The total concentrations of rare-earth elements (REE) in the mined kaolin (0.02–0.06 wt.%), kaolin mine tailings (0.03–1.9 wt.%), and the kaolin-associated Marion Member sand lithology (0.03–4.6 wt.%) opened questions regarding the modes of occurrence of the REE and the role(s) of chemical weathering and secondary processes to explain the presence of REE in these materials. The REE were hosted primarily by phosphate minerals (monazite, xenotime) based on mineralogic analyses (scanning electron microscopy, X-ray diffraction). Enrichments in the light rare-earth elements (LREE: La–Gd) and the high correlation coefficient values were noted between P and the total REE concentrations (r2 = 0.99) for the sands and the mine tailings. Lower correlation coefficient values were noted between total REE concentrations and Zr (r2 = 0.31). The coarse fractions of the mined kaolins were enriched in the heavy rare-earth elements (HREE: Y, Tb–Lu) relative to the kaolin-associated sand lithologies. The REE inventory cannot be explained solely by mineral inheritance within the mined kaolins. Lower correlation coefficient values between P and total REE, positive Eu/Eu* anomalies, and the presence of xenotime overgrowths on zircon showed the importance of the role of chemical weathering of the detrital minerals during post-depositional processes (such as diagenesis) leading to redistributed and fractionated REE within the mined kaolin. The possibility of adsorption of the REE to kaolin mineral surfaces in the fine fraction of the mined kaolins remains open and permits further study to characterize fully the multi-modal fractionation of REE possible in the Georgia kaolin deposits.

The crystal chemistry and crystal structure of the rare earth element phosphates, monazite-(Ce), Ce(PO4), and xenotime-(Y), Y(PO4), as well as the arsenates, gasparite-(Ce), Ce(AsO4), and chernovite-(Y), Y(AsO4), from the hydrothermal quartz-bearing fissures, related to pegmatites overprinted by amphibolite facies, cropping out at Mt. Cervandone, Western Alps, Piedmont, Italy, have been investigated by means of electron microprobe analysis in wavelength dispersion mode and single-crystal X-ray diffraction. The chemical data reveal the occurrence of a full solid solution among the isostructural chernovite-(Y) and xenotime-(Y) with tetragonal symmetry, whereas a wide miscibility gap is observed for the isostructural gasparite-(Ce) and monazite-(Ce) of Mt. Cervandone, with monoclinic symmetry. A significant chemical heterogeneity has been observed for several investigated samples, especially related to the Th content, which is locally enriched in ThSiO4 grains. The analysis of the refined structural models demonstrates the significant control played by the composition of the tetrahedrally-coordinated (As,P)-bearing sites on the bulk unit-cell volume, and on the size and shape of the (REE)-coordination polyhedra.

A geochemical and mineralogical study has allowed us to address the factors controlling distribution pattern, residence and behaviour of rare earth elements (REE) during kaolinization of Variscan granitoids in NW Spain. Mineral composition of the deeply weathered samples is dominated by kaolinite, with minor amounts of quartz, muscovite-illite, alkaline feldspar and traces of resistant minerals (rutile, ilmenite, zircon and monazite). Variable amounts of Si, Na, Ca, K, Rb, Cs, Ba, U and P were lost from the weathering profile, as a result of feldspars, mica and apatite breakdown, whereas Al, Fe, Ti, Zr, Th, Hf and REE were concentrated in the residual kaolin. Chondrite-normalized REE patterns of the kaolins show an overall enrichment of light REE (LaN/SmN = 1.22–2.53), heavy REE depletion (GdN/YbN = 2.42–15.10) and a strong negative Eu anomaly (Eu/Eu* = 0.11–0.25), probably inherited from the parent granite. Nevertheless, the normalization to the parent granite reveals some REE fractionation and increasing positive Eu anomalies with advancing weathering, in response to the breakdown of feldspars. Different grain-size fractions show similar REE distribution patterns, but differ in concentration levels. Although the fine fractions are the most important REE reservoir, there is no positive correlation with clay mineralogy. The correlative behaviour among P2O5, Th and REE in the <2 mm fraction suggests that monazite plays a dominant role controlling the REE budget in the weathering profile.

Monazite is a light rare-earth element (LREE)-bearing accessory phase common in felsic granitic rocks, and strongly influences LREE concentrations in granites and the chemistry of melts and residues formed during partial melting. Cheralite-rich (high-Th) monazite-(Ce) has been recorded as rims on partially dissolved cores in a suite of granulite-facies migmatites generated by disequilibrium melting. High-Th monazite has previously been recorded only in granitic-pegmatite occurrences. Subidiomorphic monazite-(Ce) from leucosome, melanosome and mesosome consists of complexly zoned cores (up to 300 µm in diameter) containing 5.17–9.87 wt.% ThO2, overgrown by essentially unzoned rims (containing up to 21.4 wt.% ThO2). Uranium contents are average for Th-rich monazite-(Ce) (0.22–3.17 wt.% UO2). Th enrichment (relative to LREE) in monazite-(Ce) rims is ascribed to the presence of fluorine-bearing melts (formed during the incongruent breakdown of biotite to produce a water-undersaturated melt), allowing the formation of REE-fluoride complexes in the melt, coupled with the increased charge balanced substitutions Th4+ + Si4+ ⇌ REE3+ + P5+ and Th4+ + Ca2+ ⇌ 2REE3+ into monazite-(Ce). Fractionation of Th and U (reflected by an increased in Th/U in rims relative to cores) may have occurred due to the removal by a CO2-rich fluid phase in the melt. These interpretations are consistent with elevated CO2 and F contents of granitic liquids produced during the water-undersaturated breakdown of biotite under granulite-facies conditions. Evidence for restricted monazite-(Ce)-melt equilibration and rapid melt removal is provided by the ubiquitous presence of partially embayed cores and unzoned rims.

Combined microfocus XAS and XRD analysis of α-particle radiation damage haloes around thorium-containing monazite in Fe-rich biotite reveals changes in both short- and long-range order. The total α-particles flux derived from the Th and U in the monazite over 1.8 Ga was 0.022 α particles per atomic component of the monazite and this caused increasing amounts of structural damage as the monazite emitter is approached. Short-range order disruption revealed by Fe K-edge EXAFS is manifest by a high variability in Fe–Fe bond lengths and a marked decrease in coordination number. XANES examination of the Fe K-edge shows a decrease in energy of the main absorption by up to 1 eV, revealing reduction of the Fe3+ components of the biotite by interaction with the 24He2+, the result of low and thermal energy electrons produced by the cascade of electron collisions. Changes in d spacings in the XRD patterns reveal the development of polycrystallinity and new domains of damaged biotite structure with evidence of displaced atoms due to ionization interactions and nuclear collisions. The damage in biotite is considered to have been facilitated by destruction of OH groups by radiolysis and the development of Frenkel pairs causing an increase in the trioctahedral layer distances and contraction within the trioctahedral layers. The large amount of radiation damage close to the monazite can be explained by examining the electronic stopping flux.

The Carnmenellis pluton is a post-orogenic granite of Hercynian age, comprised largely of porphyritic biotite granites which possess LREE enriched patterns with slight negative Eu anomalies. Electron microprobe and ICP spectrometry data are presented for monazite, which occurs as an accessory mineral in all granite types, and it is demonstrated that this mineral is the principal host for LREE in the biotite granites. HREE are strongly partitioned into the accessory minerals xenotime, apatite, and zircon; only Eu substitutes significantly into the essential minerals. The behaviour of the REE during granite differentiation is controlled by the behaviour of the radioactive accessory minerals, which limits the usefulness of these elements in the petrogenetic modelling of granitic rocks.

Electron backscatter diffraction (EBSD) analysis of monazite requires a comparison of empirically collected electron backscatter patterns (EBSPs) with theoretical diffraction data, or ‘match units’, derived from known crystallographic parameters. Published crystallographic data derived from compositionally varying natural and synthetic monazite are used to calculate ten different match units for monazite. These match units are used to systematically index EBSPs obtained from four natural monazite samples with different compositions. Analyses of EBSD data, derived from the indexing of five and six diffraction bands using each of the ten match units for 10,000 EBSPs from each of the four samples, indicate a large variation in the ability of the different match units to correctly index the different natural samples. However, the use of match units derived from either synthetic Gd or Eu monazite crystallographic data yield good results for three of the four analysed monazites. Comparison of sample composition with published monazite compositions indicates that these match units are likely to yield good results for the EBSD analysis of metamorphic monazite. The results provide a clear strategy for optimizing the acquisition and analysis of EBSD data from monazite but also indicate the need for the collection of new crystallographic structure data and the subsequent generation of more appropriate match units for natural monazite.

The structure of the high-temperature form of CaSeO4, formed by dehydration of the gyspum-type structure dihydrate is presented. The material is equivalent to that described previously as a P212121 form, but is however, a monazite with unit cell a = 6.85661(16) Å, b = 7.04962(15) Å, c = 6.68817(15) Å and β = 104.2675(21)° in space group P121/n1. Also presented is evidence for two intermediate trigonal and pseudo-trigonal phases related to the structurally similar minerals rhabdophane, bassanite, and γ-CaSO4. This result permits closer comparisons between intermediate-temperature structures of the selenate with related sulphates, and orthophosphates with a view to extending structural stability via synthesis of solid-solutions.

Five rare earth-bearing minerals found in rocks of the Chilwa Alkaline Province, Malawi, are described. Zirconolite, occurring in nepheline syenite, is unusual in being optically zoned, and microprobe analyses indicate a correlation of this zoning with variations in Si, Ca, Sr, Th, U, Fe, Nb and probably water; it is argued that this zoning is a hydration effect. A second compositional zoning pattern, neither detectable optically nor affected by the hydration, is indicated by variations in Th, Ce and Y such that, although total REE abundances are similar throughout, there appears to have been REE fractionation during zirconolite growth from relatively heavy-REE and Th-enrichment in crystal cores to light-REE enrichment in crystal rims.

Chevkinite is an abundant mineral in the large granite quartz syenite complexes of Zomba and Mulanje, and analyses are given of chevkinites from these localities. There is little variation in composition within each complex, and only slight differences between them; they are all typically light-REE-enriched. The Mulanje material was shown by X-ray diffraction to be chevkinite and not the dimorph perrierite, but chemical arguments are used in considering the Zomba material to be the same species. Other rare earth minerals identified are monazite, fluocerite and bastnäsite. These are briefly described and microprobe analyses presented.

The crystal-chemical relationships occurring within a single grain of monazite-(Ce) from Vetralla, Vico Volcanic Complex, north of Rome, are outlined. The sample is from a miarolitic cavity in a holocrystalline ejectum consisting of K-feldspar plus minor plagioclase, mica and Fe-oxides, collected from a pyroclastic explosive level. The Gandolfi film (Cu-Kα radiation) can be indexed in space group P21/n with a = 6.816(4); b = 6.976(4); c = 6.471(3) Å; β = 103.63(3)°; V = 299.0(6) Å3. Electron-probe microanalyses plot within the field of monazite along the huttonite-monazite edge of the huttonite-monazite-brabantite triangle. Despite patchy and irregular zoning, the grain shows a clear enrichment towards pure monazite at the outer rim. A constant Th:Si ratio of 1:1 indicates the existence of a simple solid-solution between huttonite and monazite. The substitution can be written as Th4+ + Si4+ → REE3+ + P5+ without requiring any electrostatic compensation by divalent cations, or by anionic groups. The REE distribution pattern is compatible with that of monazites from syenitic rocks.

In order to better understand the formation and evolution processes of ultrahigh pressure (UHP) felsic rocks, we determined the ages of various domains of zircon and monazite crystals from the diamondiferous quartzofeldspathic rocks of the Saxonian Erzgebirge. According to cathodoluminescence imagery and Th/U ratios, three zircon zones were distinguished. Each was dated using several spot analyses from a sensitive high-resolution ion microprobe analysing Pb, U and Th isotopes. The results were: (1) core zone – 21 analyses: Th/U ≤ 40.023 and 337.0±2.7 Ma (2σ, combined 206Pb/238U-207Pb/235U age); (2) diamond-bearing intermediate zone – 23 analyses: Th/U ≥ 50.037 and 336.8±2.8 Ma; and (3) rim zone – 12 analyses: Th/U = 0.015–0.038 (plus one analysis of 0.164) and 330.2±5.8 Ma. The U-Pb obtained ages are virtually concordant. Furthermore, two oscillatory zoned zircon cores (Th/U ≥ 50.8) yielded (~concordant) ages of ~400 Ma. Six SHRIMP analyses of monazites gave an age of 332.4±2.1 Ma. In addition, Pb, Th and U contents in monazite were analysed with an electron microprobe (EMP). A mean age of 324.7±8.0 (2σ) Ma was acquired from 113 analyses.

By combining the defined ages with previously published P-T conditions, minimum velocities for burial and exhumation were estimated. In addition, we present a likely geodynamic scenario involving age data from the literature as well as this study: beginning 340 million years ago, gneisses at the base of a thickened continentalcrust (~1.8 GPa, 650ºC) were transported to depths of at least 130 km, possibly as deep as 250 km. Here they were heated (>1050ºC) and partially melted and as a result began to rise rapidly. The burial and subsequent ascent back to a depth of 50 km, where zircon rims and monazite formed, took only a few million years and perhaps significantly less.

Rare earth minerals in ankeritic ferrocar-bonatite and associated magnetite ore, as well as in hematite-calcite-(dolomite) carbonatite (rødberg) derived from the ferrocarbonatite by post-magmatic alteration, have been studied by electron microprobe. The minerals found are monazite, parisite, and bastnäsite (identifications confirmed by X-ray diffraction) as well as an aluminous silicate with allanite composition, and possibly, synchysite. The rare earth element (REE) distribution patterns of the minerals change from light rare earth (LREE)-enriched in magnetite ore and ferrocarbonatite to less LREE-enriched, or middle REE-enriched in the most strongly re-equilibrated carbonatites. Two distinct mineral varieties, monazite-(Ce,Nd) and a Nd-fluorocarbonate, have been found in rødberg. The LREE were leached from their host minerals during re-equilibration of the carbonatite, most likely because of the influence of fluoride-bearing hydrothermal solutions.

The effects of ion irradiation in the ABO4-type compounds were compared by performing experiments on four materials that include the most common crystal structures (monazite vs. zircon) and chemical compositions (phosphates vs. silicates) for these phases. Pure synthetic single crystals of ZrSiO4, monoclinic ThSiO4, LaPO4 and ScPO4 were irradiated using 800 keV Kr+ ions. Radiation damage accumulation was monitored as a function of temperature in situ in a transmission electron microscope. The activation energies for recrystallization during irradiation were calculated to be 3.1–3.3 eV for the orthosilicates but only 1.0–1.5 eV for the isostructural orthophosphates. For the ion-beam-irradiated samples, the critical temperature, above which the recrystallization processes are faster than damage accumulation and amorphization cannot be induced, is >700°C for ZrSiO4 but it is only 35°C for LaPO4. At temperatures above 600°C, zircon decomposed during irradiation into its component oxides (i.e. crystalline ZrO2 plus amorphous SiO2). The data are evaluated with respect to the proposed use of the orthophosphates and orthosilicates as host materials for the stabilization and disposal of high-level nuclear waste. The results show that zircon with 10 wt.% Pu would have to be maintained at temperatures in excess of 300°C in order to prevent it from becoming completely amorphous. In contrast, a similar analysis for the orthophosphates implies that monazite-based waste forms would not become amorphous or undergo a phase decomposition.

Millimetric, ellipsoidal monazite nodules found within Lower Palaeozoic sedimentary rocks in Wales, south-west England and Brittany are characterised by a pronounced zonation of light and heavy REE, an inclusion fabric of low-grade metamorphic minerals indistinguishable from the host rock and a low Th content. They are interpreted as the product of in situ recrystallization of detrital monazites derived from pegmatitic or granitic source rocks and are potentially useful as indicators of Lower Palaeozoic sedimentary rock provenance.

Composite populations of monazite-group minerals of both metamorphic and metasomatic origin have been discovered in thin layers of granulite-facies metabasites interlayered with metapelites, located in the Val Strona di Omegna region of the Ivrea-Verbano Zone, Italy. In addition to monazite-(Ce), which is uncommonly poor in Th and is probably formed by incongruent dissolution of apatite, these populations include members of the monazite-huttonite series. The latter minerals contain between 13 and 30.1 mol.% ThSiO4 [= huttonitic monazite-(Ce)], and are known from only half a dozen other occurrences worldwide. We propose that breakdown of primary monazite-(Ce) in the metapelites during granulite-facies metamorphism mobilized Th and the REEs, which were then transported by high-grade metamorphic fluids into the metabasite layers to form the Th-rich minerals of the monazite-huttonite series.

Oriented inclusions of monazite occur in the dark core of apatite porphyroblasts in a muscovite schist from the Archaean Hemlo gold deposit, Ontario, Canada. The monazite inclusions are elongated along the b-axis and parallel to the c-axis of the apatite host; the complete orientation relationship of the monazite/apatite intergrowth is bMnz//cAp, cMnz//aAp. From analysis by SIMS and EMP, the dark core of the apatite porphyroblasts is depleted in LREE (LaN/YbN = 0.56). The monazite inclusions are correspondingly enriched in LREE, but markedly depleted in HREE, compared with monazite grains in the rock matrix and cross-cutting veins. The monazite inclusions precipitated by oriented reaction through rock-fluid interactions during a late hydrothermal alteration. Their unusual REE composition is probably related to both a preferential leaching of LREE from the dark core and a selective transfer of HREE out of the apatite porphyroblasts.

The high-pressure monazite – scheelite structure transition has been observed at P >4.57 GPa in CaSeO4 by synchrotron X-ray powder diffraction. It is a first-order transition with a 4.5% volume change and is severely hindered kinetically. Scheelite-type CaSeO4 remains to a maximum experimental pressure of 42.2 GPa and no (002) reflection, specifically indicative of a subgroup transition to a fergusonite-type structure, is observed. Scheelite-type CaSeO4 remains at ambient conditions, where the tetragonal unit cell has parameters of a = 5.04801(11) c = 11.6644(5) Å and V = 297.21(3) Å3 with Dcalc = 4.090 g cm–3. The diffraction pattern of the recovered material was refined in space group I41/a to Rp = 0.98%, wRp = 1.91%, GoF = 0.59, RFobs = 5.04%, wRFobs = 4.27%. The oxygen is located on the general 16f site at (0.2578(8) 0.3699(14) 0.5755(4)) and shares four identical bonds with Se (4a: ½ ½ ½) at 1.644(5) Å. The Ca (4b: 0, 0, ½) is eight-coordinated via O at 4 × 2.440(6) Å and 4 × 2.504(5) Å. This is further evidence of the dissimilarity of sulfate and selenate at high pressure and temperature conditions and the closer resemblance of the selenates to the orthophosphates, arsenates and vanadates, where this type of transition sequence has been described.

Materials designed for nuclear waste disposal include a range of ceramics, glass ceramics and glass waste forms. Those with crystalline phases have provided the momentum for studies of minerals as a means to understand aspects of waste-form crystal chemistry, behaviour in aqueous systems and radiation damage over geological periods of time. Although the utility of natural analogue studies varies, depending upon the degree of analogy to the proposed geological repository and other factors such as chemical composition, the available data suggest that Th-U host phases such as brannerite, monazite, pyrochlore, zircon and zirconolite are resistant generally to dissolution in aqueous fluids at low temperatures. Geochemical durability may or may not extend to hydrothermal systems depending on the specifics of fluid composition, temperature and pressure. At elevated temperatures, for example, davidite may break down to new phase assemblages including titanite, ilmenite and rutile. Perovskite is generally less resistant to dissolution at low temperatures and breaks down to TiO2, releasing A-site cations to the aqueous fluid. Studies of radiation damage indicate that the oxide and silicate phases become amorphous as a result of the gradual accumulation of alpha-recoil collision cascades. Monazite tends to remain crystalline on geological time scales, a very attractive property that potentially eliminates major changes in physical properties such as density and volume, thereby reducing the potential for cracking, which is a major concern for zircon. In spite of recent success in describing the behaviour of Th-U minerals in geological systems, considerable work remains in order to understand the P-T-X conditions during alteration and T-t history of the host rocks.

Electron microprobe analysis (EMPA) and microscopic investigations were performed on monazite grains from the black sand deposits of northern Sinai beach. Electron microprobe backscattered electron images, X-ray mapping and wavelength dispersive spectroscopy line scans showed some grains with sector zoning and others with thorite inclusions. Based on the EMPA data, the studied monazite is grouped into monazite-(Ce) and Th-rich monazite. Monazite-(Ce) is enriched in REE and P, whereas Th-rich monazite is enriched in Th, U, Ca, Y, Si and Fe. The compositional variations of monazite are governed by the substitution of REE by Th, U, Ca and Y. The monazite grains show enriched chondrite-normalized REE patterns represented mainly by LREE and only Gd from the HREE. These patterns demonstrate negative Nd and Euanomalies. The floods associated with the pluvial periods which prevailed in Egypt during the Pleistocene, were able to erode the source rocks and liberate heavy minerals including monazite. The mineral grains were transported through several wadis and tributaries to the main channel of the River Nile. At the confluence sites, these heavy minerals were mixed with Ethiopian and central African heavy mineral assemblages. The grains continued to move together downriver until being deposited in their current locations. The analytical results suggest that pegmatites and granites of the Eastern Desert are the most likely source of the monazite. However, due to the large area of the Nile watershed, other undiscovered sources are possible.

The synthesis of monazite was first reported by Radominsky (1875). Since then various methods have been used to synthesize various end members of the monazite solid solution series, mainly CePO4 and LaPO4 (e.g. Anthony, 1957, 1965). As part of an experimental study dealing with the solubility of monazite in granitic melts (Montel, 1986, 1987, and in prep.), the synthesis of some of the end members, as well as solid solutions, was achieved.