The origin and composition of carbonatite-derived carbonate-bearing fluorapatite deposits

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

Stable H–C–O isotope and trace element geochemistry of the Cummins Range Carbonatite Complex, Kimberley region, Western Australia: implications for hydrothermal REE mineralization, carbonatite evolution and mantle source regions

The Neoproterozoic Cummins Range Carbonatite Complex (CRCC) is situated in the southern Halls Creek Orogen adjacent to the Kimberley Craton in northern Western Australia. The CRCC is a composite, subvertical to vertical stock ∼2 km across with a rim of phlogopite–diopside clinopyroxenite surrounding a plug of calcite carbonatite and dolomite carbonatite dykes and veins that contain variable proportions of apatite–phlogopite–magnetite ± pyrochlore ± metasomatic Na–Ca amphiboles ± zircon. Early high-Sr calcite carbonatites (4,800–6,060 ppm Sr; La/YbCN = 31.6–41.5; δ13C = −4.2 to −4.0 ‰) possibly were derived from a carbonated silicate parental magma by fractional crystallization. Associated high-Sr dolomite carbonatites (4,090–6,310 ppm Sr; La/YbCN = 96.5–352) and a late-stage, narrow, high rare earth element (REE) dolomite carbonatite dyke (La/YbCN = 2756) define a shift in the C–O stable isotope data (δ18O = 7.5 to 12.6 ‰; δ13C = −4.2 to −2.2 ‰) from the primary carbonatite field that may have been produced by Rayleigh fractionation with magma crystallization and cooling or through crustal contamination via fluid infiltration. Past exploration has focussed primarily on the secondary monazite-(Ce)-rich REE and U mineralization in the oxidized zone overlying the carbonatite. However, high-grade primary hydrothermal REE mineralization also occurs in narrow (<1 m wide) shear-zone hosted lenses of apatite–monazite-(Ce) and foliated monazite-(Ce)–talc rocks (≤∼25.8 wt% total rare earth oxide (TREO); La/YbCN = 30,085), as well as in high-REE dolomite carbonatite dykes (3.43 wt% TREO), where calcite, parisite-(Ce) and synchysite-(Ce) replace monazite-(Ce) after apatite. Primary magmatic carbonatites were widely hydrothermally dolomitized to produce low-Sr dolomite carbonatite (38.5–282 ppm Sr; La/YbCN = 38.4–158.4; δ18O = 20.8 to 21.9 ‰; δ13C = −4.3 to −3.6 ‰) that contains weak REE mineralization in replacement textures, veins and coating vugs. The relatively high δD values (−54 to −34 ‰) of H2O derived from carbonatites from the CRCC indicate that the fluids associated with carbonate formation contained a significant amount of crustal component in accordance with the elevated δ13C values (∼−4 ‰). The high δD and δ13C signature of the carbonatites may have been produced by CO2–H2O metasomatism of the mantle source during Paleoproterozoic subduction beneath the eastern margin of the Kimberley Craton