Redistribution Of REE Research Articles

U-Pb dating of bastnäsite from the Vuoriyarvi massif: An example application for assessing the REE potential of carbonatite-related deposits

The Vuoriyarvi massif is a Devonian multistage alkaline-ultrabasic carbonatite complex within the Kola alkaline province. Dolomite carbonatites of the Vuoriyarvi massif contain abundant rare-earth mineralization mainly represented by ancylite-(Ce) and bastnäsite-(Ce). Ancylite was previously shown to have probably formed in the Devonian (ca. 365 Ma) during an early postmagmatic overprint. Previous geological observations have revealed a much later crystallization of bastnäsite but have not been able to specify the exact age of the mineralization. The in situ U-Pb dating of bastnäsite allowed us to constrain its genesis. Bastnäsite for this study was extracted from two varieties of dolomite carbonatite breccias cemented by (1) quartz-bastnäsite and (2) strontianite aggregates (hereafter bastnäsite-rich and strontianite-rich carbonatites – BRC and SRC, respectively). The obtained age estimations (237.7 ± 9.8 Ma and 239.9 ± 4.1 Ma, respectively) indicate that both studied rocks were formed during a single event. The revealed age difference (∼125 Ma) excludes the genetic link between the bastnäsite origin and regional alkaline magmatism, pointing out an additional source for the Vuoriyarvi bastnäsite-bearing rocks. Moreover, the obtained U-Pb ages provide strong evidence that a Triassic event is responsible for the occurrence of bastnäsite mineralization due to hydrothermal REE redistribution from the Devonian ancylite-rich carbonatites. Most of the REEs released during this process via dissolution of ancylite were precipitated in situ as bastnäsite, while strontium was transported and incorporated into strontianite. The Pb isotopic characteristics of bastnäsite (206Pb/204Pb = 18.1 ± 0.1, 207Pb/204Pb = 15.3 ± 0.1, and 207Pb/206Pb = 0.84 ± 0.01) are most probably inherited from the Devonian host rocks of the Vuoriyarvi massif involved in the Triassic overprint. Isotopic signatures of Pb, Sr, and Nd show that the depleted mantle and lower crust played the leading role in formation of the Vuoriyarvi alkaline complex. Taken together, the results of the present study negate the supergene origin of the Vuoriyarvi bastnäsite, implying that the bastnäsite mineralization is not confined to near-surface layers and, therefore, may be dispersed more broadly throughout the complex. These findings raise the question on underestimation of the probable REE reserves and lay the groundwork for a reassessment of the economic potential of the Vuoriyarvi complex.

Redistribution of REE in granitic bedrocks during incipient weathering: insights into the role of groundwater in the formation of regolith-hosted REE deposit

Redistribution of REE in granitic bedrocks during incipient weathering: insights into the role of groundwater in the formation of regolith-hosted REE deposit

Fast REE re-distribution in mantle clinopyroxene via reactive melt infiltration

Fast REE re-distribution in mantle clinopyroxene via reactive melt infiltration

Paleozoic remelting of carbonatite in Bayan Obo (China): Further insights into the formation of a giant REE deposit

Currently, it has been confirmed that the ore-hosting dolomite of the giant Bayan Obo deposit is the Mesoproterozoic igneous carbonatite, but the roles, that the Paleozoic tectonothermal events played, are still poorly understood. In this study, we present a comprehensive investigation on the geochemistry of various carbonates to understand the generation of the Bayan Obo carbonatite. Hydrothermal monazite Th-Pb dating (peaking at ∼ 420 Ma) identified an atypical coarse-grained dolomite, which occurring as veins, and cutting through typical fine dolomitic facies. Typical coarse dolomitic facies and atypical coarse-grained dolomite are significantly different in terms of MgO, FeO, MnO, Y, Al, Si, V, Ti, Ni, Sc, and ∑REE contents and the C-O-Sr isotopic compositions, and atypical coarse-grained dolomite has lower Ba and Sr contents, lower Co/Ni ratio, with strong Eu positive anomaly and more scattered element concentration, suggesting that it has a different origin from typical coarse dolomitic facies, crystallizing from a relatively low-temperature and oxidized environment. The pervasiveness of magma flow structure and magnetite mass in the contact zone between the granite plutons and the fine dolomitic facies indicates that, at ∼ 270 Ma, the heat flux from granitic magma triggered melting of the fine dolomitic facies, forming remelted calcitic carbonatite. In addition, Th-Pb ages of monazite ranging from 1350 Ma to 240 Ma and the REE-poor properties of both remelted carbonatites suggest that both Paleozoic thermal events only caused REE activation and redistribution, without introducing additionally exogenous ore-forming metals. Accordingly, we propose that the dolomite mass in Bayan Obo are Mesoproterozoic mantle-derived carbonatites (including ore-hosting dolomite and carbonatite dike), which underwent remelting at ∼ 440 Ma and ∼ 270 Ma, respectively.

Survival of whole-rock Sm–Nd isotope system from REE redistribution and mineral-scale isotopic resetting amid hydrothermal alteration in REE-rich Fe-Cu deposit

The 147Sm–143Nd isotope system has long been used as a powerful tracer and geochronometer for a wide range of geological process, yet the robustness of Sm–Nd system has been questioned in the presence of multistage hydrothermal alteration. Here we provide robust evidence for the survival of whole-rock Sm–Nd isotopes from REE redistribution and mineral-scale isotopic resetting during multistage fluid infiltrations in the Lala Fe-Cu-REE deposit in Kangdian region, southwestern China.The Lala deposit is hosted in the ∼1.72–1.68 Ga rift-related Hekou Group and contains variable proportions of REE-rich apatite and fluorite in the ores. Both of the apatite and fluorite grains show textures of extensive metasomatic alteration, during which large amounts of REE, especially LREE, were leached out and mostly re-incorporated into newly-formed monazite, bastnäsite, and xenotime. Quantifying REE distribution budget at thin-section scale confirms that the amounts of REE (1583–5403 ppm) leached from primary apatite and fluorite are compatible with those (1636–5526 ppm) incorporated in the newly crystallized REE minerals, indicating that REE are internally redistributed within investigated samples. The whole ores yield an 18-point 147Sm–143Nd errorchon date of ∼1.71 Ga, which is in accordance with the other analogous Fe-Cu deposits in Kangdian region, and supports a ∼1.71 Ga primary mineralization at Lala. By contrast, SHRIMP 232Th–208Pb dating of texturally constrained monazite yield a crystallization age of ∼0.92 Ga, which corresponds well with the combined monazite-bastnäsite-apatite Sm–Nd isochron ages of representative samples, demonstrating a major REE redistribution and Sm–Nd isotopic resetting event at this time. The results suggest that Sm–Nd mobility was limited to within the whole-rock scale or even within the thin-section scale in the vast majority of cases, such that the whole-ore Sm–Nd isotopic system largely remained closed, despite complete resetting of the major REE minerals during younger fluid infiltration events. Our study exemplifies the apparent “decoupling” of Sm–Nd isotopic systems between macro- and microscales, which can advance our understanding of the complex history of hydrothermal systems. Our findings of a major transition (80–96%) in REE repositories also highlight the economic significance of hydrothermal alteration for modifying ore mineral assemblages, which resembles a natural REE refinement process and helps create beneficial REE resources to meet the society increasing demands.

Mesoarchaean banded iron formations of the Fennoscandian Shield: new zirconU-Pb (ID-TIMS and SHRIMP-II) isotope ages of noble metal mineralization and Nd-Sr data on whole rocks

ABSTRACT Banded iron formations (BIFs) are widespread over the world (3.81 Ga to 1.80 Ga) as the Algoma and Superior types. The paper provides new isotope (Nd-Sr, U-Pb) data on associated noble-metal mineralization in Algoma-type BIFs of the Fennoscandian Shield. U-Pb dating of accessory zircon applied to estimate the formation time of noble-metal-bearing skarn and related rocks in the Olenegorsk and Kirovogorsk BIFs, NW Fennoscandian Shield show that they occurred in the interval between the formation of basalt protolith (2.81 Ga amphibolites) and metamorphism in BIFs (2.75 Ga) to the formation of gold-bearing iron-rich skarn with native Au, Ag, Bi and tellurides (2.65 Ga) and low-temperature quartz-zeolite veins with redeposited Au (2.55 Ga). REE distribution in zircons and corresponding rocks indicated an important role of redox reactions in Fe and REE redistribution affected by reducing fluids on haematite-quartz protolith of BIFs.

Allanite in Variscan Post-Collisional Lamprophyre Dykes from Les Guilleries (NE Iberia) as a Part of Rare Earth Elements Recycling in Collisional Orogens

Recent studies of Late Permian calc-alkaline lamprophyre dykes located in the Les Guilleries Paleozoic massif of the Catalan Coastal Range have revealed that allanite is present as the main REE-bearing accessory phase, which is the object of this study. The lamprophyre dykes are amphibole–plagioclase-dominated spessartites with a wide variety of accessory phases, including titanite, ilmenite, allanite, fluorapatite, spinel, zircon, and sulfides, and show complex alteration textures related to secondary albite, chlorite, epidote, titanite and calcite. The allanite crystal composition, analyzed by SEM-EPMA and LA-ICP-MS, evidences the solid solution between epidote and allanite with a ferriallanite component, similar to what is found in Variscan post-collisional granitoids from western Europe. However, heterogeneity in crystal shapes, sizes, type of zoning, dissolution embayment textures, growth of epidote coronas, mineral paragenesis, and the unique geochemical characteristics of allanite crystals suggest multiple crystallization events. At least two types of allanite–epidote composite grains have been identified: allanite Type I, with regular allanite–epidote core-to-rim zoning and a secondary allanite rim; and allanite Type II, with anhedral allanite cores surrounded by epidote coronas. Additionally, irregular zoning, complex dissolution textures and REE redistribution suggest the occurrence of deuteric and/or post-magmatic processes, which are also common in Variscan post-collisional plutons from the Catalan Coastal Range and nearby Paleozoic massifs. Multivariate statistical analyses of major elements in allanite–epidote composite grains show a relationship between major textural and geochemical variations for three out of ten principal components, mainly related to cationic substitutions between ferriallanite-(Ce) and epidote, but also involving Mn and Ti(REE3+ + Fe2+ + Ti4+ + Mg2+ + Mn2+ = Al3+ + Ca2+ + Fe3+). The allanite U-Pb-Th- weighted mean age of 265 ± 15 Ma (MSWD = 0.57) is roughly similar to the age of emplacement of the lamprophyres in the upper crust in the mid–late Permian, and coincides with the period following the main tectonometamorphic and magmatic events of the post-collisional evolution in the Catalan Coastal Range. Th/U and La/Sm ratios suggest a metamorphic origin for most allanite grains, but a combination of metamorphic processes prior to partial melting, early–late magmatic crystallization, and/or post-magmatic hydrothermal processes is the most plausible explanation to account for the diversity of allanite grains in Les Guilleries lamprophyres.

Ti-Fe-Cr spinels in layered (stratified) complexes of the western slope of the Southern Urals: species diversity and formation conditions

Materials on geochemistry and ore Fe-Ti-Cr mineralization of rocks composing layered (stratified) bodies of the western slope of the Southern Urals are presented. A detailed analysis showed similarity in the redistribution of REE, noble metals, and Fe-Ti-Cr mineralization of practically all parameters in rocks of the Misaelga and Kusin-Kopan complexes. It has been established that the parameters of metamorphism, which influenced components redistribution in Fe-Ti-Cr minerals of the layered complexes, correspond to Misaelga – T = <550-750 °С, P = 0.1-2.8 kbar, Kusin-Kopan – T = <550-630 °С, P = 0.3-0.7 kbar, and Shuidinsky complexes – T = <550-760 °С, P = 0.5-2.5 kbar. The result of modelling the melt crystallization process showed that the Kusin-Kopan complex is an intrusive body with an ultramafic horizon in the idealized cross-section. Due to collisional processes, the lower part of the intrusion has been detached from the upper part. The proposed structure of the Kusin-Kopan complex sharply increases its prospects for such types of minerals as platinum group minerals + sulphide copper-nickel mine-ralization and/or chromites.

Study of rare earth elements in the coals of the Shubarkol deposit

The work studies mineralogical and geochemical features of the Jurassic coals of the Shubarkol deposit. The samples were examined using the method of scanning electron microscopy (SEM-EDX) Hitachi S-3400N, which was carried out at the Uranium Geology Research and Development Center at the Department of Geoecology and Geochemistry of TPU. Coal geochemistry was studied by instrumental neutron activation analysis (INAA) at the nuclear geochemical laboratory of the Department of Geoecology and Geochemistry of National Research Tomsk Polytechnic University (TPU). The choice of this object of study was determined by the tasks of research including the study of the patterns of accumulation of abnormal concentrations of REE, the effect of various factors of the geological environment on the levels of their accumulation in coals, as well as the conditions of its concentration and forms of occurrence in coals to expand the mineral resource base of Kazakhstan for rare earth elements. According to the results of scanning microscopic analysis, aluminosilicates, sulfides and sulfates with inclusions of microparticles of rare and rare earth elements were found in the composition of the Shubarkol deposit coals. According to the INNA results, abnormal concentrations of Sc, Ta, Nb, Hf, Zr, Ba, Sr, Ce and REE were found. Weathering processes led mainly to the loss and redistribution of REE in the coal seams of the Shubarkol deposit, which in turn led to increasing the content of rare earth elements from the bottom up the section. As a result of the action of multiple processes, increased concentrations of rare earth metals, mainly of the yttrium group, were formed. The absence of negative europium anomaly was determined, which confirms the original rocks composition peculiarity. The maximum contents of rare-earth metals are confined to weathered coals; for the medium-heavy group (Nd, PM, Sm, Eu), they are almost a hundredfold higher than the clarke in the upper continental crust. The tenfold excess of the clarke for elements from Gd to Lu was found in clayey sandstones and siltstones; for the rest of the rocks of the deposit the excess over the clarke is significantly lower. It was found that the coals of the deposit belong to the H-type and L-type of REE distribution. During the formation of oxidized H-type coals, clayey matter of terrigenous ash predominated as a carrier of REE, while unoxidized L-type coals were formed with the introduction of REE into the coal accumulation basin mainly in the composition of clay minerals and LREE-phosphates. Here the main source of REE was apparently the weathering crust over acidic rocks.

Geochemistry of rees in the natural waters and the secondary phases from thermal fields of Kamchatka

A study of the distribution of rare-earth elements in surface and underground waters, waterbearing rocks, as well as secondary mineral formed by the thermal waters of the Paratunka and Viluchinsky hydrothermal systems of Kamchatka was carried out. It was found that the REE content, their distribution and fractionation differ depending on the geochemical type of water, as well as the pH–Eh of the aquifer. All waters are characterized by the predominance of the dissolved form of the REE water transfer, which exceeds the transfer of REE with colloids by a factor of a thousand. It has been shown that in the discharge areas of the studied thermal waters carbonates, sulfates and silicates, including calcite, gypsum, and amorphous opal, are widespread. The intensity of the REE redistribution process in the rock-water-secondary deposits system is very weak in waters where REEs are associated with sulfates. At the same time, REEs bound in water with carbonate complexes most actively accumulate in newly formed mineral phases.

The role of brucite in water and element cycling during serpentinite subduction – Insights from Erro Tobbio (Liguria, Italy)

The Erro Tobbio olivine-antigorite serpentinites and associated dehydration veins represent hydrated oceanic mantle rocks that escaped complete dehydration and recycling into the mantle after subduction to ~ 550–600 °C and 2.0–2.5 GPa. These rocks thus offer valuable insights into the petrological evolution of a slice of hydrated oceanic mantle and the geochemical cycling down to intermediate subduction zone depths. Our study emphasises the role of brucite upon rock-buffered hydration and subduction dehydration employing bulk and in situ chemical data sets combined with petrology.Bulk rock data reveal a coherent mantle peridotite slice affected by variable melt depletion and refertilisation. Subsequent fluid-rock interaction stages proceeded isochemically with respect to SiO2, i.e., without significant SiO2 enrichment characteristic for hydrothermal ocean floor serpentinisation. Relicts of low-T mesh textures after olivine and preservation of precursor mineral and low-T hydration geochemical features indicate a lack of subsequent fluid and metamorphic overprinting, even on scales of tens of micrometres. Fluid-mobile element enrichments are modest with exceptions for B and W. Enrichment signatures of U/Cs < 1 and Rb/Cs of 4–26 are characteristic of shallow forearc hydration within or atop the slab by fluids derived from breakdown of clays or first dehydration of altered oceanic crust with a subordinate sedimentary pore fluid component. Overall, the geochemical and petrological changes of the Erro Tobbio peridotites during fluid-rock interactions were rock-buffered, in contrast to fluid-buffered hydration accompanied with significant SiO2 metasomatism at, e.g., mid ocean ridges.Silica-neutral rock-buffered serpentinisation resulted in prominent brucite formation upon olivine hydration. In absence of excess SiO2, subsequent serpentine transformation of chrysotile/lizardite to antigorite likely produced even more brucite. Rock-buffered fluid-rock interactions thus provide a mechanism for stabilising brucite in subduction zone serpentinites, presumably along hydration fronts and within deeper sections of the oceanic lithospheric mantle. Finally, brucite + antigorite dehydration produced up to 40 vol% of metamorphic olivine and prominent olivine + Ti-clinohumite + magnetite vein networks at temperatures <550–600 °C, prior to complete antigorite breakdown. Wall rocks released alkali elements, B, Cr, As, Sb, and Ba into the dehydration fluids, along with substantial Sr, REE and HFSE redistribution into vein minerals.

The igneous petrogenesis and rare metal potential of the peralkaline volcanic complex of the southern Peak Range, Central Queensland, Australia

The Oligocene Peak Range Volcanics (PRV) of central Queensland have intruded through, and erupted onto, Permian sedimentary rocks of the Bowen Basin above what is likely to be a lithospheric-scale suture zone. The southern PRV consists of domes and flows of augite (bearing) trachyte, hornblende trachyte, hornblende rhyolite, arfvedsonite rhyolite and aegirine rhyolite. The aegirine rhyolite bodies represent the most evolved rock types, with peralkaline index (molar Na + K/A) values of >1.3 and extreme enrichment in trace elements, including the rare metals Zr, Hf, Nb, Ta, and REE. Clarrys Dome, one of three aegirine rhyolite domes, features a late stage magmatic agpaitic assemblage of dalyite (K2ZrSi6O15), a eudialyte-like mineral and aegirine, which is variably replaced and overprinted by secondary REE carbonates and Zr silicates.Major and trace element geochemistry are used to show that the suite of PRV rock types represent a fractionation sequence from the least evolved augite trachytes to the most evolved aegirine rhyolites. This rock type range can be modelled by extended alkali-feldspar-dominated fractional crystallisation of an alkali basalt parental melt at a shallow crustal levels. Initial εNd values across the range of rock types are between +3 to +4, which is consistent with a common mantle source. Thus, the extreme trace element enrichment and high peralkalinity of the aegirine rhyolites is the product of the extended fractionation of a melt formed by low-degree partial melting of a mildly depleted mantle source. The secondary ore mineral assemblage and REE redistribution observed in the core of Clarrys Dome is interpreted to be due to a combination of hydrothermal alteration by fluids derived from subjacent devolatilising magma bodies, and late-stage weathering.The extreme enrichment of rare metals in the aegirine rhyolite bodies in the southern PRV support their potential to represent low grade, but large tonnage (100 s of Mt) resources of rare metals. Clear evidence of hydrothermal alteration across the region also raised the potential that higher grade rare metal mineralisation produced by hydrothermal activity may exist in the region.

The role of sulfate-rich fluids in heavy rare earth enrichment at the Dashigou carbonatite deposit, Huanglongpu, China

AbstractThe Huanglongpu carbonatites are located in the north-western part of the Qinling orogenic belt in central China. Calcite carbonatite dykes at the Dashigou open pit are unusual due to their enrichment in heavy rare earth elements (HREE) relative to light rare earth elements (LREE), leading to a flatREEpattern, and in that the majority of dykes have a quartz core. They also host economic concentrations of molybdenite. The calcite carbonatite dykes show two styles of mineralogy according to the degree of hydrothermal reworking, and these are reflected inREEdistribution and concentration. TheREEin the little-altered calcite carbonatite occur mostly in magmaticREEminerals, mainly monazite-(Ce), and typically have ΣLREE/(HREE+Y) ratios from 9.9 to 17. In hydrothermally altered calcite carbonatites, magmatic monazite-(Ce) is partially replaced to fully replaced byHREE-enriched secondary phases and the rocks have ΣLREE/(HREE+Y) ratios from 1.1 to 3.8. The fluid responsible for hydrothermalREEredistribution is preserved in fluid inclusions in the quartz lenses. The bulk of the quartz lacks fluid inclusions but is cut by two later hydrothermal quartz generations, both containing sulfate-rich fluid inclusions with sulfate typically present as multiple trapped solids, as well as in solution. The estimated total sulfate content of fluid inclusions ranges from 6 to &gt;33 wt.% K2SO4equivalent. We interpret these heterogeneous fluid inclusions to be the result of reaction of sulfate-rich fluids with the calcite carbonatite dykes. The finalHREEenrichment is due to a combination of factors: (1) the progressiveHREEenrichment of later magmatic calcite created aHREE-enriched source; (2)REE–SO42–complexing allowed theREEto be redistributed without fractionation; and (3) secondaryREEmineralisation was dominated by minerals such asHREE-enriched fluorocarbonates, xenotime-(Y) and churchite-(Y) whose crystal structures tends to favourHREE.

Y-REE mineralization in biotite-arfvedsonite granites of the Katugin rare-metal deposit, Transbaikalia, Russia

We provide the results of study of the extremely enriched in Y-REE carbonate-fluorine isolations from biotite-arfvedsonite granite of the Katugin rare metal deposit. New chemical data of isolations mineral phases - gagarinite-(Y), tveitite-(Y), fluocerite-(Ce), basnaesite, fluornatropyroclore, are delivered. Carbonate-fluoride globule in quartz of hosting granite gives possibility to estimate crystallization order. This finding might be the evidence of silicate-fluorine immiscibility suggested before for Y-REE segregations in the Katugin granites. Fluorine melt segregation took likely place at the magmatic stage of biotite-arfvedsonite granite formation. It causes host granite depletion with fluorine and redistribution of REE and Y in fluorine salt melt.

An investigation into the 87Sr/86Sr radiogenic isotope geochemistry of the manganese ore of the Kalahari Manganese Field with a view on hydrothermal fluid flow and related rare earth element enrichments

Abstract The Paleoproterozoic Kalahari Manganese Field is the largest known land-based manganese (Mn) deposit on Earth and comprises five erosional relics of the iron- and manganese-rich Hotazel Formation. A total of 19 manganese ore samples from the lower manganese ore horizon of the Hotazel Formation were selected for analysis based on their relative metasomatic alteration states. These samples range from primary diagenetic, classic supergene enriched, hydrothermally enriched (Wessels-type ore) and thrusted manganese ore. When normalised to Post-Archaean Australian shale composites, rare earth elemental analyses on the selected samples indicate significant relative enrichments within the thrusted manganese ore, an ore type that hasn’t been studied from a geochemical point of view, so far. A comparison between these respective enrichments and 87Sr/86Sr ratios indicates a distinct link between REE enrichments and associated alteration events, and a progressive increase in 87Sr/86Sr isotope values. An isotopic relationship between fluid infiltration events and REE redistribution within the Hotazel Formation has been established, highlighting unique isotope signatures necessary in better defining and characterising metasomatism within the Paleoproterozoic Kalahari Manganese Field.

C–O stable isotope geochemistry and 40Ar/39Ar geochronology of the Bear Lodge carbonatite stockwork, Wyoming, USA

The carbonatite dike swarm and vein stockwork at the center of the Paleogene Bear Lodge alkaline complex (BLAC), Wyoming, USA, is host to diverse REE mineral assemblages that are largely a result of subsolidus modification and REE redistribution. Pseudomorphic replacement of primary burbankite by an assemblage of ancylite, strontianite, and barite is the result of interaction with late-stage hydrothermal fluids that added Sr, Ba, S, F, and REE, analogous to the replacement processes described for some carbonatite complexes of Russia's Kola Peninsula. Carbon and oxygen stable isotope ratios indicate that the primary carbonatite mineralogy experienced degassing/pneumatolysis and alteration by fluids of variable temperature, CO2/H2O ratios, and/or meteoric water content. Isotopic differences of matrix calcite between Group 1 carbonatites (avg. δ13C = −7.3‰; δ18O = 9.1‰) and Group 2 carbonatites (avg. δ13C = −9.9‰; δ18O = 10.2‰) are consistent with loss of CO2 during degassing. The open-system alteration of burbankite caused a pronounced positive δ18O-shift in bulk ancylite pseudomorphs (δ18O: 14.3–25.7‰) relative to matrix calcite (δ18O: 8.7–11.2‰). Oxygen isotope compositions of biotite (δ18O: 4.5–5.9‰) and K-feldspar (δ18O: 7.3–7.9‰) in unoxidized carbonatite are typical of primary magmatic silicates and suggest that fluids responsible for the burbankite-to-ancylite conversion remained predominantly magmatic (carbohydrothermal). Concomitant increases toward the surface in 13C and 18O, oxidation, matrix carbonate dissolution, and the replacement of REE carbonates (ancylite, carbocernaite, and burbankite) by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite) suggest interaction with late-stage, low temperature (<250 °C) fluids characterized by lower CO2/H2O ratios, and an increasing meteoric water component. The first 40Ar/39Ar ages from carbonatite-hosted biotite and K-feldspar at the BLAC are between 51.45 ± 0.08 and 51.89 ± 0.14 Ma. Although carbonatite is commonly observed as the final intrusive phase in alkaline igneous complexes, relative-age relationships and previously published geochronology for Bear Lodge rocks indicate that alkaline silicate magmatism both preceded and followed carbonatite emplacement.

Rare earth element systematics in boiled fluids from basalt-hosted geothermal systems

Hydrothermal processes that lead to REE fractionation and redistribution are important for understanding water-rock interactions in geothermal energy resources and mineral deposits, and for determining how submarine hydrothermal activity affects the composition of oceanic crust. Much previous work on REE transport and deposition has focused on submarine hydrothermal vents. We report REE concentrations in boiled fluids sampled from five subaerial, basalt-hosted geothermal fields, and explore controls on aqueous REE concentrations by ligand complexation and mineral supersaturation. Samples that boiled at pressures between 0.8 and 2.83 MPa were obtained from the Reykjanes, Svartsengi, Hellisheidi, and Nesjavellir geothermal systems in Iceland, and the Puna geothermal system in Hawaii. For comparison, we also report REE concentrations in hydrothermal fluids from the sediment hosted submarine Middle Valley hydrothermal system, which boiled at >250 MPa. The pH(25°C) values of the sampled subaerial geothermal fluids range from 3.94 to 6.77, and Cl concentrations range from near seawater (502 mmol/kg) to dilute (1.9 mmol/kg). La, Ce and Eu are the only REE present at levels above 5 picomole/kg (pmol/kg) in the boiled geothermal fluids; and there are notable CI chondrite normalized La and Eu anomalies in the saline fluids. REE concentrations in Middle Valley hydrothermal fluids fall within the typical range reported for submarine hydrothermal fluids and have around two orders of magnitude higher REE than the boiled subaerial geothermal fluids. Bulk samples of precipitates in pipes from the Reykjanes geothermal system have detectable REE, confirming that downhole fluids have lost REE during boiling and production of fluids for geothermal energy. Isenthalpic boiling models show that the proportions of La and Eu chloride complexes increase relative to other aqueous species as boiling progresses, attenuating the incorporation of La and Eu into precipitated well scale solids. Fluorapatite is calculated to precipitate on boiling of low pH and saline fluids and calcite is calculated to precipitate from dilute and near-neutral pH fluids, and these minerals likely sequester REE in boiled subaerial fluids. Submarine hydrothermal fluids are constrained to boiling at higher temperatures than subaerial geothermal fluids owing to pressure from overlying cold seawater, therefore secondary minerals and solids that incorporate REE are not extensively precipitated and REE concentrations in the fluids are higher.

Trace Elements in Alkaline Lamprophyres, Clinopyroxene, and Amphibole of the Tomtor Massif and the Ore Potential of the Melts

Data obtained on lamprophyres from the carbonatite–volcanic unit in the lower horizon of the Tomtor Massif indicate that the rocks and zoned diopside and kaersutite phenocrysts in them are enriched in incompatible elements more significantly than is typical of alkaline ultramafic rocks of the Maymecha–Kotui and Kola provinces. The concentrations of these elements and their indicator ratios in the cores and intermediate zones of the diopside and kaersutite phenocrysts significantly vary, and this suggests that the minerals might have crystallized from different melts. This is consistent with the earlier conclusions, which were derived from studying melt inclusions, that the phenocrysts crystallized from mixing alkaline mafic melts of sodic and potassic types and different Mg–number which were enriched in the carbonatite component. The cores of the diopside phenocrysts started to crystallize from sodic mafic magma in a magmatic chamber, while the intermediate and outermost zones of this mineral crystallized from mixed sodic–potassic mafic melts. The carbonatite component was separated from the sodic mafic melt at high temperature (>1150°C) during diopside core crystallization. The bulk compositions of the alkaline lamprophyres and of the diopside and kaersutite phenocrysts contain lower normalized concentrations of HREE than LREE. This led us to conclude that the parental sodic and potassic mafic melts were derived from an enriched mantle source material under garnet–facies parameters, as is typical of continental rifts. It is noteworthy that the potassic mafic melt was derived at greater depths and lower degrees of melting of the mantle source than the sodic melt. The iron–rich sodic melt from which the cores of the diopside phenocrysts started to crystallize was enriched in V, REE, Y, and volatile components (H2O, CO2, F, Cl, and S). The onset of carbonate–silicate liquid immiscibility was marked by the redistribution of REE and Y into the carbonatite melt. The potassic, more Mg–rich mafic melt from which the intermediate and outermost zones of the diopside phenocrysts crystallized was enriched in Ti, Nb, Zr, and REE and always remained homogeneous when this mineral crystallized.

Magmatism and crustal extension: Constraining activation of the ductile shearing along the Gediz detachment, Menderes Massif (western Turkey)

The Menderes Massif of western Turkey is a key area to study feedback relationships between magma generation/emplacement and activation of extensional detachment tectonics. Here, we present new textural analysis and in situ U–(Th)–Pb titanite dating from selected samples collected in the transition from the undeformed to the mylonitized zones of the Salihli granodiorite at the footwall of the Neogene, ductile-to-brittle, top-to-the-NNE Gediz–Alaşheir (GDF) detachment fault. Ductile shearing was accompanied by the fluid-mediated sub-solidus transformation of the granodiorite to orthogneiss, which occurred at shallower crustal levels and temperatures compatible with the upper greenschist-to-amphibolite facies metamorphic conditions (530–580°C and P<2GPa). The syn-tectonic metamorphic overgrowth of REE-poor titanite on pristine REE-rich igneous titanite offers the possibility to constrain the timing of magma crystallisation and solid-state shearing at the footwall of the Gediz detachment. The common Pb corrected 206Pb/238U (206Pb*/238U) ages and the REE re-distribution in titanite that spatially correlates with the Th/U zoning suggests that titanite predominantly preserve open-system ages during fluid-assisted syn-tectonic re-crystallisation in the transition from magma crystallization and emplacement (at ~16–17Ma) to the syn-tectonic, solid-state shearing (at ~14-15Ma). A minimum time lapse of ca. 1–2Ma is then inferred between the crustal emplacement of the Salihli granodiorite and nucleation of the ductile extensional shearing along the Gediz detachment. The reconstruction of the cooling history of the Salihli granodiorite documents a punctuated evolution dominated by two episodes of rapid cooling, between ~14Ma and ~12Ma (~100°C/Ma) and between ~3 and ~2Ma (~105°C/Ma). We relate the first episode to nucleation and development of post-emplacement of ductile shearing along the GDF and the second to brittle high-angle faulting, respectively. Our dataset suggests that in the Menderes Massif the activation of ductile extension was a consequence, rather than the cause, of magma emplacement in the extending crust.

Minerals of zirconolite group from fenitized xenoliths in nepheline syenites of Khibiny and Lovozero plutons, Kola Peninsula

Zirconolite, its Ce-, Nd-, and Y-analogs, and laachite, another member of the zirconolite group, are typomorphic minerals of the fenitized xenoliths in nepheline syenite and foidolite of the Khibiny–Lovozero Complex, Kola Peninsula, Russia. All these minerals are formed at the late stage of fenitization as products of ilmentie alteration under the effect of Zr-bearing fluids. The diversity of these minerals is caused by the chemical substitutions of Na and Ca for REE, Th, and U compensated by substitution of Ti and Zr for Nb, Fe and Ta, as well as by the redistribution of REE between varieties enriched in Ti (HREE) or Nb (LREE). The results obtained can be used in the synthesis of Synroc-type titanate ceramics assigned for the immobilization of actinides.