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Title: Targeting heavy rare earth elements in carbonatite complexes
Author: Broom-Fendley, Sam Louis
ISNI:       0000 0004 5365 0795
Awarding Body: University of Exeter
Current Institution: University of Exeter
Date of Award: 2015
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The HREE are generally considered to be the most critical of the REE, indispensable for many high-tech applications such as smart-phones and electric vehicles. Currently, carbonatites are the main source of REE due to their high REE grade; most carbonatites, however, are HREE-poor. This thesis presents the findings on HREE mineralisation at the Songwe Hill carbonatite, in the CAP of south-eastern Malawi. Across all carbonatite types at Songwe, whole-rock Y and P2O5 concentrations correlate positively, indicating that phosphate minerals have a strong control over the HREE contents. This is confirmed through textural and geochemical analyses (LA ICP-MS and EPMA) of apatite, which show that it can be subdivided into 5 different types (Ap-0–4), found at different stages of the paragenetic sequence. The chemistry of each of these apatite types becomes progressively more HREE-enriched, up to 3 wt. % Y2O3, and ultimately culminating in xenotime crystallisation. Cross-cutting relationships indicate that HREE-enriched apatite formed as an early crystallisation product from a late-stage, carbonatite-derived hydrothermal fluid. It is evident that LREE-fluorcarbonate mineralisation occurred after apatite crystallisation and it is assumed that crystallisation of all hydrothermal phases was though the evolution of a single fluid, rather than several different fluids. The apatite composition is compared to a compilation of analyses of apatite from other carbonatites and granitoids, as well as new analyses of late-stage apatite from the Kangankunde and Tundulu carbonatites, Malawi. Based on these analyses, it is concluded that apatite from Songwe has the highest HREE concentration compared to apatite from any previously analysed carbonatite. However, apatite from the Tundulu carbonatite has a similar geochemistry and paragenesis to the HREE-rich apatite from Songwe, suggesting that late-stage HREE enrichment may be a common process in carbonatites. In order to elucidate the fluid conditions which led to HREE mineralisation, new fluid inclusion and stable isotope data are presented to complement the mineralogical data. The fluid inclusions constrain the minimum temperature of apatite crystallisation of 160 °C, and most homogenisation temperatures in apatite are between 160-360 °C. Inclusions from apatite are CO2-rich, and it is suggested that transport of the REE occurred in carbonate complexes. Stable isotope data were obtained from both conventional C and O analyses of carbonates and from a novel method developed for acquiring δ18OPO4 from apatite. A conceptual model involving the simultaneous cooling and mixing of magmatically-derived and meteoric fluids is suggested. Two possible causes of REE fractionation are suggested: (1) a crystal-chemical control and (2) control through preferential stability of LREE and HREE complexes. However, neither mechanism is equivocal and further work on the stability of carbonate complexes is suggested in order to better understand REE mineralisation at carbonatites In addition to results on the HREE mineralisation in carbonatites, new data on the mineralogy, geochemistr y and age of the Songwe Hill carbonatite and the closely-associated Mauze nepheline syenite intr usion are presented. Songwe compr ises three stages of intr usion (C1–3): (C1) sovitic calcite carbonatite, (C2) alvikitic calcite-carbonatite and (C3) Fe-rich carbonatite. The LREE grade increases with the increasing Fe-content of the intrusion, as is common at many REE-rich carbonatites. Later-stages of the intrusion include apatite-fluorite veins (C4) and Mn-Fe-veins. The former is a volumetrically minor stage, but can contain up to 1 wt. % Y2O3, and the latter is formed through oxidation of carbonatite by supergene fluids. Samples analysed from Mauze show that it is REE- and P2O5-poor, with MREE-depleted REE distributions. U-Pb dating of zircons from Songwe and Mauze show that they are 131.5 ± 1.3 and 133.1 ± 2.0 Ma, respectively. The close temporal association of each intrusion suggests that Mauze could be a ‘heat-engine’ for hydrothermal mineralisation at Songwe.
Supervisor: Wall, Frances Sponsor: NERC
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available