This study investigates the hydrogenetic ferromanganese crust (HFMC) from the Magellan Seamounts in the northwest Pacific Ocean, focusing on its mineralogy, crystal chemistry, and paleoclimatic records. Given that ferromanganese is composed of poorly crystalline MnOx phases, such as vernadite, structural determination using conventional X-ray diffraction (XRD) methods is challenging and has very limited effectiveness. Therefore, synchrotron-based pair-distribution function (PDF) analysis of total X-ray scattering and high-resolution electron microscopy techniques were employed to characterize the structures and compositions of HFMC. The results from the synchrotron XRD and transmission electron microscopy (TEM) reveal that the studied HFMC consists primarily of poorly crystalline Fe-bearing vernadite. The chemical analysis of the HFMC layers indicates that the rare-earth elements (REE) and P were preferentially adsorbed on the Fe-rich vernadite, whereas platinum-group elements (PGE), Co, and Ni were enriched in the Mn-rich vernadite. The top layers of the HFMC display fine-scale compositional variations (cycle of ~1600 y) that signify millennial-scale paleoclimate oscillations during the Middle-Late Pleistocene and Holocene periods linked to the glacial termination event that occurred ~126,000 y ago. This millennial-scale oscillation correlates with sea-level variations influenced by the expansion and contraction of ice sheets, offering a crucial signal for understanding the paleoclimatic interpretation throughout the glacial periods. To fully decipher the fine-scale paleoclimate signals and assist in forecasting future climatic conditions, a more extensive examination of ferromanganese crusts from diverse depths, sources, and locations is necessitated.

The high-density siliciclastic minerals (e.g. zircon) in the coarse fractions (>44 mm, informally known as grit) of the mined Georgia kaolins are potential and significant sources of the rare-earth elements (REE). The abundances and provenance of the REE signature have not been studied extensively for the Georgia kaolins. The objective of the present study was, therefore, to define the contribution of these heavy minerals (e.g. zircon) to the REE inventory of the coarse fractions of Georgia kaolins. Heavy-mineral subfractions separated from the coarse fractions contained 1647 mg/kg REE from the Jeffersonville Member of the Lower Tertiary Huber Formation and 5012 mg/kg REE from the Buffalo Creek Kaolin Member of the Upper Cretaceous Galliard Formation, respectively. These heavy-mineral subfractions were enriched 10–100 times in the heavy rare-earth elements (HREE, Gd—Lu,), Hf, and Zr relative to the concentrations of these elements in Upper Continental Crust. The heavy-mineral subfractions comprised 5% of the coarse fractions (grit) of these two kaolin-producing formations. The heavy-mineral subfractions consisted of zircon, anatase, rutile, kaolinite, and minor amounts of muscovite, trace ilmenite, and staurolite. The large concentrations of REE were obtained by separating the dense heavy minerals from the coarse fraction (grit) obtained during the typical production of kaolin-group minerals (kaolinite) from kaolin ore. The amount of zircon (estimated from the 6–11 wt.% Zr) and the absence of monazite did not explain the high concentrations of REE in the heavy-mineral subfractions. The large amounts of REE could have resulted from the sorption of REE released during weathering reactions, or from the presence of small amounts (0.025 wt.%) each of monazite and xenotime in addition to the presence of zircon. This heavymineral subfraction represented a novel domestic resource of extractable REE, especially the HREE, of a grade as high as 0.50 wt.% total REE.

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.

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.

Thermodynamic properties of Nd–Bi and Nd–Sn alloys were determined via electromotive force (emf) measurements at 725–1075 K. The emf measurements of an Nd–Bi alloy at mole fraction xNd = 0.20 were conducted using a solid CaF2–NdF3 electrolyte relative to pure Nd(s). The emf values from the CaF2–NdF3 electrolyte were verified in separate experiments in molten LiCl–KCl–NdCl3 where pure Nd(s) was electrodeposited. The Nd–Bi (xNd = 0.20) exhibited two-phase behavior with a peritectic reaction (L + NdBi = NdBi2) at 926 K from differential scanning calorimetry. The two-phase Nd–Bi (xNd = 0.20) was employed as a stable reference electrode in molten LiCl–KCl–NdCl3 for emf measurements of Nd–Bi (xNd = 0.15–0.40) and Nd–Sn (xNd = 0.10) alloys. The emf measurements of these alloys were reproducible during thermal cycles over 50 h and were used to calculate thermodynamic properties, including the partial molar Gibbs energy, entropy, and enthalpy.

Fluorapatite with monazite-(Ce) and xenotime-(Y) microinclusions occurs in the lithium–caesium–tantalum pegmatite body A of the Volta Grande mine, Minas Gerais state, Southeast Brazil. The fluorapatite displays faint zoning, detected mainly by cathodoluminescence. Electron probe and laser ablation analyses indicate that zoning in the fluorapatite corresponds to variation in Mn and rare-earth element (REE) content. Such compositional variation is attributed to partial removal of the REE from the fluorapatite structure during a dissolution–reprecipitation process, forming monazite-(Ce) and xenotime-(Y) microinclusions in the REE-depleted zones of the fluorapatite. These inclusions exhibit an inherited geochemical signature, manifested by low Th and U concentrations when compared to monazite and xenotime crystallised from melts. Rhodochrosite and calcite inclusions are also associated with monazite-(Ce) and xenotime-(Y) and are probably products of the same process, recycling Ca, Mn, and CO32− from the fluorapatite through the following reaction: [Ca(5–2a–b–½x),Naa,(Y + REE)a,Mnb][(PO4)3–x(CO3)x(F)] + Fluid[a(2Ca2+ + P5+) + (x–b)(Ca2+) + H2O)] → [Ca5(PO4)3(F,OH)] + a[(Y + REE)PO4] + b[Mn(CO3)] + (x–b)[Ca(CO3)] + Fluid a[Na+].

On the basis of new fluid-inclusion analyses, we propose that a hot (T > 204.5°C), salty (16 wt.% eq. NaCl, attributed to LiCl), hydrous fluid mediated the dissolution–reprecipitation of the fluorapatite. This fluid corresponds to similarly described Li-rich fluids which were suggested to have re-equilibrated the mineralogical assemblage at the Volta Grande mine.

Ammonium illite and ammonium illite-smectite mixed layers, together with potassium illite, smectite and minute amounts of kaolinite were identified in hydrothermally altered andesite rocks from the Harghita Bãi area of the Eastern Carpathians, Romania. K-Ar dating and oxygen isotope tracing, as well as rare-earth elemental analyses were made to provide new information on the timing and crystal-chemical processes characterizing the crystallization and further evolution of these illite-type mineral phases.

The combined results suggest the occurrence of hydrothermal activity in two distinct episodes with nucleation of two generations of illite-type particles of different chemistry and morphology. About 9.5 Ma ago, potassium illite crystallized in alteration halos of the porphyry Cu system, probably at a temperature of ~270ºC from fluids having a δ18O of ~2.9% (V-SMOW). Associated smectite seems to have precipitated slightly later in external alteration halos at a similar temperature, but from fluids depleted in alkalis and with a different δ18O. Alternately, ammonium-rich illite-smectite mixed layers formed very recently, less than ~1 million years ago at a temperature of ~90ºC from fluids of probable meteoric origin that altered the previously crystallized potassium illite, resulting in the crystallization of a new generation of ammonium illite-smectite mixed layers. Evidence of this dissolution-precipitation process is provided by a significant increase in the δ18O of the mixed-layer structures and by a significant change in their REE contents and distribution patterns. Occurrence of potassium in the ammonium-rich mixed layers probably relates to the progressive alteration of the first-generation potassium illite and a discrete concomitant take up of released K by the new NH4-rich interlayers of the ammonium mixed layered sequence.

The North Qôroq syenite centre forms part of the Gardar Province of South Greenland. Extensive metasomatism, associated with the evolution of syenitic magmas, has resulted in redistribution of the rare-earth elements (REE), originally concentrated by magmatic processes, in both the syenites and surrounding granite-gneiss and quartzite country rocks. An important host for REE is apatite which can occur in significant quantities. Metasomatic apatites show complex, concentric, but irregular patterns of zonation, clearly seen using CL and BSE imaging. This zonation is related to successive pulses of metasomatising fluids. Electron microprobe analysis confirms the presence of significant quantities of REE in the apatites. The dominant cation exchange mechanism proposed is Ca2+ + P5+ ⇌ REE3+ + Si4+. In contrast to apatites from the nearby Ilímaussaq intrusion, there is no significant Na present in the structure and exchange reactions involving Na+ and REE3+ for Ca2+ have not occurred.

Apatites from the quartzite are fluor-apatites, while those from the granite-gneiss are more Cl-rich. These differences reflect the fact that granite-gneiss apatites are original and modified by metasomatism, whereas, those in the quartzite are metasomatic in origin. REE were probably transported as carbonate, fluoride or fluor-carbonate complexes, and reflect the activity of a F−-rich, CO2−3-rich fluid phase.

Electron-probe microanalysis (EPMA) is applicable to rare-earth elements (REE) in minerals with relatively high REE concentrations (e.g. hundreds of parts per million). However, given that each of the 14 REE has at least 12 X-ray lines in the L spectrum, finding peak-free regions for background measurement can be problematical. Also, measured peak intensities are liable to require correction for interferences. Hitherto, little attention has been paid to the optimisation of background offsets and the implications of the wide variation in REE distribution patterns in different minerals. The ‘Virtual WDS’ program, which enables complex multi-element spectra to be synthesised, has been used to refine the conditions used for different REE distributions. Choices include whether to use the Lβ1 rather than the Lα1 line, background offsets, and counting times for comparable relative precision. Correction factors for interferences affecting peak and background measurements have also been derived.

Hydroxyl-bastnaesite-(Nd), the Nd- and OH-dominant new member of the bastnaesite group, has been found in the red karstic bauxites near Nikšić, Montenegro. It occurs as whitish, irregular aggregates of crystals usually 100–200 µm in diameter. Hexagonal with the cell dimensions a = 7.191 and c = 9.921 Å, with Z = 6. The strongest lines of the X-ray powder diffraction pattern (d, I, hkl) are: 4.95 80(002); 3.596 79(110); 2.911 100(112); 2.077 29(300); 2.042 51(114); 1.914 30(302). The mineral is uniaxial positive, ω 1.715, ɛ 1.81; Dcalc 4.89 g/cm3.

Electron probe analysis, using garnet, apatite and synthetic glass standards, combined with thermogravimetric and evolved gas analysis, gave Y2O3 0.2, La2O3 27.1, Ce2O3 0.3, Pr2O3 8.5, Nd2O3 31.5, Sm2O3 4.4, Eu2O3 1.3, Gd2O3 1.4, CaO 0.3, F 3.3, H2O 2.26, CO2 20.63, sum 101.19, less O = F 1.39, total 99.80%. This analysis calculates to (Nd0.41La0.36Pr0.11Sm0.06Gd0.02 Eu0.02Ca0.01)Σ0.99(CO3)1.03[(OH)0.55F0.38]Σ0.93, or ideally, (Nd,La)CO3(OH,F), with Nd > La and OH > F.

Six hundred and forty four gamma-ray spectrometer assays of U and Th obtained within the late Caledonian Galway Granite western Ireland are presented. The data cover the range of granodiorites, adamellites and leucogranites (Murvey Granite) present in the batholith. There is an overall increase in U and Th abundances with petrological evolution. The broad scatter of values that characterizes the Murvey Granite reflects the geographically separate occurrences of this leucogranite. Rubidium and strontium data imply varying degrees of fractionation among these separate Murvey Granite occurrences. Y and HREE are notably enriched in the Murvey granite at Costelloe which also contains the highest Th levels amongst the leucogranites. Thorite, uraninite, monazite and Y-zircon are present in this leucogranite and are responsible for the observed enrichments in U, Th, Y and HREE.

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.

A new member of the gadolinite supergroup, gadolinite-(Nd), IMA2016-013, ideally Nd2FeBe2Si2O10, was found in the Malmkärra mine, ~3.5 km WSW of Norberg, south-central Sweden, where it occurs in association with fluorbritholite-(Ce), västmanlandite-(Ce), dollaseite-(Ce), bastnäsite-(Ce) and tremolite. Gadolinite-(Nd) forms anhedral grains up to 150 µm in size, commonly occurring as aggregates of olive green colour. The crystals are transparent with vitreous to adamantine lustre. Gadolinite-(Nd) is brittle with conchoidal fracture, no cleavage or parting was observed. It has a white streak, the Mohs hardness is 6.5–7 and the calculated density is 4.86 g cm–3. Optically, the mineral is weakly pleochroic in shades of olive green, biaxial (–), nα = 1.78(1), nβ(calc.) = 1.80, nγ = 1.81(1) measured in white light, 2V(meas.) = 62(3)°. Electron-microprobe and laser ablation inductively coupled plasma mass spectrometry analysis [in wt.%] provided SiO2 21.77, Y2O3 5.49, La2O3 2.78, Ce2 O3 14.04, Pr2O3 3.28, Nd2O3 19.27, Sm2O3 5.30, Eu2O3 0.24, Gd2O3 4.10, Tb2O3 0.36, Dy2O3 1.32, Ho2O3 0.18, Er2O3 0.38, MgO 0.51, CaO 0.14, MnO 0.10, FeO 10.62, B2O3 0.10, BeOcalc. 8.99, H2Ocalc. 0.55 and total 99.52 giving the following empirical formula (based on 2 Si): (Nd0.632 Ce0.472Y0.268Sm0.168Gd0.125Pr0.110La0.094Dy0.039Ca0.014Er0.011Tb0.011Eu0.008Ho0.008)∑1.957(Fe0.816Mg0.070Mn0.008)∑0.894(Be1.984B0.016)∑2.000Si2O9.660OH0.337. A weak Raman vibration band at ~3525 cm–1 confirms the presence of water in the structure. Gadolinite-(Nd) is monoclinic, P21/c, with a = 4.8216(3) Å, b = 7.6985(4) Å, c = 10.1362(6) Å, β = 90.234(4)°, V = 376.24(6) Å3 and Z = 2. The strongest X-ray diffraction lines are [dobs in Å (hkl) Irel]: 4.830 (100) 72, 3.603 (021) 37, 3.191(-112) 52, 3.097 (013) 35, 2.888 (121) 100, 2.607(113) 49, 2.412 (200) 24. Along with the Malmkärra mine, gadolinite-(Nd) was also recorded also at Johannagruvan and Nya Bastnäs. The minerals of the gadolinite subgroup together with fluorbritholite-(Ce) incorporate the highest fraction of medium-to-heavy rare-earth elements among associated rare-earth element minerals in the Malmkärra mine and possibly in all Bastnäs-type deposits.

Eudialyte-group minerals (EGM) are very common in highly evolved SiO2-undersaturated syenites and are characteristic minerals of agpaitic rocks. Conversely, they are extremely rare in peralkaline granites, with only a handful of EGM occurrences reported worldwide. Here, we study two new examples of EGM occurrence in two types of peralkaline pegmatitic granites from the Cenozoic Ambohimirahavavy complex, and assess the magmatic conditions required to crystallize EGM in peralkaline SiO2-oversaturated rocks. In the transitional granite (contains EGM as accessory minerals) EGM occur as late phases and are the only agpaitic and major rare-earth element (REE) bearing minerals. In the agpaitic granite (contains EGM as rock-forming minerals) EGM are early-magmatic phases occurring together with two other agpaitic minerals, nacareniobsite-(Ce) and turkestanite. In these granites, EGM are partly-to-completely altered and replaced by secondary assemblages consisting of zircon and quartz in the transitional granite and an unidentified Ca-Na zirconosilicate in the agpaitic granite. Ambohimirahavavy EGM, as well as those from other peralkaline granites and pegmatites, are richer in REE and poorer in Ca than EGM in nepheline syenites. We infer that magmatic EGM are rare in SiO2-oversaturated rocks because of low Cl concentrations in these melts. At Ambohimirahavavy, contamination of the parental magma of the agpaitic granite with Ca-rich material increased the solubility of Cl in the melt promoting EGM crystallization. In both granite types, EGM were destabilized by the late exsolution of a fluid and by interaction with an external Ca-bearing fluid.

Nanoscale characterization (TEM on FIB-SEM-prepared foils) was undertaken on feldspars undergoing transformation from early post-magmatic (deuteric) to hydrothermal stages in granites hosting the Olympic Dam Cu-U-Au-Ag deposit, and from the Cu-Au skarn at Hillside within the same iron-oxide copper-gold (IOCG) province, South Australia. These include complex perthitic textures, anomalously Ba-, Fe-, or REE-rich compositions, and REE-flourocarbonate + molybdenite assemblages which pseudomorph pre-existing feldspars. Epitaxial orientations between cryptoperthite (magmatic), patch perthite (dueteric) and replacive albite (hydrothermal) within vein perthite support interface-mediated reactions between pre-existing alkali-feldspars and pervading fluid, irrespective of micro-scale crystal morphology. Such observations are consistent with a coupled dissolution-reprecipitation reaction mechanism, which assists in grain-scale element remobilization via the generation of transient interconnected microporosity. Micro-scale aggregates of hydrothermal hyalophane (Ba-rich K-feldspar), crystallizing within previously albitized areas of andesine, reveal a complex assemblage of calc-silicate, As-bearing fluorapatite and Fe oxides along reaction boundaries in the enclosing albite-sericite assemblage typical of deuteric alteration. Such inclusions are good REE repositories and their presence supports REE remobilization at the grain-scale during early hydrothermal alteration. Iron-metasomatism is recognized by nanoscale maghemite inclusions within ‘red-stained’ orthoclase, as well as by hematite in REE-fluorocarbonates, which reflect broader-scale zonation patterns typical for IOCG systems. Potassium-feldspar from the contact between alkali-granite and skarn at Hillside is characterized by 100–1000 ppm REE, attributable to pervasive nanoscale inclusions of calc-silicates, concentrated along microfractures, or pore-attached. Feldspar replacement by REE-fluorcarbonates at Olympic Dam and nanoscale calc-silicate inclusions in feldspar at Hillside are both strong evidence for the role of feldspars in concentrating REE during intense metasomatism. Differences in mineralogical expression are due to the availability of associated elements. Lattice-scale intergrowths of assemblages indicative of Fe-metasomatism, REE-enrichment and sulfide deposition at Olympic Dam are evidence for a spatial and temporal relationship between these processes.

The Late Cretaceous Itatiaia complex is made up of nepheline syenite grading to peralkaline varieties, quartz syenite and granite, emplaced in the metamorphic rocks of the Serra do Mar, SE Brazil. The nepheline syenites are characterized by assemblages with alkali feldspar, nepheline, Fe-Ti oxides, clinopyroxene, amphibole, apatite and titanite, while the peralkaline nepheline syenites have F-disilicates (rinkite, wöhlerite, hiortdahlite, låvenite), britholite and pyrophanite as the accessory phases. The silica-oversaturated rocks have alkali feldspar, plagioclase, quartz, amphibole, clinopyroxene and Fe-Ti oxides; the chevkinite-group minerals are the featured accessory phases and are found with allanite, fluorapatite, fluorite, zircon, thorite, yttrialite, zirconolite, pyrochlore and yttrocolumbite. The major- and trace-element composition of the Itatiaia rocks have variations linked to the amount of accessory phases, have smooth, enriched chondritenormalized rare-earth element (REE) distribution patterns in the least-evolved nepheline syenites and convex patterns in the most-evolved nepheline syenites. The REE distribution patterns of the quartz syenites and granites show a typical pattern caused by fractional crystallization of feldspar and amphibole, in an environment characterized by relatively high oxygen fugacity (>NiNiO buffer) and high concentrations of H2O and F, supporting the crystallization of hydrous phases, fluorite and F-disilicates. The removal of small amounts of titanite in the transition from the least-evolved to the most-evolved nepheline syenites stems from petrogenetic models involving REE, and is shown to be a common feature of the magmatic evolution of many other syenitic/ trachytic/ phonolitic complexes of the Serra do Mar and elsewhere.

The Zagros orogenic and metallogenic belt is characterized by the widespread occurrence of manganese and ferromanganese deposits. These deposits are spatially associated with radiolarian cherts and basaltic rocks, which cap the ophiolite sequences. The present work provides a review on the rare-earth element (REE) geochemistry coupled with major- and trace-element geochemical characteristics of the Nasirabad and Abadeh Tashk manganese deposits (associated with the Neyriz ophiolite), and Sorkhvand manganese deposit (associated with the Kermanshah ophiolite). These data are used to gain an insight into the primary ore-forming processes that control the deposition of manganese ores. All of the selected manganese deposits have consistently high Ba contents and low concentrations of trace elements (Co, Cu and Ni) with high Mn/Fe ratios typical of hydrothermal activity. A relatively low REE abundance, Lan/Ndn ratios (>3), and position on a Lan/Cen vs. Al2O3/(Al2O3 + Fe2O3) discrimination plot indicate a distal hydrothermal source for almost all of the selected manganese deposits. Most of the deposits are characterized by Ceanom < –0.1 which reflects the prevailing oxidative conditions during the deposition of manganese ores. Importantly, this is consistent with the occurrence of non-sulfide oxic Mn mineralization in all the manganese deposits of the Zagros orogeny. The comparison of the Sorkhvand, Abadeh Tashk and Nasirabad manganese deposits with other manganese deposits elsewhere in the world indicates that major- and trace-element characteristics, as well as the REE composition of the Zagros manganese deposits are analogous to those typical of hydrothermal deposits.

Continuous development of advanced technologies has created increasing demand for rare-earth elements (REE), with global emphasis on identifying new alternate sources to ensure adequate supply. Ore deposits containing physically adsorbed lanthanides are substantially lower grade than other REE deposit types; however, the low mining and processing costs make them economically attractive as sources of REE. To evaluate the commercial potential for the recovery of REEs from ion-adsorption deposits in a systematic manner, a standardized procedure for REE leaching was developed previously. Using this procudure it was found that, regardless of variations in ore origin and REE content, all REE consistently reached peak extraction levels under ambient conditions with fast kinetics. Various techniques to improve the REE extraction through process variations were also investigated: it was found that decreasing the L:S ratio, re-using leachate on fresh ores and counter-current leaching were all capable of increasing REE concentrations in the resultant leachate, albeit at the expense of REE extraction levels. In addition, the water content trapped in the leached material was found to contain significant amounts of REE and residual lixiviant requiring thorough washing of the solid residue.

Kamotoite-(Y) is a rare supergene product of uraninite hydration–oxidation weathering and its structure is unknown. Based on single-crystal X-ray diffraction data collected with high-redundancy using a microfocus source, kamotoite-(Y) is monoclinic, has space group P21/n,with a = 12.3525(5), b = 12.9432(5), c = 19.4409(7) Å, β = 99.857(3)°, V = 3069.8(2) Å3 and Z = 4. Crystals are pervasively twinned (two-fold rotation around [0.75 0 0.75]), giving a strongly pseudo-orthorhombic diffractionpattern. The pseudoorthorhombic pattern can be described with an orthorhombic super-cell (transformation matrix 0,1,0/1,0,1/3,0,1), approximately four times larger in volume then a true monoclinic unit cell. This unit-cell is the same as the cell given elsewhere for the structure of bijvoetite-(Y),another (REE)-containing uranyl carbonate. The successful structure solution and refinement (R = 0.044 for 6294 unique observed reflections), carried out using our choice of unit cell, as well as the superstructure refinement and comparison of the original structure data forbijvoetite-(Y) reveal that these two crystal structures are identical. The crystal structure of kamotoite-(Y) consists of electroneutral sheets of the bijvoetite-(Y) uranylanion topology and an interlayer with H2O molecules not-coordinated directly to any metal cation. Despite determinationof the kamotoite-(Y) structure and demonstration that bijvoetite-(Y) has the same structure, the identity of these two minerals cannot be proved without additional study of the holotype material.