Xenotime-(Gd), ideally GdPO4, is a new mineral of the xenotime group. It was discovered at the Zimná Voda REE–U–Au occurrence near Prakovce, Western Carpathians, Slovakia. It forms rare crystal domains (≤20 μm, usually ≤10 μm in size) in Gd-rich xenotime-(Y) crystals (≤100 μm in size), in association with monazite-group minerals, uraninite, fluorapatite and uranyl arsenates–phosphates. The hydrothermal REE–U–Au mineralisation occurs in a quartz–muscovite vein, hosted in Palaeozoic phyllites near exocontact with Permian granites. The density is 5.26 g/cm3, based on calculated average empirical formula and unit-cell parameters. The average chemical composition (n = 6) measured by electron microprobe is as follows (wt.%): P2O5 30.1, As2O5 0.5, SiO2 0.2, UO2 0.3, Y2O3 15.7, (La, Ce, Pr, Nd)2O3 0.5, Sm2O3 5.7, Eu2O3 1.4, Gd2O3 29.2, Tb2O3 3.9, Dy2O3 10.4, Ho2O3 0.4, (Er, Tm, Yb, Lu)2O3 2.1, (Ca, Fe, Pb, Mn, Ba)O 0.1, total 100.5. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.37Y0.32Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Tm0.01Nd0.01…)Σ1.01(P0.98As0.01Si0.01)O4. The empirical formula of the Gd-richest composition is: (Gd0.38Y0.31Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Nd0.01Ho0.01…)Σ1.01(P0.98As0.01Si0.01)O4. The ideal formula is GdPO4. The xenotime-type structure has been confirmed by micro-Raman spectroscopy and a Fast Fourier-Transform pattern using HRTEM. Xenotime-(Gd) is tetragonal, space group I41/amd, a = 6.9589(5) Å, c = 6.0518(6) Å, V = 293.07(3) Å3 and Z = 4. The new mineral is named as an analogue of xenotime-(Y) and xenotime-(Yb) with Gd dominant among the REE. The middle REE enrichment of xenotime-(Gd) is shared with the associated monazite-(Gd) and Gd-rich hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing minerals is a product of selective complexing and enrichment in MREE in low-temperature hydrothermal fluids by alteration of uraninite, brannerite and fluorapatite on a micro-scale. The existence of xenotime-(Gd) and monazite-(Gd) is the first naturally documented dimorphism among REE phosphates. In addition, xenotime-(Gd) is only the third approved Gd-dominant mineral, after lepersonnite-(Gd) and monazite-(Gd).

During an electron microscope study of the weathering of granite from southern New South Wales, Australia, an assemblage of minerals including florencite and rhabdophane was discovered replacing apatite. Light rare earth elements released from allanite early in weathering apparently combined with P released by leaching of primary apatite to form secondary phases exhibiting a range of morphologies and compositions. Chondrite normalized fractionation patterns La > Nd > Sm > Ce; La > Ce > Nd ≥ Sm and La = Sm = Nd > Ce were identified. The rare earth elements were present in very small crystals and aggregates of secondary minerals (< 10 μm) and coexisted with clays and secondary Fe-Ti oxides. The weathered granite was enriched about 6 to 10 times in all rare earth elements except Ce relative to fresh granite if the abundances were corrected for apparent enrichment due to reduction in density. The rare earth elements were probably derived from higher in the weathering profile, possibly by destruction of florencite and rhabdophane in very intensively weathered rock. Ce remained relatively immobile during weathering, probably due to its oxidation to Ce4+.

Reaction of hydroxy-Al oligocations with Ce3+- and La3+-exchanged montmorillonites, using 1.25, 1.60, or 2.0 mmole Al/g smectite, yielded partially pillared hydroxy-Al montmorillonite products containing a significant concentration of residual Ce3+ or La3+. After heat treatment at 250°C these products showed high surface areas (∼340–500 m2/g) and high basal X-ray powder diffraction spacings (18.0–18.6 Å). Calcination at 400°–700°C resulted in lower surface areas of ∼200–450 m2/g and basal spacings of 16.3–18.3 Å, the values showing a gradual decrease with a decrease in the Al/smectite weight ratio and/or increase in the heat-treatment temperature. A major modification and improvement in the cross-linking procedure was achieved by fast aging (6–48 hr) of the hydroxy-Al oligomeric solution at 95°–100°C, instead of conventional aging for 2–3 weeks at 25°C.

Fluorinated NH4+-montmorillonites, containing 0.4 to 2.1 wt. % F, were prepared by reaction of NH4+-montmorillonite at 60°C with 1.0 to 3.0 N aqueous solutions of NH4F. Interaction of the fluorinated montmorillonites with hydroxy-Al oligocations, using a ratio of 2.0 mmole Al/g smectite, yielded a series of cross-linked fluorinated montmorillonites with basal spacings of 17.9–18.0 Å and surface areas of 180–325 m2/g after heat treatment at 250°C. Calcination at 400°–500°C resulted in lower d(001) (16.6–17.7 Å) and surface-area values (140–300 m2/g). Increase in the fluorine content caused gradual decrease in both values. Transmission electron microscopy of pillared Ce-montmorillonite showed a highly oriented network of well-separated, parallel unit layers with an interlayer distance, Δd(001), of 9–10 Å. Calculated lateral (interpillar) distances were in good agreement with the pore-size distributions determined in independent adsorption studies.

The clay mineralogy and major element geochemistry of four distinct layers within the Cretaceous/Tertiary (K/T) boundary marl (i.e., II, IIIa, IIIb, and IV) at Stevns Klint, Denmark, including “impact layer” (layer IIIa), were examined, and there was not a marked change in the clay mineralogy throughout this K/T boundary marl. A magnesium smectite (i.e., Mg-smectite) was the predominant clay mineral at the K/T boundary not only at Stevns Klint and at Nye Kløv; it was also found to be the predominant clay mineral in the K/T boundary at Karlstrup Quarry. In addition, Mg-smectite was found in a smectitic marl 32 meters below the K/T boundary at the Limhamn Quarry (near Malmö, Sweden), and it did not have anomalous concentrations of iridium or other siderophile trace elements. Given its occurrence in a Maastrichtian marl, it is therefore argued that the Mg-smectite is not derived from meteorite impact.

The rare earth element (REE) signatures of the Mg-smectites ranged from being comparable to the North American Shale Standard (NASC) to being one-half an order of magnitude depleted relative to NASC. One Mg-smectite collected from layer IIIb, immediately above the “impact/red layer,” was depleted in REE by one order of magnitude relative to NASC, and these levels of REE are comparable to those of smectite and illite/smectite (I/S) formed authigenically in bentonites and K-bentonites, respectively. Thus, the REE data suggest this Mg-smectite in all likelihood was formed authigenically from a glassy precursor. The presence of the low levels of REE of the Mg-smectite in the layer IIIb has no particular significance other than to suggest that this Mg-smectite separate was the least contaminated with illite or apatite having higher REE levels. With better separation, the other Mg-smectites would be expected to have comparably low levels of REE. Given the presence of the Mg-smectite throughout the K/T boundary and in Maastrichtian and Danian marls, the Mg-smectite is thought to be of volcanic origin. However, is not certain whether the Mg-smectite formed from volcanic glass deposited at the K/T boundary or whether it was formed from volcanic glass as young as late Cretaceous.

Upper Cretaceous-Tertiary marine clayey-calcareous rocks of the Hekimhan basin contain fibrous clay minerals in significant amounts. Ophiolitic rocks in the provenance area have contributed the elements to form the clay minerals. XRD, SEM, major, trace and REE analyses were applied to samples taken from several stratigraphic sections. Diagenetic minerals such as smectite, dolomite, calcite, gypsum, celestite and quartz/chalcedony are associated with sepiolite-palygorskite group clays. Trace and rare earth elements (REE) are more abundant in palygorskite than sepiolite. REE abundances in the sepiolite-palygorskite are characterized by negative Eu and positive Nd anomalies when normalized with respect to chondrite and shale. Sepiolites with sharp XRD peaks are formed by diagenetic replacement of dolomite and diagenetic transformation of palygorskite, or by direct crystallization from solution. The average structural formula of the sepiolite is:

(Mg7.15Al0.13Fe0.31Cr0.06Ni0.04)(Si11.98Al0.02)O30(OH)4(OH2)4Ca0.03Na0.02K0.02.8H2O

Palygorskite appears to be authigenic by direct precipitation from solution. It exists in both monoclinic and orthorhombic forms with the mean structural formula given below

(Mg2.22Al1.00Ti0.04Fe0.77Cr0.01Ni0.02)(Si7.68Al0.32)O20(OH)2(OH2)4Ca0.07Na0.05K0.10.4H2O

The chemical composition of the source magma along with the physiochemical conditions of the depositional environment are the main controlling factors in determining the behavior and mobility of trace elements and rare earth elements (REEs) during the transformation of volcanic ash to bentonite. The purpose of the present study was to determine the distribution pattern and mobility of trace elements and REEs in several bentonite deposits formed by diagenetic alteration of volcanic ash in shallow alkaline water in eastern Iran. Using geochemical and statistical data, the degree of weathering in the parent rocks and the distribution and mobility of trace elements and REEs during the alteration process at seven deposits (Chah-Taleb, Chah-Keshmir, Chah-Golestan, Chah-Pirouz, Gholeh-Gelia, Kharman-Sar, and Khal-Kooh) were studied. None of the parent rocks showed an advanced degree of depositional reworking and, therefore, their chemical composition is representative of the volcanic ash from which the bentonites were formed. In the chondrite-normalized REE patterns of both parent rocks and bentonites, the light rare earth elements (LREEs) were found to be enriched relative to the heavy rare earth elements (HREEs). The variation in δEu and δCe values suggested a high-temperature (<200°C), suboxic, aquatic environment in which the conversion of volcanic ash to bentonite occurred. In the bivariate correlation analysis, Si showed a strong inverse relationship with Al and LREEs, while large ion lithophile elements (LILEs), high field strength elements (HFSEs), HREEs, and LREEs displayed a positive correlation between the elements of their respective groups. The R2 values in the binary diagram of potential immobile elements against Al suggest a qualitative classification in which Ti, Gd, Ga, Pr, Tb, Nd, Sm, Ce, and Nb are considered immobile, and U, Dy, In, Sc, Hf, Zr, La, and Eu are considered to have had poor mobility during formation of the Eastern Iranian bentonite deposits.

Ion adsorption-type rare earth deposits (IADs) are developed via prolonged weathering of REE-rich volcanic and metamorphic rocks. Intense magmatic activity which occurred during the Yanshanian (199.6–65.5 Ma) and Caledonian periods (542–359.2 Ma) provided an abundant material basis for the formation of IADs in South China. High concentrations of REE and the high proportion of ion-exchangeable REE were found in the Maofeng Mountain regolith, Guangzhou city. However, the geochemical patterns and mechanisms of REE enrichment in the regolith were still poorly understood. The present study investigated the regolith profile (0–8 m) developed in Maofeng Mountain based on metallogenic and geochemical characteristics, sequential extraction, and physical and chemical parameters of the regolith profile. The bedrock contained abundant REE resources (245–287 mg kg–1) and the chondrite-normalized REE patterns showed the enrichment of light REE (LREE) and negative cerium (Ce) and europium (Eu) anomalies. The distribution patterns of REE in the bedrock were inherited by the regolith. REE enrichment of the regolith occurred mainly in the completely weathered layer (B1, B2, and B3 horizons), particularly in the depth range 2.5–4.5 m (849–2391 mg kg–1). The position of REE enrichment was controlled by the soil pH (5.52–6.02), by the amount of kaolinite and halloysite, and by the permeability of the metamorphic rock. In the REE-enriched horizon (2–8 m), the REE were hosted mainly in ion-exchangeable fractions (75–2158 mg kg–1), representing 79% of the total REE. Given the pH of 4.73–6.02, REE fractionation driven by the adsorption of kaolinite was limited. Fe–Mn (oxyhydr)oxides played an important role in REE enrichment and the reducible fraction holds up to 21% (139 mg kg–1) of the total REE. The enrichment of LREE was observed in the reducible fraction potentially because of the preferential release of LREE from the LREE-bearing minerals (monazite) and then scavenged by Fe–Mn (oxyhydr)oxides. Positive Ce anomalies (Ce/Ce*: 10) were found in the reducible fraction because trivalent Ce was oxidized by Fe–Mn (oxyhydr)oxides to cerianite (CeO2). The present study helps to understand the enrichment and fractionation of REE in the IADs of South China.

The deep regolith of the southeastern United States has undergone rapid erosion in the last two centuries due to intensive agricultural practices, which has altered the landscape and its inherent fertility. Parent material, landscape position, and land use are important factors in controlling the mineral and elemental composition of soil profiles. Independent quantitative X-ray diffraction (QXRD) and whole-rock chemical analysis of eight weathering profiles agreed well and allow mineral reaction pathways to be constrained as particles are conveyed in the subsurface. QXRD analysis of saprolite, argillic, and soil A-horizons in the profiles highlights the imprint of bedrock on the regolith, which includes Neoproterozoic meta-tonalitic to meta-granodioritic and Paleozoic meta-granitic to biotite- and amphibolite-gneissic lithologies. Also, aeolian input slightly influenced A-horizon composition. The clay mineral assemblage is dominated by kaolinite, but profiles differ in the amount of interstratified clay minerals, halloysite, hematite, goethite, and gibbsite. Rare-earth element totals vary between 30 and 1048 ppm and are generally correlated positively with clay and clay mineral content. Eu and Ce anomalies reflect parent rocks and subsequent hydrolysis and redox history, with trends depending upon landscape position and clay content in the weathering profile. Weathering profiles on a high-order interfluve and those that were actively cultivated have thick argillic horizons (as defined by clay mineral abundance) and are depleted in alkali and alkaline-earth elements. Profiles proximally developed on old-field pine and never-cultivated hardwood forest land do not show large differences in mineral composition trends, whereas profiles on old-field sites with ongoing cultivation exhibit assemblages enriched in clay minerals and (oxyhydr)oxides. Old-field pine sites that were historically eroded by previous cultivation tend to have shallower and thinner argillic horizons, which may well impact critical-zone processes involving gas and water fluxes. This study highlights that mineral compositions of deep regolith, saprolite, and shallow soil horizons are dependent on local geomorphology (i.e. watershed- and hillshed-orders). Quantifying soil and regolith compositional trends across the landscape is a prerequisite for determining rates of chemical and physical erosion on human and geologic time scales.

The wide application of rare earth elements (REEs) in the development of a carbon–neutral society has urged resource exploration worldwide in recent years. Regolith-hosted REE deposits are a major source of global REE supply and are hosted mostly in clay minerals. Nonetheless, the ways in which changes in the physicochemical properties of clay minerals during weathering affect the concentrations of REEs in the regolith are not well known. In the current study, a world-class regolith-hosted REE deposit (Bankeng, South China) has been studied to illustrate further the effect of clay minerals on sorption and fractionation of REEs during weathering to form economic deposits. In the weathering profile, halloysite and illite are abundant in the saprolite due to weathering of feldspars and biotite from the bedrock. During weathering, halloysite and illite transform gradually to kaolinite and vermiculite. The large specific surface area, pore volume, and cation exchange capacity of the clay mineral assemblages are favorable to the sorption of REEs, probably because of the formation of vermiculite. The abundance of vermiculite could explain the enrichment of REEs in the upper part of the lower pedolith. For the saprolite-pedolith interface, halloysite is probably the main sorbent for the REEs, as indicated by the distinctive appearance of pore sizes of 2.4–2.8 nm characteristic of halloysite. The progressive transformation of halloysite to kaolinite reduces the pores and desorbs the REEs, causing REE depletion in the shallower soils. As a result, REEs were mobilized downward and re-sorbed in the lower pedolith-upper saprolite causing gradual enrichment and formation of these regolith-hosted deposits.

Eocene-aged bentonite deposits in Gonzalez (Texas, USA) carrfy scattered manganese oxide-rich pods where rare earth element (REE) concentrations as high as 7800 ppm have been detected — 10 times greater than in the already enriched bentonite. This study investigated the nature of the association between REEs and Mn oxides as well as REE modes of occurrence in these pods, in order to understand the processes that mobilize and accumulate REEs in the low-temperature depositional environment of the Texas coastal plain. Embedded, polished blocks of Mn pods were analyzed by Scanning Electron Microscopy (SEM); sections were then extracted by the FIB liftout technique from regions bearing REEs for further analysis by Transmission Electron Microscopy (TEM). The SEM and TEM results revealed the presence of abundant yttrium phosphate nanoparticles identified as xenotime, forming large globular aggregates that reach a few microns in diameter; these xenotime aggregates also host trace concentrations of Zr, Dy, Er, Yb, and Ce. Further, rhabdophane nanoparticles were detected that host predominantly light REEs and Y. The relative proportions of REEs in rhabdophane vary between particles and show decoupling of Ce from other light REEs, suggesting oxidation from Ce3+ to Ce4+. The REE enrichment of these Mn pods is due to extensive weathering along fractures cutting through the bentonite deposit that drove their remobilization and transport downward. At the base of the bentonite, where fractures terminate against the boundary with a cemented sandstone, changes in flow regime combined with gradual downward changes in fluid composition, prompted co-precipitation of Mn oxides and REE phosphates (xenotime and rhabdophane).

Monazite-(Gd), ideally GdPO4, is a new mineral of the monazite group. It was discovered near Prakovce-Zimná Voda, ~23 km WNW of Košice, Western Carpathians, Slovakia. It forms anhedral domains (≤100 μm, mostly 10–50 μm in size), in close association with monazite-(Sm), Gd-bearing xenotime-(Y), Gd-bearing hingganite-(Y), fluorapatite and uraninite. All these minerals are hosted in a REE–U–Au quartz–muscovite vein, hosted in phyllites in an exocontact to granites. The density calculated using the average empirical formula and unit-cell parameters is 5.55 g/cm3. The average chemical composition measured by means of electron microprobe is as follows (wt.%): P2O5 29.68, As2O5 0.15, SiO2 0.07, ThO2 0.01, UO2 0.04, Y2O3 1.30, La2O3 3.19, Ce2O3 6.93, Pr2O3 1.12, Nd2O3 10.56, Sm2O3 17.36, Eu2O3 1.49, Gd2O3 22.84, Tb2O3 1.57, Dy2O3 2.27, CaO 0.21, total 99.67. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.30Sm0.24Nd0.15Ce0.10La0.05Dy0.03Y0.03Tb0.02Eu0.02Pr0.02Ca0.01)0.98P1.01O4. The ideal formula is GdPO4. The monazite-type structure has been confirmed by micro-Raman spectroscopy and selected-area electron diffraction. Monazite-(Gd) is monoclinic, space group P21/n, a = 6.703(1) Å, b = 6.914(1) Å, c = 6.383(1) Å, β = 103.8(1)°, V = 287.3(1) Å3 and Z = 4. The middle REE enrichment of monazite-(Gd) is shared with the associated Gd-bearing xenotime-(Y) to ‘xenotime-(Gd)’ and Gd-bearing hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing mineral assemblage is a product of selective complexing and enrichment in middle REE in low-temperature hydrothermal fluids by alteration of primary uraninite, brannerite and fluorapatite on a micro-scale. The new mineral is named as an analogue of monazite-(La), monazite-(Ce), monazite-(Nd) and monazite-(Sm) but with Gd dominant among the REE.

The Twyfelskupje carbonatite complex, Southern Namibia, exhibits the typical igneous emplacement structures of carbonatites, including plugs, cone sheets and dyke stockworks. The excellent exposure allows for detailed studies of the high-level geochemical and structural evolution of the carbonatite, and the nature of the concomitant rare earth element mineralization. Radiogenic isotope analyses (Sr, Nd, Pb) reveal that, in common with many other carbonatites, the Twyfelskupje carbonatite complex appears to be predominantly derived from mixing between HIMU and EM1 mantle end-members. Following partial melting of these mantle sources, the geochemical and structural evolution of the Twyfelskupje carbonatite complex proceeded by a staged process involving separate magma pulses, a series of emplacement structures, sub-solidus crystallization, fractionation and low-temperature hydrothermal alteration. The dominant rare earth element minerals in the Twyfelskupje carbonatite complex are fluorcarbonates and monazite, and are characterized by variable Ca, high F and light rare earth elements in the order Ce>La>Nd. Comparison between the rare earth element concentrations of the whole rocks, dominant rare earth element minerals and carbonates suggests that ∼95 % of the total rare earth element abundance of the Twyfelskupje carbonatite complex is contained within fluorcarbonates and monazite. Overall, the early calcio-carbonatite plugs are rare earth element enriched (mean 4.47 wt % rare earth oxides) relative to the magnesio-carbonatite cone sheets (mean 2.51 wt % rare earth oxides).

Carbonatites are igneous carbonate rocks. They are the main source of the rare earth elements (REE) that are essential in low carbon and high technology applications. Exploration targeting and mine planning would both benefit from a better understanding of the processes that create the almost ubiquitous alkaline and REE-bearing metasomatic aureoles in the surrounding country rocks.

Using scanning electron microscopy and whole-rock geochemistry, we investigated the composition and mineralogy of the fenite aureoles developed around the REE-poor Chilwa Island carbonatite and the REE-rich Kangankunde carbonatite, which intrude similar country rocks in the Chilwa Alkaline Province of Southern Malawi. Although common characteristics and trends in their mineralogy and composition may be typical of fenites in general, there are significant differences in their petrography and petrogenesis. For example, the mineralogically diverse breccia at Kangankunde contrasts with the intensely altered potassic breccia of Chilwa Island. This might be caused by differing sequences of fluids expelled from the carbonatites into the aureoles. The main REE-bearing mineral in fenite is different at each complex, and reflects the characteristic REE-bearing mineral of the main carbonatite: fluorapatite at Chilwa Island; and monazite at Kangankunde. Each fenite has distinctive mineral assemblages, in which the relative abundance of the REE-bearing minerals appears to be determined by the mineralogy of their respective host carbonatites.

At both localities, the REE minerals in fenite are less enriched in lanthanum and cerium than their equivalents in carbonatite, a characteristic that we attribute to REE fractionation within fluids in the aureole.

Identifying the mineral assemblages present in fenite and understanding the sequence of alkaline and mineralising fluid events could therefore be useful in predicting whether a fenite is associated with a REE-rich carbonatite. Detailed studies of other aureoles would be required to assess the reliability of these characteristics.

The Mount Mather Creek sodalite-bearing carbohydrothermal breccia dyke is located ~35 km northwest of Golden, British Columbia, Canada, within the Foreland Belt on the eastern side of the Mississippian-to-Devonian British Columbia Alkaline Province. The dyke occurs in situ on the western side of the Mount Mather Creek gully, cropping out over a distance of ~80 m with a thickness of up to 10 m, intruding a syncline of Middle and Upper Cambrian Chancellor Group carbonate rocks. To date, no parental alkaline complex has been found adjacent or proximal to the dyke. The breccia dyke is flow-banded and matrix-supported and consists of host rock clasts, medium- to coarse-grained, anhedral-to-poikilitic carbonate-rich syenite segregations that occur as veins and pods, and fine-grained banded sodalite plus carbonate fragments in a carbonate-rich matrix. The sodalite-carbonate segregations consist dominantly of sodalite, ferroan dolomite, calcite and microcline, with an extensive suite of trace minerals enriched in rare earth elements (REE), Na, Ba and Sr, including albite, analcime, ancylite-(Ce), chabazite-Na, fluorapatite, baryte, barytocalcite, cancrinite, galena, goethite, gonnardite, harmotome, edingtonite, a potentially new Mg-bearing edingtonite-like mineral, natrolite, nordstrandite, pyrite, quintinite and sphalerite. Alteration of the primary silicate–carbonate assemblage has resulted in a secondary assemblage of hydrothermal or carbohydrothermal REE–Ba–Sr–Na phases including albite, analcime, cancrinite, gonnardite and nordstrandite after sodalite, together with complex intergrowths of ancylite-(Ce), barytocalcite, edingtonite, and a potentially-new Mg-bearing edingtonite-like mineral. Remobilisation of Ba and Sr from barytocalcite resulted in crystallisation of late-stage baryte and Sr-rich calcite. Mount Mather Creek is only the fifth Canadian occurrence of the Ba-zeolite, edingtonite, and the second Canadian occurrence of the rare layered double hydroxide quintinite. The Mount Mather Creek breccia is a carbohydrothermal deposit, the product of a low temperature (<450°C), highly evolved, alkaline, SiO2-undersaturated, Na–Ba–REE–Cl-rich, residual carbonated silicate melt whose parental origins remain unknown.

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.

Rare earth elements (REEs, ‘lanthanides’) constitute a vital commodity for technological applications. Although these elements occur at trace levels in many minerals, they can comprise major constituents of low abundance phosphate, carbonate, silicate and oxide minerals, some of which form during granite weathering. REE-phosphate phases can be a source of phosphorus for essential biomolecules and certain REEs are required by some bacterial enzymes involved in the oxidation of methanol, an important compound in the global biogeochemical carbon cycle. The mechanisms that promote the dissolution of lanthanide phosphate minerals are largely unknown, but probably vary with the lanthanide phosphate mineralogy of weathered rock and soil. Here, we studied weathering of five I-type, three S-type and one A-type granite to determine the extent of weathering of primary REE- and/or P-bearing minerals apatite, allanite and monazite, and the formation of secondary REE/P-bearing minerals. We found evidence for greater mobilisation of REE and P in weathered I-type and A-type granites than in S-types, reflecting the higher solubility of apatite and allanite relative to monazite. Although monazite persisted in highly weathered S-type granites, some alteration was detected. Secondary REE/P-bearing minerals were not detected in two S-type profiles, while spherical secondary REE/P-bearing mineral aggregates were abundant throughout the third S-type profile. Secondary euhedral REE/P-bearing crystals were abundant even in the slightly weathered I-type and A-type granite material, yet they were not detected in the highly weathered material, indicating that these minerals had dissolved. Our findings indicate that mineralogy constrains substantially, but does not control completely, lanthanide availability as a function of degree of weathering. These results have implications for predicting REE and phosphate bioavailability in soils derived from granitic rock types and suggest that highly weathered I-type granites may provide inocula for bioleaching experiments.

The line connecting rare earth elements (REE) in chondrite-normalised plots can be represented by a smooth polynomial function using λ shape coefficients as described by O'Neill (2016). In this study, computationally generated λ combinations are used to construct artificial chondrite-normalised REE patterns that encompass most REE patterns likely to occur in natural materials. The dominant REE per pattern is identified, which would lead to its inclusion in a hypothetical mineral suffix, had this mineral contained essential REE. Furthermore, negative Ce and Y anomalies, common in natural minerals, are considered in the modelled REE patterns to investigate the effect of their exclusion on the relative abundance of the remainder REE. The dominant REE in a mineral results from distinct pattern shapes requiring specific fractionation processes, thus providing information on its genesis. Minerals dominated by heavy lanthanides are rare or non-existent, even though the present analysis shows that REE patterns dominated by Gd, Dy, Er and Yb are geologically plausible. This discrepancy is caused by the inclusion of Y, which dominates heavy REE budgets, in mineral name suffixes. The focus on Y obscures heavy lanthanide mineral diversity and can lead to various fractionation processes to be overlooked. Samarium dominant minerals are known, even though deemed unlikely by the computational model, suggesting additional fractionation processes that are not well described by λ shape coefficients. Positive Eu anomalies only need to be moderate in minerals depleted in the light REE for Eu to be the dominant REE, thus identifying candidate rocks in which the first Eu dominant mineral might be found. Here, I present an online tool, called ALambdaR that allows interactive control of λ shape coefficients and visualisation of resulting REE patterns.

Rare earth element extraction induces environmental damages and the balance problem. In this article, we show that recycling can challenge both problems in a two-period framework. We also find other results depending on the amount of scrap that can be recycled. If the recycling activity is not limited by available scrap, it does not change extraction in the first period. Environmental taxes on extracted quantities reduce extraction and favor recycling. But if the recycling is limited, the extractor reduces extraction in period one, adopting a foreclosure strategy, and environmental taxes can decrease recycling. In all cases, environmental taxes are never equal to the marginal damage from pollution, in order to take into account the recycling effect.