Carbonatites are familiar to students of petrology as rare igneous rocks formed predominantly of carbonate, whose only modern expression is a single active volcano that erupts strongly alkaline carbonate lavas with no direct match in Earth’s geological record (see Lengai movie in the electronic version of this chapter or on the MSA RiMG website). Based on their Sr-Nd-Pb isotopic data, stable isotopic compositions, noble gases, and experimental phase equilibria, they are derived from the mantle, showing almost no sign of contamination by the crust.

As liquids, carbonate melts have remarkable physical properties, which set them apart from the alkaline silicate melts with which they are often temporally associated. They show very high solubilities of many elements considered rare in silicate magmas, and they have the highest known melt capacities for dissolving water and other volatile species like halogens at crustal pressures. They are highly efficient transport agents of carbon from the mantle to the crust, remaining mobile over extraordinary ranges of temperature, and their very low viscosity should enhance connectivity along grain boundaries in the mantle where they are implicated in geochemical enrichment processes related to metasomatism.

Most carbonatites have unambiguous origins in the mantle and the limit to their depth is not known, but the likelihood that they may exist in the lower mantle (Kaminsky et al. 2009, 2012; Stoppa et al. 2009) needs to be appraised since they may exert a fundamental control on the mobility and long-term storage of deep carbon in Earth. Ultimately the stability of carbonate melt is an extension of the stability of carbonate minerals (Hazen et al. 2013a,b) subject critically to the mantle oxidation state (Luth 1993; Frost and McCammon 2008); carbonate-melts have also been predicted in the oceanic low-velocity zone and deep mantle (Hauri et al. 1993 …

Carbonate Melts and Carbonatites

The Vuoriyarvi Devonian carbonatite–ijolite–pyroxenite–olivinite complex comprises several carbonatite fields: Neske Vara, Tukhta-Vara, and Petyayan-Vara. The most common carbonatites in the Tukhta-Vara and Neske-Vara fields are calciocarbonatites, which host several P, Fe, Nb, and Ta deposits. This paper focuses on the Petyayan-Vara field, in which the primary magmatic carbonatites are magnesian. The least altered magnesiocarbonatites are composed of dolomite with burbankite and are rich in REE (up to 2.0 wt. %), Sr (up to 1.2 wt. %), and Ba (up to 0.8 wt. %). These carbonatites underwent several stages of metasomatism. Each metasomatic event produced a new rock type with specific mineralization. The introduction of K, Si, Al, Fe, Ti, and Nb by a F-rich fluid (or fluid-saturated melt) resulted in the formation of high-Ti magnesiocarbonatites and silicocarbonatites, composed of dolomite, microcline, Ti-rich phlogopite, and Fe–Ti oxides. Alteration by a phosphate–fluoride fluid caused the crystallization of apatite in the carbonatites. A sulfate-rich Ba–Sr–rare-earth elements (REE) fluid (probably brine-melt) promoted the massive precipitation of ancylite and baryte and, to a lesser extent, strontianite, bastnasite, and synchysite. Varieties of carbonatite that contain the highest concentrations of REE are ancylite-dominant. The influence of sulfate-rich Ba-Sr-REE fluid on the apatite-bearing rocks resulted in the dissolution and reprecipitation of apatite in situ. The newly formed apatite generation is rich in HREE, Sr, and S. During late-stage transformations, breccias of magnesiocarbonatites with quartz-bastnasite matrixes were formed. Simultaneously, strontianite, quartz, calcite, monazite, HREE-rich thorite, and Fe-hydroxides were deposited. Breccias with quartz-bastnasite matrix are poorer in REE (up to 4.5 wt. % total REE) than the ancylite-dominant rocks (up to 11 wt. % total REE).

The Petyayan-Vara Carbonatite-Hosted Rare Earth Deposit (Vuoriyarvi, NW Russia): Mineralogy and Geochemistry

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, Catalao 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.

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

Carbonatites undergo various magmatic-hydrothermal processes during their evolution that are important for the enrichment of rare earth elements (REE). This geochemical, petrographic, and multi-isotope study on the Kangankunde carbonatite, the largest light REE resource in the Chilwa Alkaline Province in Malawi, clarifies the critical stages of REE mineralization in this deposit. The δ56Fe values of most of the carbonatite lies within the magmatic field despite variations in the proportions of monazite, ankerite, and ferroan dolomite. Exsolution of a hydrothermal fluid from the carbonatite melts is evident based on the higher δ56Fe of the fenites, as well as the textural and compositional zoning in monazite. Field and petrographic observations, combined with geochemical data (REE patterns, and Fe, C, and O isotopes), suggest that the key stage of REE mineralization in the Kangankunde carbonatite was the late magmatic stage with an influence of carbothermal fluids i.e. magmatic–hydrothermal stage, when large (~200 µm), well-developed monazite crystals grew. The C and O isotope compositions of the carbonatite suggest a post-magmatic alteration by hydrothermal fluids, probably after the main REE mineralization stage, as the alteration occurs throughout the carbonatite but particularly in the dark carbonatites.

D.P. Hammond

Papers

Geology of the Ngualla carbonatite complex, Tanzania, and origin of the Weathered Bastnaesite Zone REE ore