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Apatite is an excellent tracer of petrogenetic processes as it can incorporate a large range of elements that are sensitive to melt evolution (LREE-MREE, Sr, Pb, Mn, halogens, Nd isotopes). Recent advances in the understanding of trace element concentrations and isotope ratios in apatite provide a novel tool to investigate magmatic petrogenesis and sediment provenance. Recent experimental work has better characterized trace element partition coefficients for apatite, which are sensitive to changes in magma composition (e.g., SiO2 and the aluminum saturation index value). The chemistry of apatites from granitoids has been suggested to reflect the composition of the host magma and yield information about petrogenetic processes that are invisible at the whole-rock scale (mixing, in situ crystal fractionation, metasomatism). Nd isotopes in apatite can now be analyzed by LA-MC-ICP-MS to constrain mantle and crustal contributions to the source(s) of the studied magma. These recent advances highlight exciting new horizons to understand igneous processes using accessory minerals. In this contribution, we use a compilation of recent data to show that apatite in the matrix and as inclusions within zircon and titanite is useful for providing insights into the nature and petrogenesis of the parental magma. Trace element modeling from in situ analyses of apatite and titanite can reliably estimate the original magma composition, using appropriate partition coefficients and careful imaging. This provides a new way to look at magmatic petrogenesis that have been overprinted by metamorphic processes. It also provides the rationale for new investigations of sedimentary provenance using detrital accessory minerals, and could provide a powerful new window into early Earth processes if applied to Archean or Hadean samples.

The 2060 Ma old Palabora Carbonatite Complex (PCC), South Africa, comprises diverse REE mineral assemblages formed during different stages and reflects an outstanding instance to understand the evolution of a carbonatite-related REE mineralization from orthomagmatic to late-magmatic stages and their secondary post-magmatic overprint. The 10 rare earth element minerals monazite, REE-F-carbonates (bastnasite, parisite, synchysite), ancylite, britholite, cordylite, fergusonite, REE-Ti-betafite, and anzaite are texturally described and related to the evolutionary stages of the PCC. The identification of the latter five REE minerals during this study represents their first described occurrences in the PCC as well as in a carbonatite complex in South Africa.The variable REE mineral assemblages reflect a multi-stage origin: (1) fergusonite and REE-Ti-betafite occur as inclusions in primary magnetite. Bastnasite is enclosed in primary calcite and dolomite. These three REE minerals are interpreted as orthomagmatic crystallization products. (2) The most common REE minerals are monazite replacing primary apatite, and britholite texturally related to the serpentinization of forsterite or the replacement of forsterite by chondrodite. Textural relationships suggest that these two REE-minerals precipitated from internally derived late-magmatic to hydrothermal fluids. Their presence seems to be locally controlled by favorable chemical conditions (e.g., presence of precursor minerals that contributed the necessary anions and/or cations for their formation). (3) Late-stage (post-magmatic) REE minerals include ancylite and cordylite replacing primary magmatic REE-Sr-carbonates, anzaite associated with the dissolution of ilmenite, and secondary REE-F-carbonates. The formation of these post-magmatic REE minerals depends on the local availability of a fluid, whose composition is at least partly controlled by the dissolution of primary minerals (e.g., REE-fluorocarbonates).This multi-stage REE mineralization reflects the interplay of magmatic differentiation, destabilization of early magmatic minerals during subsequent evolutionary stages of the carbonatitic system, and late-stage fluid-induced remobilization and re-/precipitation of precursor REE minerals. Based on our findings, the Palabora Carbonatite Complex experienced at least two successive stages of intense fluid-rock interaction.

Tapiolite [FeTa2O6] and columbite-group minerals [(Fe,Mn)(Ta,Nb)2O6] are common Nb-Ta-bearing accessory minerals in rare-element granites and pegmatites. Their compositional gap has inspired several experimental studies, but none of them have succeeded in reproducing the parameters that influence the compositional gap. In this study, tapiolite and columbite-group minerals (CGM) were crystallized from water-saturated, flux-rich granitic melts at various conditions of pressure, temperature, oxygen fugacity, and Ti contents. Crystals with a size as small as 500 nm were analyzed with a field emission gun (FEG) electron microprobe. The results show that temperature, pressure, and Ti content only slightly affect the compositional gaps between tapiolite and CGM, whereas high fO2 leads to complete solid solution between a rutile-structured component Fe3+TaO4 and (Fe,Mn)Ta2O6. The experimental CGM-tapiolite compositional gaps are compared with natural CGM-tapiolite pairs from rare-element granites and pegmatites worldwide. This study reveals that the crystallographic structure of tapiolite and CGM could be the dominant parameter that influences the position of the compositional gap. Order-disorder in CGM and tapiolite is tightly linked to disequilibrium crystallization triggered by supersaturation. Significant isothermal Nb-Ta fractionation is observed inside CGM crystals that grow at high degrees of supersaturation. The effect of supersaturation prevails over the solubility effect that is known to increase the Ta/(Ta+Nb) ratio in CGM and coexisting melts. Thus, even if global equilibrium in terms of the solubility of Nb-Ta-bearing minerals is attained, the Ta/(Nb+Ta) ratio in the crystals may differ significantly from equilibrium. It implies that Nb-Ta fractionation in Nb-Ta oxides is controlled by crystallization kinetics rather than equilibrium chemical fractionation (or any other processes such as F-complexing of Ta or fluid exsolution) in dynamic systems that can rapidly reach supersaturated conditions. These results have important implications for the understanding of crystallization processes in highly evolved and pegmatite-forming magmas.

The Mangodara district (southwestern of Burkina Faso, West African Craton) consists of a regional-scale Eburnean dome cored by granitoid-gneisses comprising rafts of migmatitic paragneisses and amphibolites of the Paleoproterozoic Birimian series. The occurrence of rare metal-bearing pegmatites in diffuse contact with these migmatitic and granitoid gneisses suggests that they originated from the segregation of a residual melt of these partially molten hosts. In this paper, we constrain the petrogenetic link between pegmatites and their hosts, and the mechanisms of rare metal fractionation in Lithium-Cesium-Tantalum (LCT) vs Niobium-Yttrium-Fluorine (NYF) petrogenetic signatures by the geochemistry of micas, apatite, columbite-group minerals, garnet, and zircon. Titanite-allanite pegmatites (containing titanite, allanite, epidote, zircon, and apatite as accessory minerals) and their evolved equivalent, apatite-zircon pegmatites (richer in apatite, lower K/Rb and Fe/Mn ratio in biotite but Li-depleted) are poorly mineralized metaluminous pegmatites. They display a continuous evolution trend in K/Rb and Fe/Mn in biotite and similar REE patterns in apatite, which favor an origin by segregation of residual melt within tonalitic-trondhjemitic gneiss in the core of the Mangodara dome. Garnet-columbite pegmatites containing REE-bearing phosphates and Zr-U-Th-bearing metamict minerals are mixed LCT + NYF pegmatites. Their micas, slightly enriched in Li, LREE-rich apatite, and Nb–Ta-U-rich garnet, are consistent with an origin by partial melting of a metasedimentary source, with dehydration of biotite (reservoir of Li, Rb, Nb) and dissolution of apatite-monazite (reservoir of REE). Apatite crystals in one garnet-columbite pegmatite reveal an inherited REE signature typical of apatite-zircon pegmatite, which suggests mingling of a LCT pegmatite-forming melt with the residual melt derived from crystallization of metaluminous pegmatites. Garnet-REE pegmatites, containing ilmenite-pyrophanite and euxenite-aeschynite), are NYF pegmatites that should originate from melt segregation within granodioritic gneiss associated with breakdown/entrainment of amphibole (reservoir of REE, Y) and LREE segregation by allanite and phosphates in the source. These data show that the LCT vs NYF signature of pegmatites of the Mangodara district results primarily from the chemical composition of the partially-molten source and the minerals involved in the partial melting reactions, which vary as a function of increasing depth (mica, phosphate, amphibole, garnet). The trace-element signature of anatectic peraluminous pegmatite-forming melt might then be affected by mingling with residual Nb-enriched metaluminous melt.

Accessory minerals contain a robust and accessible record of magma evolution. However, they may reflect relatively late-stage conditions in the history of the host magmas. In the normally zoned Criffell granitic pluton (Scotland), whole-rock (WR) compositions reflect open system assimilation and fractional crystallisation at depths of >11 km, whereas amphibole barometry and the absence of inherited zircon suggest that the observed mineral assemblages crystallised following emplacement of magmas with little or no crystal cargo at depths of 4–6 km. The crystallisation history is documented by large trace-element variations amongst apatite crystals from within individual samples: decreasing LREE and Th concentrations in apatite crystals from metaluminous samples reflect broadly synchronous crystallisation of allanite, whereas lower LREE and Th, and more negative Nd anomalies in apatites from peraluminous samples reflect the effects of monazite crystallisation. WR evolution is likely to have occurred within a deep crustal hot zone where H 2 O-rich (~6 wt%), low-viscosity magmas segregated and ascended adiabatically in a super-liquidus state, leading to resorption of most entrained crystals. Stalling, emplacement and crystallisation resulted from intersection with the H 2 O-saturated liquidus at ~4 km. H 2 O contents are as important as temperature in the development of super-liquidus magmas during ascent, blurring distinctions between apparently ‘hot’ and ‘cold’ granites. The trace-element contents of most accessory minerals are controlled by competitive crystallisation of other accessory minerals in small melt batches, consistent with the incremental assembly of large granitic plutons.

Monazite, a common accessory rare-earth orthophosphate mineral in the continental crust widely used in U-Pb geochronology, holds promise for (U-Th)/He thermochronology and for the immobilization of Pu and minor actinides (MA) coming from spent nuclear fuel reprocessing. Previous results obtained on natural and plutonium-doped monazite have demonstrated the ability of this structure to maintain a crystalline state despite high radiation damage levels. However, the low critical temperature (180 °C), above which amorphization cannot be achieved in natural monazite under ion irradiation, does not explain this old and unsolved paradox: why do natural monazites, independent of their geological history, remain crystalline even when they did not experience any thermal event that could heal the defects? This is what the present study aims to address. Synthetic polycrystals of LaPO4-monazite were irradiated sequentially and simultaneously with α particles (He) and gold (Au) ions. Our results demonstrate experimentally for the first time in monazite, the existence of the defect recovery mechanism, called α-healing, acting in this structure due to electronic energy loss of α particles, which explains the absence of amorphization in natural monazite samples. This mechanism is critically important for monazite geo- and thermochronology and to design and predictively model the long-term behavior of ceramic matrices for nuclear waste conditioning.

Circumstantial evidence for the sources of uranium in ore deposits may be drawn from the study of deposit geochemistry and mineralogy. However, direct evidence supporting uranium leaching from source rocks has rarely been found. This study investigates the source of uranium in the Baiyanghe deposit in the Xiemisitai Mountains, northwest China. The main uranium ore bodies occur as fracture-fillings along contact zones between the Yangzhuang granite porphyry and the Devonian volcanic rocks. Zircon, thorite, columbite-(Mn), and bastnäsite are the dominant accessory minerals that host uranium in the granite porphyry. In situ columbite-(Mn) LA-ICP-MS U-Pb dating yields a weighted mean Pb/ U age of 310 ± 4 Ma, suggesting that the Yangzhuang granite porphyry was emplaced during the Late Carboniferous. Backscattered electron (BSE) images reveal that various degrees of alteration of these same accessory minerals may be observed in the granite porphyry, and the altered domains of these minerals have lower BSE intensities compared to the unaltered domains. Results indicate that the altered domains of zircon grains have lower concentrations of Zr, Si, and U, and higher concentrations of Y, Fe, Ca, and P relative to the unaltered domains, and the altered domains of columbite-(Mn) grains are enriched in Ti and Fe and are depleted in Nb, Ta, Mn, U, and Zr. The altered domains of thorite grains have higher concentrations of Zr, Fe, Ca, Nb, and P, and lower Th and U compared to those of the relict domains. The petrochemical data indicate that the granite porphyry experienced losses in U, Be, F, Ba, Sr, Pb, Zr, Mo, Nb, Ta, and Hf during alteration. These results suggest that the past-magmatic hydrothermal fluids might be responsible for the mobilization of uranium form minerals in the granite porphyry. It is concluded that U-bearing accessory minerals in the granite porphyry were the primary source of uranium, and that post-magmatic hydrothermal processes caused remobilization and significant localized enrichment of the uranium to form high-grade ores as fracture-fillings along its contacts.

Translating burial and exhumation histories from the petrological and geochronological record of high-pressure assemblages in subduction channels is key to understanding subduction channel processes. Convective return flow, either serpentinite or sediment hosted, has been suggested as a potential mechanism to retrieve rocks from significant depths and exhume them. Numerical modelling predicts that during convective flow, subducted material can be cycled within a serpentinite-filled subduction channel. Geochronological and petrological evidences for such cycling during subduction are preserved in lawsonite eclogite from serpentinite melange in the Southern New England Orogen, eastern Australia. Ar–Ar, Rb–Sr phengite and U–Pb titanite geochronology, supported by phase equilibrium forward modelling and mineral zoning, suggest Cambro–Ordovician eclogite underwent two stages of burial separated by a stage of partial exhumation. The initial subduction of the eclogite at ca. 490 Ma formed porphyroblastic prograde-zoned garnet and lawsonite at approximate P–T conditions of at least 2.9 GPa and 600 °C. Partial exhumation to at least 2.0 GPa and 500 °C is recorded by garnet dissolution. Reburial of the eclogite resulted in growth of new Mg-rich garnet rims, growth of new prograde-zoned phengite and recrystallization of titanite at P–T conditions of approximately 2.7 GPa and 590 °C. U–Pb titanite, and Ar–Ar and Rb–Sr phengite ages constrain the timing of reburial to ca. 450 Ma. This was followed by a second exhumation event at approximately 1.9 GPa and 520 °C. These conditions fall along a cold approximate geotherm of 230 °C/GPa. The inferred changes in pressure suggest the lawsonite eclogite underwent depth cycling within the subduction channel. Geochronological data indicate that partial exhumation and reburial occurred over ca. 50 M y., providing some estimation on the timescales of material convective cycling in the subduction channel.

The Singhbhum Shear Zone in eastern India hosts several Fe oxide–Cu–Au (IOCG)-type polymetallic deposits, mined primarily for U, Cu and apatite, with elevated concentrations of rare earth elements, Ni, Co, Mo, Te and Au in association with low-Ti magnetite. Although the main stages of hydrothermal U, Cu and rare earth element mineralization are known to be Palaeoproterozoic in age, the age of shear deformation in the host shear zone has hitherto not been constrained. Here, we report Re–Os ages of syn-shearing massive molybdenite occurring along shear surfaces transecting the uranium ores in the Jaduguda uranium deposit. Integrating the obtained Re–Os age of c. 1.64–1.59 Ga of molybdenite, the known ages of mineralization and the known tectonothermal events in the adjoining Proterozoic Mobile Belt, we propose that the main stages of polymetallic hydrothermal mineralization pre-dated the pervasive shear deformation event in the Singhbhum Shear Zone. We further suggest that the shear zone was not the principal foci of the hydrothermal mineralization of the main stages. Instead, the shear zone was localized during the Palaeoproterozoic to Mesoproterozoic transition (c. 1.64–1.59 Ga) along pre-existing crustal-scale extensional faults which had earlier been the foci of hydrothermal alteration and mineralization in Palaeoproterozoic time (c. 1.9–1.8 Ga). Shear deformation and metamorphism have reconstituted/redistributed existing mineral/metal inventories with/without neo-mineralization.