Thematic Articles

The Distinctive Mineralogy of Carbonatites

The mineralogy of carbonatites reflects both the diversity of the sources of their parent magmas and their unusual chemistry. Carbonatites contain diverse suites of both primary magmatic minerals and later hydrothermal products. We present a summary of the variety of minerals found in carbonatites, and note the economic importance of some of them, particularly those that are major sources of “critical elements”, such as Nb and rare earth elements (REEs), which are essential for modern technological applications. Selected mineral groups are then discussed in detail: the REE carbonates, the alkali-rich ephemeral minerals that are rarely preserved but that may be important in the petrogenesis of carbonatites and their metasomatic haloes in adjacent rocks, and the Nb-rich oxides of the pyrochlore supergroup.

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Formation of Rare Earth Deposits in Carbonatites

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 crystallising 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.

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Carbonatitic Melts and Their Role in Diamond Formation in the Deep Earth

Carbonatitic high-density fluids and carbonate mineral inclusions in ­lithospheric and sub-lithospheric diamonds reveal comparable compositions to crustal carbonatites and, thus, support the presence of carbonatitic melts to depths of at least the mantle transition zone (~410–660 km depth). Diamonds and high pressure–high temperature (HP–HT) experiments confirm the stability of lower mantle carbonates. Experiments also show that carbonate melts have extremely low viscosity in the upper mantle. Hence, carbonatitic melts may participate in the deep (mantle) carbon cycle and be highly effective metasomatic agents. Deep carbon in the upper mantle can be mobilized by metasomatic carbonatitic melts, which may have become increasingly volumetrically significant since the onset of carbonate subduction (~3 Ga) to the present day.

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Evolution of Carbonatite Magmas in the Upper Mantle and Crust

Carbonatites are the most silica-poor magmas known and are amongst Earth’s most enigmatic igneous rocks. They crystallise to rocks dominated by the carbonate minerals calcite and dolomite. We review models for carbonatite petrogenesis, including direct partial melting of mantle lithologies, exsolution from silica-undersaturated alkali silicate melts, or direct fractionation of carbonated silicate melts to carbonate-rich residual melts. We also briefly discuss carbonatite–mantle wall-rock reactions and other processes at mid- to upper crustal depths, including fenitisation, overprinting by carbohydrothermal fluids, and reaction between carbonatite melt and crustal lithologies.

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Carbonatites: Contrasting, Complex, and Controversial

Carbonatites are unique, enigmatic, and controversial rocks directly sourced from, or evolved from, mantle melts. Mineral proportions and chemical compositions of carbonatites are highly variable and depend on a wide range of processes: melt generation, liquid immiscibility, fractional crystallization, and post-magmatic alteration. Observations of plutonic carbonatites and their surrounding metasomatic rocks (fenites) suggest that carbonatite intrusions and volcanic rocks do not fully represent the true compositions of the parental carbonatite melts and fluids. Carbonatites are enriched in rare elements, such as niobium and rare earths, and may host deposits of these elements. Carbonatites are also important for understanding the carbon cycle and mantle evolution.

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Forming Earth’s Continental Crust: A Nontraditional Stable Isotope Perspective

The formation of continental crust via plate tectonics strongly influences the physical and chemical characteristics of Earth’s surface and may be the key to Earth’s long-term habitability. However, continental crust formation is difficult to observe directly and is even more difficult to trace through time. Nontraditional stable isotopes have yielded significant insights into this process, leading to a new view both of Earth’s earliest continental crust and of what controls modern crustal generation. The stable isotope systems of titanium (Ti), zirconium (Zr), molybdenum (Mo), and thallium (Tl) have proven invaluable. Processes such as fractional crystallization, partial melting, geodynamic setting of magma generation, and magma cooling histories are examples of processes illuminated by these isotope systems.

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Ironing Out Isotopic Differences Among Rocky Bodies

T he variability of iron isotopes among rocky bodies in the inner Solar System provides a window onto the diversity of materials and mechanisms from which they formed. The magnitude of isotopic variation in mantle-derived rocks within a given body is similar to that between different planetary bodies. Isotopic signatures arising from primordial events, namely, evaporation/condensation, core formation and melting/crystallization, may be progressively diluted, modified, and redistributed over time by global recycling processes such as plate tectonics. Here, we assess the relative influence of these primordial mechanisms on the iron isotope compositions of igneous rocks and their implications for the structure and accretion histories of rocky planets.

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Planetary Evaporation

Evaporation of magma oceans exposed to space may have played a role in the chemical and isotopic compositions of rocky planets in our Solar System (e.g., Earth, Moon, Mars) and their protoplanetary antecedents. Chemical depletion of moderately volatile elements and the enrichment of these elements’ heavier isotopes in the Moon and Vesta relative to chondrites are clear examples. Evaporation is also thought to be an important process
in some exoplanetary systems. Identification of evaporation signatures among the rock-forming elements could elucidate important reactions between melts and vapors during planet formation in general, but the process is more complicated than is often assumed.

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Planetary Genealogy

The detection of exoplanets and accretion disks around newborn stars has spawned new ideas and models of how our Solar System formed and evolved. Meteorites as probes of geologic deep time can provide ground truth to these models. In particular, stable isotope anomalies in meteorites have recently emerged as key tracers of material flow in the early Solar System, allowing cosmochemists to establish a “planetary isotopic genealogy”. Although not complete, this concept has substantially advanced our understanding of Solar System evolution, from the collapse of the Sun’s parental molecular cloud to the accretion of the planets.

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Unlocking the Single-Crystal Record of Heavy Stable Isotopes

Stable isotopes provide deep insights into processes across a wide range of scales, from micron- to cosmic-size systems. Here, we review how continued advances in mass-spectrometry have enabled the analysis of ever-smaller samples and brought the field of heavy stable isotope geochemistry to its next frontier: the single-crystal scale. Accessing this record can be as enlightening as it is challenging. Drawing on novel systematics at different stages of development (from well-established to nascent), we discuss how the isotopes of heavy elements, such as magnesium, iron, zirconium, or uranium, can be used at the single-crystal and subcrystal scales to reconstruct magma thermal histories, crystal growth timescales, or, possibly, magma redox conditions.

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