Rare earths concentrate by complexing with alkalis in carbonatite-derived hydrothermal fluids.

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.

Nolans-type ore deposits contain REE and Th mineralization hosted in fluorapatite veins. These veins intrude granulite facies rocks and are surrounded by a diopside selvage. Nolans-type deposits are thought to form by REE, F and P-rich hydrothermal fluids derived from alkali or carbonatitic intrusions. However, REE are not effectively transported in F and P-rich systems. REE ore deposits are commonly hydrothermally overprinted, possibly obscuring the igneous nature of the primary mineralization. We conducted a series of piston cylinder “sandwich” experiments, testing the hydrothermal fluid hypothesis, and a newly suggested process of carbonatite metasomatism. Our results confirm theoretical predictions that REE are hydrothermally immobile in these systems and the experimental phase assemblage is not compatible with the natural rocks. Our results show that fluorapatite can only host several weight percent levels of REE at temperatures higher than ∼600 °C. Below that temperature, a miscibility gap exists between REE-poor fluorapatite and REE-rich silicates such as britholite or cerite. In contrast, experiments reacting P and REE-rich carbonatite with silicate rock above 700 °C closely resemble natural rocks from Nolans-type deposits. Selvage mineralogy is sensitive to the MgO content of the carbonatite. A diopside selvage formed at carbonatite MgO/(CaO+MgO) ≈ 0.2 while wollastonite and forsterite formed at lower and higher ratios, respectively. Phosphate solubility in carbonatites decreases with decreasing MgO contents. As diopside formed, REE-rich fluorapatite preferentially crystallized from the selvage inwards. Thus, carbonatites are effective at simultaneously mobilizing REE, F and P to the site of deposition. Nolans-type deposits are the cumulate residue of this reaction, with the carbonatite liquid migrating elsewhere. At temperatures below 700 °C the carbonatite–silicate reaction additionally formed monticellite, cuspidine and magnesioferrite, resembling a skarn assemblage. Whereas skarns form by infiltration of silicate magmas or related fluids to carbonate rocks, our experiments are the opposite: intrusion of carbonatite into silicate rock. These mid-crustal skarn-like rocks may host elevated ore elements of carbonatitic affinity, such as F, P, Y, REE, Th, Ba, Sr, and Nb. We propose the term “antiskarn” to describe such systems, and suggest they trace the migration of carbonatite liquids through the crust. Hydrothermal reworking, retrogression, or metamorphism of antiskarns may obscure the carbonatitic genesis of the rocks. These metasomatic zones are the crustal equivalent of wehrlites that form by peridotite–carbonatite reaction at mantle depths.

Plots of chondrite-normalised rare earth element (REE) patterns often appear as smooth curves. These curves can be decomposed into orthogonal polynomial functions (shape components), each of which captures a feature of the total pattern. The coefficients of these components (known as the lambda coefficients— $$\lambda $$λ ) can be derived using least-squares fitting, allowing quantitative description of REE patterns and dimension reduction of parameters required for this. The tetrad effect is similarly quantified using least-squares fitting of shape components to data, resulting in the tetrad coefficients ( $$\tau $$τ ). Our method allows fitting of all four tetrad coefficients together with tetrad-independent $$\lambda $$λ curvature. We describe the mathematical derivation of the method and two tools to apply the method: the online interactive application BLambdaR, and the Python package pyrolite. We show several case studies that explore aspects of the method, its treatment of redox-anomalous REE, and possible pitfalls and considerations in its use.

Nolans Bore is a rare earth element (REE) ore deposit in the Reynolds Range, Aileron Province, Northern Territory, Australia. It consists primarily of fluorapatite and alteration products thereof, surrounded by a diopside-dominated selvage. Previously considered to form via hydrothermal fluids, we now suggest that the deposit formed by a metasomatic reaction between a mantle-derived carbonatite and granulite-facies felsic host rocks, after peak metamorphism. REE patterns of fluorapatite are strongly light REE (LREE) enriched, convex with maxima at Ce to Nd, and contain a weak negative Eu anomaly. Textural and geochemical properties of the fluorapatite are consistent with its formation from a carbonatite liquid. Sinusoidal REE patterns in diopside along with strong Yb–Lu enrichment relative to coexisting titanite are suggestive of derivation from a Ca-rich carbonatite. Likewise, hyalophane present in the selvages forms by reaction of a BaCO3 component in the carbonatite with K-feldspar in the silicate host rocks. The overall morphology of Nolans Bore is consistent with carbonatite–silicate reaction experiments, with the carbonatite itself migrating elsewhere owing to the open-system nature of Nolans Bore. Ekanite veins in massive fluorapatite zones and allanite–epidote crusts on fluorapatite in contact with the diopside selvages formed by hydrothermal fluids exsolved from the carbonatite. Minor interstitial calcite was not igneous but was the last mineral to crystallize from the carbonatite-exsolved fluid. Y/Ho ratios qualitatively trace the transition from mantle-dominated igneous minerals to later low-temperature hydrothermal minerals. Rb–Sr and Sm–Nd analyses of unaltered minerals (fluorapatite, allanite, calcite) show that the carbonatite had homogeneous initial 87Sr/86Sr ≈ 0·7054 and εNd ≈ –4 at 1525 Ma, the best age estimate of the mineralization. Fluorapatite–allanite Sm–Nd dating results in an age of 1446 ± 140 Ma, consistent with forming soon after the end of the Chewings Orogeny. Neodymium depleted mantle model ages are older than 2 Ga, indicating the presence of recycled crustal material within the source. We suggest that the carbonatite was sourced from a mantle enriched by subduction of LREE-rich oceanic crustal rocks, marine sediments, and phosphorites, potentially from the south, or the Mount Isa area to the east. Nolans Bore represents the root zone of a now-eroded carbonatite. Other Nolans-type deposits (Hoidas Lake, Canada and Kasipatnam, India) are similarly hosted within siliceous granulite-facies rocks in regions with a long tectonic history, suggesting common processes that led to the formation of all three deposits. The REE-rich compositions of the mid-crustal Nolans Bore fluorapatite are the cumulates hypothesized to cause REE depletion in some unmineralized carbonatites. The rocks at Nolans Bore demonstrate that carbonatites, previously thought to be mostly unreactive, can undergo modification and modify the composition of the silicate rocks which they encounter, forming an ‘antiskarn’. At igneous temperatures, the resulting mineral assemblage (other than fluorapatite) consists of diopside and titanite, both of which are common in granulite-facies rocks. Therefore, carbonatite metasomatism can remain unnoticed if the resulting assemblage does not contain distinctively carbonatitic minerals.

The geochemical behavior and genesis of rare earth element (REE) ores remains poorly understood. In addition, the processes responsible for many features observed in REE ore deposits are not easily determined. Importantly, the distinction between igneous versus post-magmatic genesis, or the nature of the mineralizing and modifying fluids or melts, remains in dispute. Nolans Bore is a P-REE-Th deposit in the Northern Territory, Australia, hosting REE mineralization in fluorapatite and its alteration products. These mineralization textures are imaged in 3D by X-ray computed tomography and in 2D by electron microscopy, cathodoluminescence, and X-ray mapping. Primary igneous REE-rich fluorapatite was replaced in two stages. The first, at high temperature, was to endmember fluorapatite-britholite symplectite. The second, at lower temperatures, was to hydrothermal veins and patches comprised of REE-Th phosphate, silicate, and carbonate minerals. Quadrivalent Ce occurs together with Th, suggesting oxidized, low-temperature conditions. Strikingly similar textures are observed at Hoidas Lake, Saskatchewan, Canada, where igneous immiscibility or a pegmatitic boundary layer have been implicated in their formation. Our textural and chemical investigations establish that these symplectites and other similar textures are not primary igneous textures, but formed by subsequent cooling and alteration. Understanding the processes that formed these symplectic and vein textures is key to their theoretical and experimental modeling and should lead to a better understanding of “hydrothermal” REE deposits globally. The decoupling of Ce from the rest of the REE and the mineralogical preferences of the light REE versus the heavy REE should be considered when evaluating similar ore deposits for their economic value and mineral processing.