Frances Wall

Carbonatite dykes at bayan Obo, inner Mongolia, China

SummaryCalcite-rich dykes occur in the thrust fold belt near the Bayan Obo rare earth element (REE) deposit. They cut a thrust inlier of granitic migmatite within folded Bayan Obo Group sediments of Proterozoic age. Cathodoluminescence, X-ray fluorescence and microprobe studies show that the rock is a calcite carbonatite with Sr-Mn-bearing calcite, magnesio-riebeckite, apatite, pyrochlore, K-feldspar and biotite. One dyke was chosen for detailed analysis. Its margin is strongly REE-mineralized with much monazite developed adjacent to zoned apatite. Secondary alteration is marked by the introduction of Fe and Mn. The adjacent migmatite is fenitized to a magnesio-riebeckite-albite rock. The sedimentary dolomite of the Bayan Obo Group is composed mainly of Mn-Sr-RE-hearing ferroan dolomite and contains bands of opaque grains, apatite, monazite, fluorite and taeniolite. Many trace element and isotope similarities between the carbonatite dyke and the sedimentary dolomite are revealed, and the evidence supports the possibility that the dolomite is a dolomitized carbonatite tuff. The Bayan Obo REE mineralization also shows geochemical similarities with the mineralization seen in the carbonatites, and a possible genetic connection is presented.ZusammenfassungKalzit-reiche Gänge kommen im Faltengürtel in der Nähe der Seltenen-Erd-Lagerstätte Bayan Obo vor. Es handelt sich um hellbräunliche, 1–2 m mächtige Gänge, die migmatitische Orthogneise von granitischer Zusammensetzung innerhalb der gefalteten Sedimente der Bayan Obo Gruppe durchsetzen. Chemische Daten, die auf Kathoden-Lumineszenz, Röntgen-Fluoreszenz und Mikrosondenuntersuchungen beruhen, zeigen, daß es sich hier um einen Kalzit-KazhooudimdSr-Mo-führeodem Kalzit, Magnesio-Riebeckit Apatit, Pyrochlor Alkalifelds und Biotit handelt. Einer dieser Gänge wurde für eine eingehende Untersuchung ausgewählt. Seine randlichen Partien sind stark mit SEE mineralisiert, und viel Monazit kommt in der Nähe von zonar gebautem Apatit vor. Sekundäre Umwandlung wird durch die Zufuhr von Fe und Mn markiert. Der benachbarte Migmatit ist fenitisiert und dadurch in ein Magnesio-Riebeckit-Gestein umgewandelt. Der sedimentäre Dolomit der Bayan-Obo-Gruppe besteht hauptsächlich aus Mn-Sr-SE-führenden eisenhaltigen Dolomit und enthält Lagen von opaken Mineralen, Apatit, Monazit, Fluorit und Taeniolit. Karbonatitgänge und der sedimentäre Dolomit zeigen Ähnlichkeiten, was den Spurenelementgehalt und die isotopische Zusammensetzung betrifft. Diese Daten weisen auf die Möglichkeit hin, daß der Dolomit ein dolomitisiert Karbonatit-Tuff ist. Die SEE-Vererzung von Bayan Obo zeigt auch geochemische Ähnlichkeiten mit der Vererzung der Karbonatite, und ein möglicher genetischer Zusammenhang wird diskutiert.

PYROCHLORE FROM WEATHERED CARBONATITE AT LUESHE, ZAIRE

Abstract A detailed study of weathered pyrochlore in the laterite above carbonatite at Lueshe, NE Zaire, has been made in order to determine its chemical and textural variations. Pyrochlore in fresh carbonatite at Lueshe is close to an ideal formula of (Ca,Na)2Nb2O6(OH,F) (where a general formula is A2−xB2O6(OH,F)1−y·zH2O). The first and principal change on weathering occurs at the base of the profile and involves the leaching and partial exchange of A cations together with hydration. This change appears common to weathered pyrochlore worldwide. As a result weathered pyrochlore at Lueshe has a large apparent A cation deficiency with A totals between 0.25 and 0.59. The B cations remain stable. Abundant kalipyrochlore is unique to Lueshe and is thought to be related to the abundance of potassium feldspar in the fresh carbonatite, showing that the actual composition of weathered pyrochlore is a characteristic of a particular deposit. Weathered profiles at I,ueshe are not simple trends from the least to most leached compositions. Further factors including variation in whole rock mineralogy and chemistry, and cation exchange and uptake are responsible for local concentrations of strontio-, bario- and calcium-rich, sodium-poor pyrochlore in the ore body, as well as rims of ceriopyrochlore on kalipyrochlore. The most important textural relationship in the Lueshe pyrochlore is the intimate intergrowth with crandallite in the most weathered parts of the laterite. Although pyrochlore persists throughout the weathering profile, niobium-beating goethite is thought to represent the final product of pyrochlore breakdown.

Burbankite group minerals and their alteration in rare earth carbonatites—source of elements and fluids (evidence from C–O and Sr–Nd isotopic data)

The 370–380 Ma Khibina and Vuoriyarvi complexes on the Kola Peninsula, Russia, which form part of the Palaeozoic Kola Alkaline Province, contain REE-rich carbonatites with burbankite (Na,Ca)3(Sr,Ca,REE,Ba)3(CO3)5 or calcioburbankite (Na,Ca)3(Ca,Sr,REE,Ba)3(CO3)5 as the principal primary REE mineral. Within each complex the C–O and Sr–Nd isotopic data are similar for burbankite group minerals and co-existing calcite or dolomite (Khibina: δ13C(V-PDB)=−6.4 to−5.8‰, δ18O(V-SMOW)=7.3–7.7‰, (87Sr/86Sr)370=0.70390–0.70404 and (143Nd/144Nd)370=0.51230–0.51235; Vuoriyarvi: δ13C=−4.2 to −3.0‰, δ18O=8.1–9.4‰, (87Sr/86Sr)370=0.70313–0.70315 and (143Nd/144Nd)370=0.51243–0.51245). This indicates that the REE mineralization and its host carbonatites in each complex are derived from the same source and are co-genetic. There is, however, a great difference between the Sr, Nd and C isotopic signatures from Khibina and Vuoriyarvi, whereas the δ18O ranges are similar. This suggests that the REE carbonatites of the two complexes originate from sources with different isotopic signatures. At least three mantle components are needed to explain the variations in Sr and Nd compositions in the carbonatites from Kola. The δ13C ranges of primary carbonatites with low δ18O values are quite different for Khibina and Vuoriyarvi and show correlation with the radiogenic isotope compositions. The data may be best explained by subduction-related source contamination that caused δ13C variations in different mantle components. During late-stage processes burbankite and calcioburbankite have been replaced by various assemblages of REE–Sr–Ba minerals. The alteration of burbankite group minerals is an open-system hydrothermal process leading to multiple element transfer. It has produced mineral assemblages which are characterized by high δ18O values (Khibina: δ18O(V-SMOW)=11.4–13.9‰ and Vuoriyarvi: δ18O=17.1–18.0‰) compared to primary burbankite and calcioburbankite. Co-existing calcite and dolomite have retained their original C and O isotope compositions, and one calcite sample from Khibina shows strong positive δ13C–δ18O shifts similar to those of the pseudomorph. The high δ18O and sometimes high δ13C values can be attributed to low-temperature isotope exchange between minerals and fluid with variable CO2/H2O ratio taking place during and/or after crystallization as usually observed in carbonatites. The Sr and Nd isotope compositions of pseudomorphs and associated calcite/dolomite in general are identical to those of burbankite/calcioburbankite and associated carbonates suggesting that the fluids which caused burbankite alteration are from the same source, i.e. carbonatitic. Small variations in the Sr and Nd isotope signatures point to interaction of the pseudomorph-forming fluid with alkali silicate wall rocks.

Differential REE uptake by sector growth of monazite

Abstract Monazite-(Ce) from a dolomite carbonatite at Kangankunde, Malawi, is sector-zoned with variation in La2O3 of up to 6.0 wt.% and in Nd2O3 of up to 3.9 wt.% between sectors. Single crystal X-ray diffraction, backscattered electron imaging and microprobe analysis have been used to establish the relationship between the morphology and sector chemistry of this low-Th monazite, (Ce,La,Nd)PO4. Uptake of La by {011} sector surfaces is enhanced relative to that of {1̅01} and {100} sectors; Ce shows no partitioning differences; and uptake of Nd is more easily facilitated on {1̅01} and {100} surfaces relative to {011}. There appears to be a distinct relationship between the size of the REE ion and the probability of uptake via the different growth surfaces. Interpretation of this uptake behaviour, based on theories involving ‘protosites’, involves an investigation of the possible kink site geometries at edge-steps during growth. Part-formed kink sites with small entrance sizes are calculated to occur with higher frequency on {1̅01} relative to {011}, and this correlates with an increase in the smaller- sized REE (Nd) uptake by {1̅01} growth surfaces. The overall morphology and sector growth is suggested to be a function of uptake chemistry.

Compositional variation in pyrochlore from the Bingo carbonatite, Zaïre

Abstract The composition of pyrochlore from the calcite carbonatite and its associated laterite at Bingo, Zaire was determined and compared with pyrochlore from the nearby and geologically-similar carbonatite at Lueshe. Large compositional variations exist in the Bingo pyrochlore which relate both to primary magmatic zonation and, more commonly, a secondary alteration process. Altered pyrochlore is rich in Ba and Si. At Lueshe an identical primary magmatic trend is observed, but secondary alteration is subordinate. Pyrochlore from the Bingo laterite is bariopyrochlore, whereas at Lueshe the predominant variety is kalipyrochlore.

Aragonite in olivine from Calatrava, Spain—Evidence for mantle carbonatite melts from >100 km depth

Aragonite, as an inclusion in olivine from a leucitite lava flow, provides evidence for high-pressure crystallization and carbonatitic activity beneath the geophysical lithosphere in Calatrava, Spain. The aragonite occurs as a single crystal within olivine (Fo 87 ), interpreted to have crystallized from a carbonated silicate melt at mantle depths. Experimental data constrain the stability of aragonite to depths of >100 km at CO 2 -H 2 O-bearing mantle solidus temperatures. This is the first documented evidence of magmatic aragonite crystallized in the mantle. Entrained as xenocrysts, the olivines have not crystallized from the carrier melts, which must have formed deeper within the mantle. Lead isotope data of the leucitite and carbonate inclusions indicate that the source melts show isotopic enrichment relative to mid-oceanic ridge basalt and most ocean island basalt. Our evidence strengthens the argument for direct and deep mantle-derived volcanic carbonatite in alkaline volcanic provinces containing maar-type volcanism, such as Calatrava.

Compositional variation in the chevkinite group: new data from igneous and metamorphic rocks

Abstract Electron microprobe analyses are presented of chevkinite-group minerals from Canada, USA, Guatemala, Norway, Scotland, Italy and India. The host rocks are metacarbonates, alkaline and subalkaline granitoids, quartz-bearing pegmatites, carbonatite and an inferred K-rich tuff. The analyses extend slightly the range of compositions in the chevkinite group, e.g. the most MgO-rich phases yet recorded, and we report two further examples where La is the dominant cation in the A site. Patchily-zoned crystals from Virginia and Guatemala contain both perrierite and chevkinite compositions. The new and published analyses are used to review compositional variation in minerals of the perrierite subgroup, which can form in a wide range of host rock compositions and over a substantial pressure-temperature range. The dominant substitutions in the various cation sites and a generalized substitution scheme are described.

Evidence for dissolution-reprecipitation of apatite and preferential LREE mobility in carbonatite-derived late-stage hydrothermal processes

Abstract 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. The changing REE distribution in the apatite, from early to late in the paragenetic sequence, is interpreted to be caused by a combination of dissolution-reprecipitation of the original apatite and the preferential transport of the LREE complexes by F- and Cl-bearing hydrothermal fluids. Successive pulses of these fluids transport the LREE out of the original apatite, preferentially re-precipitating it on the rim. Some LREE remained in solution, precipitating later in the paragenetic sequence, as synchysite-(Ce). The presence of F is supported by the F content of the apatites, and presence of REE-fuorcarbonates. Cl is not detected in the apatite structure, but the role of Cl is suggested from comparison with apatite dissolution experiments, where CaCl2 or NaCl cause the reprecipitation of apatite without associated monazite. This study implies that, despite the typically LREE enriched nature of carbonatites, significant degrees of hydrothermal alteration can lead to certain phases becoming residually enriched in the HREE. Although at Tundulu the LREE-bearing products are re-precipitated relatively close to the REE source, it is possible that extensive hydrothermal activity in other carbonatite complexes could lead to significant, late-stage fractionation of the REE and the formation of HREE minerals.

A review of the potential for rare earth element resources from European red muds: examples from Seydişehir, Turkey and Parnassus-Giona, Greece

Abstract Rare-earth elements (REE) are viewed as ‘critical metals’ due to a complex array of production and political issues, most notably a near monopoly in supply from China. Red mud, the waste product of the Bayer process that produces alumina from bauxite, represents a potential secondary resource of REE. Karst bauxite deposits represent the ideal source material for REE-enriched red mud as the conditions during formation of the bauxite allow for the retention of REE. The REE pass through the Bayer Process and are concentrated in the waste material. Millions of tonnes of red mud are currently stockpiled in onshore storage facilities across Europe, representing a potential REE resource. Red mud from two case study sites, one in Greece and the other in Turkey, has been found to contain an average of ~1000 ppm total REE, with an enrichment of light over heavy REE. Although this is relatively low grade when compared with typical primary REE deposits (Mountain Pass and Mount Weld up to 80,000 ppm), it is of interest because of the large volumes available, the cost benefits of reprocessing waste, and the low proportion of contained radioactive elements. This work shows that ~12,000 tonnes of REE exist in resources existing across Europe as a whole.

The Rare Earth Elements: Demand, Global Resources, and Challenges for Resourcing Future Generations

AbstractThe rare earth elements (REE) have attracted much attention in recent years, being viewed as critical metals because of China’s domination of their supply chain. This is despite the fact that REE enrichments are known to exist in a wide range of settings, and have been the subject of much recent exploration. Although the REE are often referred to as a single group, in practice each individual element has a specific set of end-uses, and so demand varies between them. Future demand growth to 2026 is likely to be mainly linked to the use of NdFeB magnets, particularly in hybrid and electric vehicles and wind turbines, and in erbium-doped glass fiber for communications. Supply of lanthanum and cerium is forecast to exceed demand. There are several different types of natural (primary) REE resources, including those formed by high-temperature geological processes (carbonatites, alkaline rocks, vein and skarn deposits) and those formed by low-temperature processes (placers, laterites, bauxites and ion-adsorption clays). In this paper, we consider the balance of the individual REE in each deposit type and how that matches demand, and look at some of the issues associated with developing these deposits. This assessment and overview indicate that while each type of REE deposit has different advantages and disadvantages, light rare earth-enriched ion adsorption types appear to have the best match to future REE needs. Production of REE as by-products from, for example, bauxite or phosphate, is potentially the most rapid way to produce additional REE. There are still significant technical and economic challenges to be overcome to create substantial REE supply chains outside China.