Carbonatites and related rocks are the premier source for light rare earth element (LREE) deposits. Here, we outline an ore formation model for LREE-mineralised carbonatites, reconciling field and petrological observations with recent experimental and isotopic advances. The LREEs can strongly partition to carbonatite melts, which are either directly mantle-derived or immiscible from silicate melts. As carbonatite melts evolve, alkalis and LREEs concentrate in the residual melt due to their incompatibility in early crystal-lising minerals. In most carbonatites, additional fractionation of calcite or ferroan dolomite leads to evolution of the residual liquid into a mobile alkaline “brine-melt” from which primary alkali REE carbonates can form. These primary carbonates are rarely preserved owing to dissolution by later fluids, and are replaced in-situ by monazite and alkali-free REE-(fluor)carbonates.

The Tundulu and Kangankunde carbonatite complexes in the Chilwa Alkaline Province, Malawi, contain late-stage, apatite-rich lithologies termed quartz-apatite rocks. Apatite in these rocks can reach up to 90 modal% and displays a distinctive texture of turbid cores and euhedral rims. Previous studies of the paragenesis and rare earth element (REE) content of the apatite suggest that heavy REE (HREE)-enrichment occurred during the late-stages of crystallization. This is a highly unusual occurrence in intrusions that are otherwise light REE (LREE) enriched. In this contribution, the paragenesis and formation of the quartz-apatite rocks from each intrusion is investigated and re-evaluated, supported by new electron microprobe (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data to better understand the mechanism of HREE enrichment. In contrast to the previous work at Tundulu, we recognize three separate stages of apatite formation, comprising an “original” euhedral apatite, “turbid” apatite, and “overgrowths” of euhedral late apatite. The crystallization of synchysite-(Ce) is interpreted to have occurred subsequent to all phases of apatite crystallization. The REE concentrations and distributions in the different minerals vary, but generally higher REE contents are found in later-stage apatite generations. These generations are also more LREE-enriched, relative to apatite that formed earlier. A similar pattern of increasing LREE-enrichment and increased REE concentrations toward later stages of the paragenetic sequence is observed at Kangankunde, where two generations of apatite are observed, the second showing higher REE concentrations, and relatively higher LREE contents.

Stable (C and O) isotope data from carbonates are one of the most important methods used to infer genetic processes in carbonatites. However despite their ubiquitous use in geological studies, it is suspected that carbonates are susceptible to dissolution-reprecipitation and isotopic resetting, especially in shallow intrusions, and may not be the best records of either igneous or hydrothermal processes. Apatite, however, should be much less susceptible to these resetting problems but has not been used for O isotope analysis. In this contribution, a novel bulk-carbonatite method for the analysis of O isotopes in the apatite PO4 site demonstrates a more robust record of stable isotope values. Analyses of apatite from five carbonatites with magmatic textures establishes a preliminary Primary Igneous Apatite (PIA) field of δ18O = + 2.5 to + 6.0‰ (VSMOW), comparable to Primary Igneous Carbonatite (PIC) compositions from carbonates.\ud \ud Carbonate and apatite stable isotope data are compared in 10 carbonatite samples from Songwe Hill, Malawi. Apatite is heavy rare earth element (HREE) enriched at Songwe and, therefore, oxygen isotope analyses of this mineral are ideal for understanding HREE-related mineralisation in carbonatites. Carbonate C and O isotope ratios show a general trend, from early to late in the evolution, towards higher δ18O values (+ 7.8 to + 26.7‰, VSMOW), with a slight increase in δ13C (− 4.6 to − 0.1‰, VPDB). Oxygen isotope ratios from apatite show a contrary trend, decreasing from a PIA field towards more negative values (+ 2.5 to − 0.7‰, VSMOW). The contrasting results are interpreted as the product of the different minerals recording fluid interaction at different temperatures and compositions. Modelling indicates the possibility of both a CO2 rich fluid and mixing between meteoric and deuteric waters. A model is proposed where brecciation leads to depressurisation and rapid apatite precipitation. Subsequently, a convection cell develops from a carbonatite, interacting with surrounding meteoric water. REE are likely to be transported in this convection cell and precipitate owing to decreasing salinity and/or temperature

Carbonate-bearing fluorapatite rocks occur at over 30 globally distributed carbonatite complexes and represent a substantial potential supply of phosphorus for the fertiliser industry. However, the process(es) involved in forming carbonate-bearing fluorapatite at some carbonatites remain equivocal, with both hydrothermal and weathering mechanisms inferred. In this contribution, we compare the paragenesis and trace element contents of carbonate-bearing fluorapatite rocks from the Kovdor, Sokli, Bukusu, Catalão I and Glenover carbonatites in order to further understand their origin, as well as to comment upon the concentration of elements that may be deleterious to fertiliser production. The paragenesis of apatite from each deposit is broadly equivalent, comprising residual magmatic grains overgrown by several different stages of carbonate-bearing fluorapatite. The first forms epitactic overgrowths on residual magmatic grains, followed by the formation of massive apatite which, in turn, is cross-cut by late euhedral and colloform apatite generations. Compositionally, the paragenetic sequence corresponds to a substantial decrease in the concentration of rare earth elements (REE), Sr, Na and Th, with an increase in U and Cd. The carbonate-bearing fluorapatite exhibits a negative Ce anomaly, attributed to oxic conditions in a surficial environment and, in combination with the textural and compositional commonality, supports a weathering origin for these rocks. Carbonate-bearing fluorapatite has Th contents which are several orders of magnitude lower than magmatic apatite grains, potentially making such apatite a more environmentally attractive feedstock for the fertiliser industry. Uranium and cadmium contents are higher in carbonate-bearing fluorapatite than magmatic carbonatite apatite, but are much lower than most marine phosphorites.

Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and ⁸⁷Sr/⁸⁶Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8–15 wt% REE₂O₃, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The ⁸⁷Sr/⁸⁶Sr values (0.70302–0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (δ¹⁸O + 3 to + 5‰_VSMOW and δ¹³C − 3.5 to − 3.2‰_VPDB). In contrast, dolomite in the same samples has similar δ¹³C values but much higher δ¹⁸O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar δ¹⁸O and ⁸⁷Sr/⁸⁶Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: δ¹⁸O + 7.7 to + 10.3‰ and δ¹³C −5.2 to −6.0‰; ⁸⁷Sr/⁸⁶Sr 0.70296–0.70298) is not directly linked with the REE mineralisation.

Songwe Hill, Malawi, is one of the least studied carbonatites but has now become particularly important as it hosts a relatively large rare earth deposit. The results of new mapping, petrography, geochemistry and geochronology indicate that the 0.8 km diameter Songwe Hill is distinct from the other Chilwa Alkaline Province carbonatites in that it intruded the side of the much larger (4 × 6 km) and slightly older (134.6 ± 4.4 Ma) Mauze nepheline syenite and then evolved through three different carbonatite compositions (C1–C3). Early C1 carbonatite is scarce and is composed of medium–coarse-grained calcite carbonatite containing zircons with a U–Pb age of 132.9 ± 6.7 Ma. It is similar to magmatic carbonatite in other carbonatite complexes at Chilwa Island and Tundulu in the Chilwa Alkaline Province and others worldwide. The fine-grained calcite carbonatite (C2) is the most abundant stage at Songwe Hill, followed by a more REE- and Sr-rich ferroan calcite carbonatite (C3). Both stages C2 and C3 display evidence of extensive (carbo)-hydrothermal overprinting that has produced apatite enriched in HREE (<2000 ppm Y) and, in C3, synchysite-(Ce). The final stages comprise HREE-rich apatite fluorite veins and Mn-Fe-rich veins. Widespread brecciation and incorporation of fenite into carbonatite, brittle fracturing, rounded clasts and a fenite carapace at the top of the hill indicate a shallow level of emplacement into the crust. This shallow intrusion level acted as a reservoir for multiple stages of carbonatite-derived fluid and HREE-enriched apatite mineralisation as well as LREE-enriched synchysite-(Ce). The close proximity and similar age of the large Mauze nepheline syenite suggests it may have acted as a heat source driving a hydrothermal system that has differentiated Songwe Hill from other Chilwa carbonatites