustal contamination and is younger than the maximum age of 1328 ± 58 Ma (U Pb in zircon). We suggest that the Morro dos Seis Lagos carbonatite complex represents the upper-most parts of a differentiated carbonatite magmatic system, and that the siderite carbonatite is related to late-magmatic-to-carbo-hydrothermal processes.

The Qinling molybdenum belt is a prominent metallogenic structure in central China hosting several significant porphyry- and porphyry–skarn-type deposits. The Huanglongpu Mo deposit in the north-western part of the belt is unique in that it is associated with carbonatite dykes, rather than felsic magmatism. The carbonatites are composed largely of Sr–Mn-rich calcite and characterized by high concentrations of Sr and rare-earth elements (REE), and stable-isotope values indicative of a mantle source (δ13CPDB = − 6.7 ± 0.2‰ and δ18OSMOW = 8.2 ± 1.0‰). Molybdenite is associated with galena and REE minerals (parisite, bastnasite and monazite). Both molybdenite and galena are characterized by high Re contents (up to 0.4 and 0.2 wt.%, respectively) and Re/(Mo, Pb) ratios approaching the primitive-mantle values. In contrast to the rock-forming calcite, the REE minerals are enriched in light REE, whose relative proportion increases from parisite-(Ce) [average (La/Nd)n = 2.1] to bastnasite-(Ce) and monazite-(Ce) [average (La/Nd)n = 3.1, 4.6, respectively]. The whole-rock compositions are characterized by some of the highest Mo and heavy REE abundances reported for carbonatites to date: up to 1010 ppm Mo, 1130 ppm Y + Gd…Lu and (La/Yb)n = 1.2–2.7. The unusual trace-element geochemistry of the Huanglongpu rocks may ultimately reflect the composition of their mantle source, but their enrichment in Mo + Re was undoubtedly enhanced through preferential partitioning of these elements into a light REE–Pb–S-rich fluid derived from the carbonatitic magma modified by calcite fractionation. The present work shows that Mo can be retained, transported and deposited by carbonatitic fluids capable of generating economic Mo deposits.

A unique REE–Y–(Th)–P–As–(Si)–(Nb)–(S) accessory assemblage was identified in a small body of Lower Triassic A-type rhyolite of the Silicic Superunit near Tisovec-Rejkovo, Central Slovakia. Arsenian monazite-(Ce)–phosphatian gasparite-(Ce) and arsenian xenotime-(Y)–phosphatian chernovite-(Y) solid solutions in association with REE carbonates (bastnasite, parisite, rontgenite?, synchysite) and rare cerianite-(Ce) form anhedral to subhedral grains and aggregates (≤ 0.3 mm), scattered in the groundass or as intergrowths with zircon and Fe–Ti oxides. Compositions show a wide AsP− 1 substitution in monazite–gasparite and xenotime–chernovite solid solutions; atom. % As/(As+P) = 0.00 to 0.73 and 0.10 to 0.94, respectively. The presence of S in monazite–gasparite s.s. (≤ 0.14 apfu), together with Ca enrichment indicates “clinoanhydrite“ substitution, CaS(REE,Y)− 1 (P,As)− 1, rather than the incorporation of brabantite, along the CaTh(REE,Y)− 2 exchange vector. Moreover, the Th- and Nb-rich members reveal thorite and fergusonite substitutions, ThSi(Y,REE)− 1 (P,As)− 1 and Nb(P,As)− 1, respectively. The As-rich REE phases originated probably during the post-magmatic alteration of primary monazite-(Ce) and xenotime-(Y) by As-rich, high fO2 fluids, whereas cerianite-(Ce) and the REE carbonates are products of a later hydrothermal overprint of the rhyolite by CO2-rich solutions.