The hot spring water discharging from a flank of an active volcano is precipitating unique monomineralic manganese deposits over volcanic terrain. The major and trace element chemistry, XRD mineralogy, DTA, and SEM observations indicate that the deposits consist of 10 Å phyllomanganate (buserite) accommodating inter-layer Ca and Mg with negligible amounts of detrital minerals. Other metallic elements can be accommodated by buserite, but concentrations are negligible ranging less than 10 ppm to 500 ppm. Abundance and pattern of REE (less than 100 ppm in total) are similar to those from hydrothermal manganese deposits. The buserite is enriched in Ca and Mg but depleted in Na in comparison with those in the spring water. The distribution coefficients for Ca, Mg and Na between the buserite and the host water were calculated assuming an ion-exchange equilibrium in the Yuno-Taki Fails, which proved applicable to other manganese deposits from surficial environments on land and oceans.

Ce/Al- and La/Al-pillared smectites were prepared by cation exchange of bentonite, saponite and laponite with hydrothermally treated (130–160 °C for 16–136 h) solutions containing mixtures of aluminumchlorohydrate (ACH) and Ce3+-/and La3+-salts. After calcination at 500 °C, the pillared products are characterized by basal spacings between 24.8 and 25.7 Å and surface areas of approximately 430 m2 g−1. The products are hydrothermally stable at 500 °C after 2 h in steam. The large basal spacings are due to the formation of a large Ce/La-bearing Al-polyoxocation, whose formation is favored by initially high Al concentrations ≥3.7 M and an OH/Al molar ratio of approximately 2.5. The Ce/Al or La/Al molar ratios can be as low as 1/30. 27Al nuclear magnetic resonance (NMR) spectroscopy has shown that the polyoxocation has a higher Altetrahedral/Aloctahedral ratio than the Keggin structure Al13, which may partly explain the higher stability compared to normal Al-pillared clays. Hydroconversion of n-heptane indicated that the activity of the Pt-loaded pillared products is higher than that of a conventional Pt-loaded amorphous silica-alumina catalyst. Selectivity is strongly dependent on the type of starting clay and its acidity. In industrial hydrocracking of normal feedstock, a Ni/W-loaded Ce/Al-pillared bentonite catalyst showed rapid deactivation due to coke-formation reducing the surface area and the pore volume. Additionally, coke-formation is facilitated by the relatively high iron content of the pillared bentonite (3.43 wt% Fe2O3).

Clay-rich deposits of Upper Cretaceous levels in the Taveiro (Reveles and S. Pedro) and Aveiro (Bustos) regions of west-central Portugal are economically and environmentally important, but detailed chemical and mineralogical characterization is lacking. The purpose of this study was to partially fill that gap by correlating the trace-element geochemistry (particularly the rare earth elements, REE) with the mineralogy of both the whole rock and of the <2 μm fraction along selected stratigraphic levels of the formations. The results will help the ceramics industry in the region and will be important in paleoreconstruction environmental studies.

Mineralogical and chemical characterizations were carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), and instrumental neutron activation analysis (INAA). The following clay-mineral associations were identified: (1) at Reveles — smectite, illite, and kaolin minerals; (2) at S. Pedro — kaolin minerals and illite; and (3) at Bustos — illite, kaolin minerals, and mixed-layer illite-smectite. The distribution of trace elements in the <2 μm fraction depended on the clay mineralogy, suggesting that the trace elements were incorporated in, adsorbed to, or even replaced major elements in the clays, as follows: (1) first-row transition elements, particularly Zn and Ga, were enriched when smectite predominated; (2) As, Rb, and Cs were enriched in this fraction of the S. Pedro deposit, the only one with Fe (oxyhydr)oxides and a high proportion of illite; and (3) REE were more concentrated when kaolin minerals predominated. Eu was enriched in the <2 μm fraction, which was due to preferential incorporation in the Fe (oxyhydr)oxides and/or carbonates.

Talc deposits, located mainly in three areas of north-central Turkey, are present in the ophiolitic series of the Cretaceous and in siliciclastic rocks of the Paleocene. Talc deposits related to ophiolites are between tectonite and cumulate occurring as beds and/or lenses and 0.1–3 cm thick fracture fillings within a 5 m brecciated zone with a vein-type bedding. Sedimentary-hosted talc beds and semi-rounded to angular talc grains (0.1–2 cm) range in thickness from 0.1 to 30 cm within marls and conglomerates. Talc veins form lenses (a few meters long) and spheroidal and/or ellipsoidal nodules (1–10 cm). Calcite, dolomite, serpentine and/or mixed-layered illite-smectite (I-S) minerals are encountered in the talc samples. Serpentine with positive U and Hf anomalies, and talc with positive Nb and Zr anomalies, and negative Ta and Ce anomalies are typically depleted in P and Ti, based on chondrite-normalized trace element patterns. The light rare earth element content of sedimentary-hosted talc with a negative Gd anomaly is richer than those of ultramafic-hosted talc with a negative anomaly for Eu as well as serpentine. Significantly, talc with a uniquely sedimentary origin tends to be the principal source of Nb, Hf, Zr, La, Ce, Pr and Nd with respect to serpentine. δ18O and δD values for talc range from +13.8 to +17.5‰ and −60 to −36‰, and those of serpentine are +9.4 and −88‰, indicating supergene conditions for sedimentary-hosted talc and hypogene for ultramafic-hosted talc. When compared with seawater, δ18O data indicate temperatures of 68°C and 80–98°C for the sedimentary- and ultramafic-hosted talc formations, respectively, and 100°C for serpentine, suggesting that talcification and serpentinization of ultramafic rocks both occurred at nearly the same time with various stages. All data show that the talc occurrences are divided into two types based on their mode of formation. The first corresponds to a serpentinization stage within the ophiolites. The others are the neoformation products of sedimentary deposition, diagenetic and post-diagenetic processes, respectively. Sedimentary-hosted talc also seems to have inherited trace element and isotopic compositions from the parent ultramafic rocks.

Large kaolin deposits developed by weathering on Precambrian granitic rocks have been discovered in the Caluquembe area, Huíla province, Angola. To determine accuracy of analysis and to evaluate the kaolinite grade, a full-profile Rietveld refinement by X-ray Powder Diffraction (XRPD) and Thermal Gravimetric Analysis (TGA) was used. Caluquembe kaolin is composed mainly of kaolinite (44–93 wt.%), quartz (0–23 wt.%), and feldspar (4–14 wt.%). The Aparicio-Galán-Ferrell index (AGFI), calculated by XRPD profile refinement, indicates low- and medium-defect kaolinite. Kaolinite particles show a platy habit and they stack together forming ‘booklets’ or radial aggregates; they also occur as small anhedral particles in a finer-grained mass. Muscovite-kaolinite intergrowths have also been found. Whole-rock chemical analysis included major, trace, and Rare Earth Elements (REE). Chondrite-normalized REE patterns show the same tendency for all samples, with a significant enrichment in Light Rare Earth Elements (LREE). Mineralogical and compositional features of the Caluquembe kaolin indicate that it is a suitable material for the manufacture of structural products, such as bricks, paving stones, and roofing tiles. In addition, the significant REE contents of the Caluquembe kaolin can be considered as a potential future target of mining exploration.

The Eocene-Oligocene Transition at c. 34 million years ago (Ma) marked the global change from greenhouse to icehouse and the establishment of the East Antarctic Ice Sheet (EAIS). How the ice-sheet behaviour changed during interglacials across this climate transition is poorly understood. We analysed major, trace and rare earth elemental data of late Eocene interglacial mudstone from Prydz Bay at Ocean Drilling Program Site 1166 and early Oligocene interglacial mudstone from Integrated Ocean Drilling Program Site U1360 on the Wilkes Land continental shelf. Both sites have comparable glaciomarine depositional settings. Lithofacies and provenance at Site 1166 in Prydz Bay are indicative of a late Eocene glacial retreat in the Lambert Graben. Palaeoclimate proxies, including the Chemical Index of Alteration, mean annual temperature and mean annual precipitation, show a dominant warm and humid palaeoclimate for the late Eocene interglacial. In contrast, at Site U1360, in the early Oligocene, the provenance and interglacial weathering regime remained relatively stable with conditions of physical weathering. These results confirm that the EAIS substantially retreated periodically during late Eocene interglacials and that subglacial basins probably remained partially glaciated during interglacials in the earliest Oligocene.

To ascertain weathering, provenance, and paleoclimate of the last ca. 29 ka in mainland Gujarat, western India, a sedimentary profile of ~7.5 m was measured, described, and sampled at Pratappura and a multiproxy analysis was conducted. To determine weathering, silty-sand and sandy-silt facies were analyzed, and log Na2O/K2O versus log SiO2/Al2O3 was plotted, which shows clustering in the quartz arenite and sub-litharenite categories, indicating low to moderate weathering. The chemical index of alteration (CIA) is 55–74, and was plotted versus the index of chemical variability (ICV) of 1.50, with samples clustered mainly between subalkali basalt and picrite, indicating the dominance of a mafic component. While depleted chondrite normalized light rare earth element (REE) (La/Yb <1) levels suggest the prevalence of a mafic source in the catchment, identical chondrite normalized REE patterns indicate that sediments were well homogenized. Using multiple proxies, the measured profile was subdivided into five paleoclimatic zones. Zone-I (29–18 ka) exhibits decreasing moisture, Corg, χlf, Al2O3, TiO2, and Fe2O3 trends, while higher values of CO3−2 and δ13C indicate a change from a warm-humid to semiarid climate. Zone-II (18–11 ka) shows signs of the beginning of aridity ca. 18 ka during the Last Glacial Maximum (LGM). Several proxies in zone-III show wetter climatic conditions from the early Holocene (ca. 11–4 ka) due to the onset of the SW monsoon, with the trend continuing in zone-IV (4–2 ka). In zone-V, the climate appears to have been similar to the modern conditions in the area from 2 ka–present.

Bridgesite-(Ce), (IMA2019-034), was discovered at Tynebottom Mine, Cumbria, UK. It occurs as thin (1–2 μm) translucent blue crystals with a lath-like to acicular habit, aggregated into thin crusts and is associated mainly with brochantite, malachite, serpierite, devilline, gypsum, aragonite, jarosite, pyrite, lanthanite-(Ce) and undifferentiated iron oxyhydroxides, it is often intergrown with these other minerals. The lustre, hardness, cleavage and parting could not be determined, nor could density be measured due to crystal size. It has a pale blue streak and is brittle with a splintery fracture. Bridgesite-(Ce) is biaxial (–), shows no pleochroism and has refractive indices (white light): α = 1.526(2), β = 1.564(2), γ = 1.572(2) and 2V(calc) = 48.3°. The empirical formula calculated on the basis of 44 negative charges is Ca0.86REEΣ1.99Al0.07Cu5.95(SO4)3.99(SiO4)0.05(PO4)0.02(OH)11.52⋅8H2O. The idealised formula is CaCe2Cu6(SO4)4(OH)12⋅8H2O, requiring (wt.%): 3.91 CaO, 22.89 Ce2O3, 33.28 CuO, 22.33 SO3 and 17.59 H2O. Bridgesite-(Ce) is monoclinic, space group C2/m, a = 24.801(5), b = 6.3520(13), c = 11.245(2) Å, β = 114.51(3)°, V = 1611.9(6) Å and Z = 2. The five most intense X-ray diffraction peaks in the measured pattern are [d in Å (I, %) (hkl)]: 11.3 (100) (200), 6.391 (15) (201), 2.770 (8) (420), 3.194 (6) (402) and 4.858 (5) (310). The crystal structure was solved using single crystal data and refined to an R1 index of 5.86%. Bridgesite-(Ce) contains three distinct Cu sites containing Cu2+, two are coordinated octahedrally and one is square pyramidal. The octahedra form chains through edge sharing parallel to the b-axis which are linked by the square pyramid to form sheets oriented parallel to {100}. Sulfate tetrahedra decorate the sheets which are held together by interstitial REE3+, Ca2+ and hydrogen bonding. The structure is unique. Despite apparent similarity in chemical formula, bridgesite-(Ce) is not closely related to any other natural Cu-sulfate mineral. An FTIR absorption spectra is presented for reference purposes.

This paper reports a novel approach in the study of trace-element mobility during the argillization of volcanic glass that is based on in situ laser ablation inductively coupled plasma mass spectrometry glass analyses and that of spatially related illite-smectite collected in the form of fraction separates. The material studied originates from lacustrine sediments of the Dinaride Lake System that bear evidence of intensive weathering of distal tephra during the Miocene climatic optimum. Yttrium and HREE were probably mobilized from decomposing glass in the form of carbonate complexes and were consequently depleted significantly in the clays studied. On the other hand, the Mg-rich illite-smectite demonstrates an elevated adsorption potential of solvated LREE complexes. This may be explained through clay surface geochemistry controlled largely by Mg for Al octahedral substitution. This paper highlights the role of eogenetic 2:1 clay aluminosilicates that, under favourable geological conditions, may be conducive to secondary REE enrichment and the formation of potential ion adsorption-type deposits.

We used a multidisciplinary approach integrating major, trace and rare earth element geochemistry, mineralogy of rocks and sediments along with the ionic composition of water reservoirs of Admiralty Bay, King George Island, to evaluate the record of water-rock interactions under Maritime Antarctic conditions. Our results showed that the ionic compositions of the streams and meltwaters predominantly reflect the atmospheric inputs, while lake waters have higher Na/Cl, Ca/Mg and HCO3/Cl ratios related to chemical weathering in lake sediments, but this did not allow for distinguishing purely silicate sources. Consistent with the trace and rare earth element data, various alteration indices and Index of Compositional Variability values denote the low degree of chemical weathering in the lake sediments. The records from the previously unexplored Mud Lake and Upper Lake suggest that the lakes of Admiralty Bay are better places to trace the impacts of a succession of environmental changes that have occurred in the watershed, while the stream channel sediments, when accompanied by water chemistry data, may provide a more representative composition of the source rocks than the lake sediments. These findings may help revealing the intensity of contemporary weathering in a colder climate with relatively few mineralogical changes accompanied by a lesser degree of elemental loss.

A nomenclature scheme has been set up for the nordite supergroup of minerals, which have the general formula A2BXYZT6O17 and where A = Na; B = Na, Ca; X = Sr, Ca, Ba; Y = REE, Sr; Z = Zn, Fe, Mn, Mg and T = Si. The nordite supergroup includes nordite-(La), nordite-(Ce), ferronordite-(La), ferronordite-(Ce) and manganonordite-(Ce), as well as meieranite which is considered as an unassigned member of the nordite supergroup. In the known nordite-group minerals the Y site is occupied by rare earth elements (REE), while in meieranite the Y site is occupied by Sr. The dominant element on the tetrahedral Z site determines the prefix used in the mineral name. New rootnames must be given to species with a different dominant element on the A, B or X sites. Nordite supergroup minerals are orthorhombic, although nordite-group minerals and meieranite crystallise in the Pcca and P21nb space groups, respectively. The proposed nomenclature scheme for the nordite supergroup has been approved by the Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association (IMA). In addition, new chemical and structural investigations were performed on nordite-(Ce) from Illutalik (Igdlutalik), South Greenland, leading to the first crystal structure refinement for nordite-(Ce).

At present, a significant portion of rare-earth elements (REEs) are sourced from weathering profiles. The mineralogy of the protolith plays an important role in controlling the fate of REEs during weathering, as accessory minerals contain the bulk the REE budget in most rocks, and different minerals vary in their susceptibilities to weathering processes. REE supergene deposits (‘adsorption clay deposits’) are associated with deep weathering in tropical environments, which often precludes characterisation of the incipient steps in REE liberation from their host minerals in the protolith. Here we have targeted a weathered REE-enriched lithology from a sub-arid environment undergoing relatively rapid uplift, namely the Yerila Gneiss from the Northern Flinders Ranges, Australia, where regolith was shallow or absent and parent rock material had yet to completely break down. Results from X-ray fluorescence mapping, scanning electron microscopy (SEM), SEM-focussed ion beam milling (FIB-SEM), inductively-coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS highlight the migration pathways of REEs and associated U and Th from allanite-(Ce) grains that are the main REE host within Yerila Gneiss material. Migration of light REEs and Th away from the allanite-(Ce) grains via radial cracks resulting from allanite-(Ce) metamictisation was interpreted to result from weathering, as Ce is partially present in its tetravalent oxidation state and Th mobility is most easily explained by the involvement of organic ligands. FIB-SEM provides further evidence for the importance of biogenic processes in REE+U/Th mobility and fractionation in uranothorite-associated spheroidal structures associated with the weathering of allanite-(Ce). Organic carbon was also found in association with a xenotime-(Y) grain; in this case, REE liberation is most likely a by-product of biogenic phosphate utilisation. These results highlight that local controls (at mineral interfaces) mediated by biota and/or biogenic organic matter can control the initiation of REE (+Th,U) mobilisation during weathering.

The mineralogy and geochemistry of the clay fraction of Victoria Land Basin (Ross Sea, Antarctica) sediments was investigated, to determine the origin of clay minerals and the features of authigenic smectite. The investigated core (CRP-3) is ~800 m long, mostly of Oligocene age. The clay fraction of the upper sequence consists of mica, chlorite and detrital smectite, while that of the central and lower part is largely made up of authigenic smectite. Authigenic smectites are ditrioctahedral, with a composition close to saponite, while detrital smectites such as Al-Fe beidellites are dioctahedral. Authigenic smectites have no illite mixed layers, show a higher degree of crystallization, higher MgO, Fe2O3, V, Cr, Co, Ni and Sc contents and lower SiO2, Al2O3, K2O, TiO2, Ba, Rb and Zr contents with respect to detrital clay minerals, and a clear depletion of LREE with respect to HREE. Authigenic smectite formed from the alteration of volcanic materials and clay minerals.

A detailed electron microprobe (EMP) and laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) study of zircon from six types of miaskitic and agpaitic alkaline pegmatite from the Larvik Plutonic Complex, Oslo rift valley, Norway, was undertaken to shed light on the pegmatite petrogenesis. Detailed rare earth element (REE) analyses indicate important differences between the zircon from each type of pegmatite. Primary zircon from miaskitic Stavern-, Tvedalen- and Stålaker-type pegmatites has a mean ΣREE = 704 ppm, is depleted in LREE and has a significant positive Ce anomaly (Ce/Ce* = 44–67) and negative Eu anomaly (Eu/Eu* = 0.15–0.18). Secondary Tvedalen-type zircon is REE-enriched (ΣREE = 5035 ppm), with a flatter REE pattern, Ce/Ce* = 0.97 and a Eu anomaly similar to primary Tvedalen-type zircon (Eu/Eu* = 0.21). Secondary zircon from agpaitic Langesundsfjord-type pegmatites display a distinctive flat REE pattern characterized by overall REE enrichment (ΣREE = 967), Ce/Ce* = 1.92, and a minor negative Eu anomaly (Eu/Eu* = 0.37). Zircon from agpaitic Bratthagen-type pegmatites occurs as both altered primary and secondary phases and is strongly enriched in REE relative to other zircon (ΣREE = 4178 and 8388, respectively). Primary Bratthagen-type zircon has a similar REE pattern to miaskitic zircon, with a steeper HREE profile and smaller Ce and Eu anomalies (Eu/Eu* = 0.73; Ce/Ce* = 6.22). Secondary Bratthagen-type zircon is strongly enriched in LREE compared to primary zircon, does not display a positive Ce anomaly and has Eu/Eu* = 0.56. The altered primary and secondary Bratthagen-type zircons have elevated Th/UN ratios, suggesting a different melt source for Bratthagen-type agpaitic pegmatites. Zircon from external pegmatites has trace-element signatures similar to Stavern-, Tvedalen- and Staålaker-type primary zircon with Ce/Ce* = 214 and Nb/Ta and Th/U ratios that are similar to those of secondary Langesundsfjord- and Bratthagen-type zircon. It is suggested that the parental melt of the external pegmatites is the same as the miaskitic pegmatites, but that it has undergone alteration by hydrothermal fluids derived from the host basalt, or by post-magmatic F-rich fluids which mobilize Nb and Th. On the basis of texture, morphology and geochemistry, two populations of zircon can be recognized: (1) primary zircon from miaskitic pegmatites; and (2) secondary zircon from post-magmatic, hydrothermal assemblages. The U–Th–Pb isotope analyses indicate that the secondary and altered zircon are depleted in 238U, and enriched in LREE. Interaction of a post-magmatic hydrothermal fluid with an externally derived meteoric fluid is suggested to have influenced the REE signatures, and in particular the Eu and Ce anomalies of the late-stage zircons.

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.

New data on rare earth element (REE) concentrations and distribution patterns of columbite-tantalite minerals from Ta-ore provinces worldwide are presented. The REE geochemistry was studied by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Five major types of chondrite-normalized REE distribution patterns are defined for columbite-group minerals (CGM) from lithium-caesium-tantalum (LCT) pegmatites and rare-metal granites. Features to discriminate between the types include (1) the shape of the pattern (e.g. flat or concave), (2) calculated ratios between groups of the REE (e.g. heavy REEN/middle REEN), and (3) the presence and intensity of anomalies (e.g. Ce*, Eu*). Four pegmatites in central and southern Africa are used as case studies to discuss application of the types of REE patterns in individual deposits. The REE fractionation during progressive evolution of the melt in a pegmatite body (either Nb → Ta or Fe → Mn fractionation lines, or both) results in smaller heavy REEN/middle REEN ratios whereas replacement of primary CGM by secondary CGM produces modifications in the light REEN patterns and the heavy REEN/middle REEN ratios also. Critical features of REE patterns such as highly variable heavy REEN/middle REEN ratios or striking differences in the appearance of Eu anomalies are discussed considering structural data of the host minerals and the differentiation behaviour of the pegmatitic melt. In general, CGM from each individual Ta-ore province are characterized by a predominance of one type of REE distribution pattern. Consequently, these patterns are suitable for tracing the origin of tantalum ore concentrates (e.g. as a forensic tool).

The formation of crystalline rare earth element (REE) (e.g. La, Ce, Pr, Nd) carbonates from aqueous solutions was examined at ambient temperature using UV-Vis spectrophotometry, combined with X-ray diffraction, high-resolution microscopy and infrared spectroscopy. In all experiments REE-lanthanites (REE2(CO3)3·8H2O) formed via a highly hydrated, nanoparticulate and poorlyordered REE-carbonate precursor. The lifetime of this precursor as well as the kinetics of crystallization of the various REE-lanthanites were dependent on the specific REE3+ ion involved in the reaction. The induction time and the time needed to fully form the crystalline REE-lanthanite end products increase linearly with the ionic potential. The authors show here that the differences in ion size and ionic potential as well as differences in dehydration energy of the REE3+ ions control the lifetime of the poorly ordered precursor and thus also the crystallization kinetics of the REE-lanthanites; furthermore, they also affect the structural characteristics (e.g. unit-cell dimensions and idiomorphism) of the final crystalline lanthanites.

Relative concentrations of elements in the minerals of fine-grained sediments can be inferred from element-mineral correlation coefficients. The technique is applied to the distribution of REE in Middle Ordovician shales from South Wales analysed by ICPAES, Leco C/S125 and XRD. Phosphate and chlorite show mid-REE enrichment; muscovite + biotite shows mid-REE depletion. The complementarity of the chlorite and muscovite + biotite patterns may be due to fractionation during diagenetic recrystallisation. Partial correlation analysis is used to infer the presence of zircon.

The Virulundo carbonatite in Angola is one of the largest in the world and contains pyrochlore as an accessory mineral in all of the carbonatite units (calciocarbonatites, ferrocarbonatites, carbonatite breccias and trachytoids). The primary magmatic pyrochlore is fluorine dominant and typically contains about equal molar quantities of Ca and Na at the A site. High-temperature hydrothermal processes have resulted in the pseudomorphic replacement of the primary pyrochlore by a second generation of pyrochlore with less F and Na. Low-temperature hydrothermal replacement of the first and second generation pyrochlore, associated with quartz-carbonate-fluorite vein formation in the carbonatite, has produced a third generation of pyrochlore, with a high Sr content. The Sr appears to have been released by low-temperature hydrothermal replacement of the primary magmatic carbonates. Finally, supergene alteration processes have produced late-stage carbonates, goethite, hollandite and rare earth element (REE) minerals (mainly synchysite-(Ce), britholite-(Ce), britholite-(La), cerite-(Ce)). Cerium separated from the other REE s in oxidizing conditions and Ce4+ was incorporated into a late generation of supergene pyrochlore, which is strongly enriched in Ba and strongly depleted in Ca and Na.