Structural state of rare earth elements in eudialyte-group minerals

This work was carried out under the NERC-funded SOS RARE consortium [grant NE/M010856/1 to AMB, NJH and AF]. We thank Diamond Light Source and KIT Karlsruhe Light Source for beam time at I18 [grants SP14793 and SP15903 to AMB and AF] and SUL-X, respectively. PG was funded by the People Programme (Marie Curie Actions) in the EU Seventh Framework Programme (FP7/2007-2013), REA grant agreement no. 609405 (COFUNDPostdocDTU).Eudialyte-group minerals (EGM) attract global interest as potential resources for high-field-strength elements (e.g. Zr, Nb, Ta, and rare-earth elements), i.e. critical materials for modern technologies. They are particularly valued for their relative enrichment in the most critical lanthanides, i.e. Nd and heavy rare earth elements (Gd–Lu). However, rare earth element (REE) substitution mechanisms into the EGM structure are still poorly understood. Light and heavy REE may occupy different sites and there may be ordering and/or defect clustering in the structure. This study uses X-ray absorption spectroscopy to determine the structural state of REE in EGM from prospective eudialyte-bearing complexes. Yttrium K-edge and Nd L3-edge spectra were collected as proxies for heavy and light REE, respectively, and compared to natural and synthetic REE-bearing standards. Extended X-ray absorption fine structure data yield best fits for Y in six-fold coordination with Y–O distances of 2.24–2.32 Å, and a second coordination sphere comprising Fe, Na, Ca, Si and O at radial distances of 3.6–3.8 Å. These findings are consistent with dominant Y3+ substitution for Ca2+ on the octahedral M1 site in all the samples studied, and exclude preferential substitution of Y3+ onto the smaller octahedral Z site or the large low-symmetry N4 site. Using lattice strain theory, we constructed relative partitioning models to predict site preferences of lanthanides we have not measured directly. The models predict that all REE are favoured on the Ca-dominant M1 site and that preferential partitioning of heavy over light REE increases in EGM containing significant Mn in the M1-octahedral rings (oneillite subgroup). Thus, the flat REE profiles that make EGM such attractive exploration targets are not due to preferential partitioning of light and heavy REE onto different sites. Instead, local ordering of Mn- and Ca-occupied M1 sites may influence the capacity of EGM to accommodate heavy REE.Publisher PDFPeer reviewe

Mantle sources and magma evolution in Europe's largest rare earth element belt (Gardar Province, SW Greenland) : new insights from sulfur isotopes

This work is a contribution to the HiTech AlkCarb project and was funded by the European Union's Horizon 2020 research and innovation programme under grant agreement No. 689909. W.H. also acknowledges support from a UKRI Future Leaders Fellowship (MR/S033505/1). A.J.B. is funded by the NERC National Environment Isotope Facility award (NE/S011587/1) and the Scottish Universities Environmental Research Centre.Alkaline igneous complexes are often rich in rare earth elements (REE) and other metals essential for modern technologies. Although a variety of magmatic and hydrothermal processes explain the occurrence of individual deposits, one common feature identified in almost all studies, is a REE-enriched parental melt sourced from the lithospheric mantle. Fundamental questions remain about the origin and importance of the mantle source in the genesis of REE-rich magmas. In particular, it is often unclear whether localized enrichments within an alkaline province reflect heterogeneity in the mantle source lithology (caused by prior subduction or plume activity) or variations in the degree of partial melting and differentiation of a largely homogeneous source. Sulfur isotopes offer a means of testing these hypotheses because they are unaffected by high temperature partial melting processes and can fingerprint different mantle sources. Although one must be careful to rule out subsequent isotope fractionation during magma ascent, degassing and crustal interactions. Here, we present new S concentration and isotope (δ34S) measurements, as well as a compilation of major and trace element data, for a suite of alkaline magmatic units and crustal lithologies from the Mesoproterozoic Gardar Province. Samples span all phases of Gardar magmatism (1330–1140 Ma) and include regional dykes, rift lavas and the alkaline complexes Motzfeldt and Ilímaussaq, which represent two of Europe's largest REE deposits. We show that the vast majority of our 115 samples have S contents >100 ppm and δ34S of −1 to 5‰. Only 8 samples (with low S contents, <100 ppm) show evidence for crustal interactions, implying that the vast majority of Gardar melts preserve the S isotopic signature of their magma source. Importantly, samples from across the Gardar Province δ34S have above the canonical mantle range (≤−1.4‰) and therefore require recycled surface S in their mantle source. Elevated values are explained by a period of Andean-style subduction and mantle metasomatism which took place ∼500 Ma before rift onset and are also supported by trace elements signatures (e.g. Ba/La) which match modern subduction zones. Comparing the various generations of Gardar magmas, we find that δ34S  values, large ion lithophile elements (K, Ba, P) and selective incompatible elements (Nb and light REE) are particularly enriched in the Late Gardar dykes, alkaline complexes and clusters of silica-undersaturated dykes spatially associated with the alkaline complexes. These data indicate that subduction-related metasomatism of the Gardar mantle was spatially heterogeneous, and that alkaline complexes are sourced from localized mantle domains highly enriched in 34S, REE, alkalis and volatiles (particularly, F). Since alkalis and volatiles play an essential role in driving extreme differentiation of alkaline melts and fluids, we suggest the co-location of these species plus incompatible metals at high concentrations in the lithospheric mantle is a critical first-step in the genesis of a world-class alkaline REE deposit. S isotopes are powerful tools for identifying enriched mantle domains and the sources of mineralized alkaline igneous bodies.Publisher PDFPeer reviewe

Hydrothermal alteration of eudialyte-hosted critical metal deposits : fluid source and implications for deposit grade

MV, AB and AF were funded by the NERC-funded SOS RARE consortium, grant number NE/M010856/1.Eudialyte-hosted critical metal deposits potentially represent major sources of rare earth elements (REE), zirconium and niobium. Here, we study the chemical and isotopic composition of fresh and altered eudialyte in nepheline syenite from the Ilímaussaq Complex, Greenland, one of the world’s largest known eudialyte-hosted deposits. Late-magmatic hydrothermal alteration caused partial replacement of primary magmatic eudialyte by complex pseudomorph assemblages of secondary Zr-, Nb-, and REE-minerals. Three secondary assemblage types are characterised by the zirconosilicates catapleiite, gittinsite and zircon, respectively, of which the catapleiite type is most common. To investigate elemental exchange associated with alteration and to constrain the nature of the metasomatic fluids, we compare trace elements and Sm/Nd isotope compositions of unaltered eudialyte crystals and their replaced counterparts from five syenite samples (three catapleiite-type, one gittinsite-type, and one zircon-type assemblage). Trace element budgets for the catapleiite-type pseudomorphs indicate a 15–30% loss of REE, Ta, Nb, Zr, Sr and Y relative to fresh eudialyte. Moreover, the gittinsite- and zircon-type assemblages record preferential heavy REE (HREE) depletion (≤50%), suggesting that the metasomatic fluids mobilised high field strength elements. Initial Nd isotope ratios of unaltered eudialyte and catapleiite- and gittinsite-type pseudomorphs are indistinguishable, confirming a magmatic fluid origin. However, a higher initial ratio and stronger HREE depletion in the zircon-type pseudomorphs suggests a different source for the zircon-forming fluid. Although alteration reduces the metal budget of the original eudialyte volume, we infer that these elements re-precipitate nearby in the same rock. Alteration, therefore, might have little effect on overall grade but preferentially separates heavy and light REE into different phases. Targeted processing of the alteration products may access individual rare earth families (heavy vs. light) and other metals (Zr, Nb, Ta) more effectively than processing the fresh rock.Publisher PDFPeer reviewe

Adsorption of rare earth elements in regolith-hosted clay deposits

Global resources of heavy Rare Earth Elements (REE) are dominantly sourced from Chinese regolith-hosted ion-adsorption deposits in which the REE are inferred to be weakly adsorbed onto clay minerals. Similar deposits elsewhere might provide alternative supply for these high-tech metals, but the adsorption mechanisms remain unclear and the adsorbed state of REE to clays has never been demonstrated in situ. This study compares the mineralogy and speciation of REE in economic weathering profiles from China to prospective regoliths developed on peralkaline rocks from Madagascar. We use synchrotron X-ray absorption spectroscopy to study the distribution and local bonding environment of Y and Nd, as proxies for heavy and light REE, in the deposits. Our results show that REE are truly adsorbed as easily leachable 8- to 9-coordinated outer-sphere hydrated complexes, dominantly onto kaolinite. Hence, at the atomic level, the Malagasy clays are genuine mineralogical analogues to those currently exploited in China

Alkaline-Silicate REE-HFSE Systems

Development of renewable energy infrastructure requires critical raw materials, such as the rare earth elements (REEs, including scandium) and niobium, and is driving expansion and diversification in their supply chains. Although alternative sources are being explored, the majority of the world’s resources of these elements are found in alkaline-silicate rocks and carbonatites. These magmatic systems also represent major sources of fluorine and phosphorus. Exploration models for critical raw materials are comparatively less well developed than those for major and precious metals, such as iron, copper, and gold, where most of the mineral exploration industry continues to focus. The diversity of lithologic relationships and a complex nomenclature for many alkaline rock types represent further barriers to the exploration and exploitation of REE-high field strength element (HFSE) resources that will facilitate the green revolution. We used a global review of maps, cross sections, and geophysical, geochemical, and petrological observations from alkaline systems to inform our description of the alkaline-silicate REE + HFSE mineral system from continental scale (1,000s km) down to deposit scale (~1 km lateral). Continental-scale targeting criteria include a geodynamic trigger for low-degree mantle melting at high pressure and a mantle source enriched in REEs, volatile elements, and alkalies. At the province and district scales, targeting criteria relate to magmatic-system longevity and the conditions required for extensive fractional crystallization and the residual enrichment of the REEs and HFSEs. A compilation of maps and geophysical data were used to construct an interactive 3-D geologic model (25-km cube) that places mineralization within a depth and horizontal reference frame. It shows typical lithologic relationships surrounding orthomagmatic REE-Nb-Ta-Zr-Hf mineralization in layered agpaitic syenites, roof zone REE-Nb-Ta mineralization, and mineralization of REE-Nb-Zr associated with peralkaline granites and pegmatites. The resulting geologic model is presented together with recommended geophysical and geochemical approaches for exploration targeting, as well as mineral processing and environmental factors pertinent for the development of mineral resources hosted by alkaline-silicate magmatic systems

Impact of the Introduction of Calcimimetics on Timing of Parathyroidectomy in Secondary and Tertiary Hyperparathyroidism

Hyperparathyroidism (HPT), both secondary and tertiary, is common in patients with end-stage renal disease, and is associated with severe bone disorders, cardiovascular complications, and increased mortality. Since the introduction of calcimimetics in 2004, treatment of HPT has shifted from surgery to predominantly medical therapy. The aim of this study was to evaluate the impact of this change of management on the HPT patient population before undergoing (sub-)total parathyroidectomy (PTx). Overall, 119 patients with secondary or tertiary HPT undergoing PTx were included in a retrospective, single-center cohort. Group A, who underwent PTx before January 2005, was compared with group B, who underwent PTx after January 2005. Patient characteristics, time interval between HPT diagnosis and PTx, and postoperative complications were compared. Group A comprised 70 (58.8 %) patients and group B comprised 49 (41.2 %) patients. The median interval between HPT diagnosis and PTx was 27 (interquartile range [IQR] 12.5-48.0) and 49 (IQR 21.0-75.0) months for group A and B, respectively (p = 0.007). Baseline characteristics were similar among both groups. The median preoperative serum parathyroid hormone (PTH) level was 936 pg/mL (IQR 600-1273) for group A versus 1091 pg/mL (IQR 482-1373) for group B (p = 0.38). PTx resulted in a dramatic PTH reduction (less than twofold the upper limit: A, 80.0 %; B, 85.4 %), and postoperative complication rates were low in both groups (A: 7.8 %; B: 10.2 %) [p = 0.66]. The introduction of calcimimetics in 2004 is associated with a significant 2-year delay of surgery with continuously elevated preoperative PTH levels, while parathyroid surgery, even in a fragile population, is considered a safe and effective procedure

Zahvala autorima Sestrinski glasnik/Nursing Journal 2013 godina Thanking to authors Sestrinski glasnik/Nursing Journal year 2013

Earth’s surface and mantle sulphur reservoirs are connected via subduction, crustal recycling and volcanism. Although oceanic hotspot lavas currently provide the best constraints on the deep sulphur cycle, their restricted age range (&lt;200 Ma) means they cannot reveal temporal variations in crustal recycling over Earth history. Sulphur-rich alkaline magmas offer the solution because they are associated with recycled sources (i.e. metasomatized lithospheric mantle and plumes) and, crucially, are found throughout the geological record. Here, we present a detailed study of sulphur isotope fractionation in a Mesoproterozoic alkaline province in Greenland and demonstrate that an enriched subduction-influenced source (δ34S of +1 to +5‰) can be reconstructed. A global δ34S compilation reveals secular variation in alkaline magma sources which support changes in the composition of the lithospheric mantle and/or Ga timescales for deep crustal recycling. Thus, alkaline magmas represent a powerful yet underutilized repository for interrogating crustal recycling through geological time

Alkaline-Silicate REE-HFSE Systems

Development of renewable energy infrastructure requires critical raw materials, such as the rare earth elements (REEs, including scandium) and niobium, and is driving expansion and diversification in their supply chains. Although alternative sources are being explored, the majority of the world’s resources of these elements are found in alkaline-silicate rocks and carbonatites. These magmatic systems also represent major sources of fluorine and phosphorus. Exploration models for critical raw materials are comparatively less well developed than those for major and precious metals, such as iron, copper, and gold, where most of the mineral exploration industry continues to focus. The diversity of lithologic relationships and a complex nomenclature for many alkaline rock types represent further barriers to the exploration and exploitation of REE-high field strength element (HFSE) resources that will facilitate the green revolution. We used a global review of maps, cross sections, and geophysical, geochemical, and petrological observations from alkaline systems to inform our description of the alkaline-silicate REE + HFSE mineral system from continental scale (1,000s km) down to deposit scale (~1 km lateral). Continental-scale targeting criteria include a geodynamic trigger for low-degree mantle melting at high pressure and a mantle source enriched in REEs, volatile elements, and alkalies. At the province and district scales, targeting criteria relate to magmatic-system longevity and the conditions required for extensive fractional crystallization and the residual enrichment of the REEs and HFSEs. A compilation of maps and geophysical data were used to construct an interactive 3-D geologic model (25-km cube) that places mineralization within a depth and horizontal reference frame. It shows typical lithologic relationships surrounding orthomagmatic REE-Nb-Ta-Zr-Hf mineralization in layered agpaitic syenites, roof zone REE-Nb-Ta mineralization, and mineralization of REE-Nb-Zr associated with peralkaline granites and pegmatites. The resulting geologic model is presented together with recommended geophysical and geochemical approaches for exploration targeting, as well as mineral processing and environmental factors pertinent for the development of mineral resources hosted by alkaline-silicate magmatic systems

Expression, localization and polymorphisms of the nuclear receptor PXR in Barrett's esophagus and esophageal adenocarcinoma

Background: The continuous exposure of esophageal epithelium to refluxate may induce ectopic expression of bile-responsive genes and contribute to the development of Barrett's esophagus (BE) and esophageal adenocarcinoma. In normal physiology of the gut and liver, the nuclear receptor Pregnane × Receptor (PXR) is an important factor in the detoxification of xenobiotics and bile acid homeostasis. This study aimed to investigate the expression and genetic variation of PXR in reflux esophagitis (RE), Barrett's esophagus (BE) and esophageal adenocarcinoma.Methods: PXR mRNA levels and protein expression were determined in biopsies from patients with adenocarcinoma, BE, or RE, and healthy controls. Esophageal cell lines were stimulated with lithocholic acid and rifampicin. PXR polymorphisms 25385C/T, 7635A/G, and 8055C/T were genotyped in 249 BE patients, 233 RE patients, and 201 controls matched for age and gender.Results: PXR mRNA levels were significantly higher in adenocarcinoma tissue and columnar Barrett's epithelium, compared to squamous epithelium of these BE patients (P < 0.001), and RE patients (P = 0.003). Immunohistochemical staining of PXR showed predominantly cytoplasmic expression in BE tissue, whereas nuclear expression was found in adenocarcinoma tissue. In cell lines, stimulation with lithocholic acid did not increase PXR mRNA levels, but did induce nuclear translocation of PXR protein. Genotyping of the PXR 7635A/G polymorphism revealed that the G allele was significantly more prevalent in BE than in RE or controls (P = 0.037).Conclusions: PXR expresses in BE and adenocarcinoma tissue, and showed nuclear localization in adenocarcinoma tissue. Upon stimulation with lithocholic acid, PXR translocates to the nuclei of OE19 adenocarcinoma cells. Together with the observed association of a PXR polymorphism and BE, this data implies that PXR may have a function in prediction and treatment of esophageal disease

Опыт использования акустического доплеровского измерителя течений (АDCP) в условиях Черного моря

В статье излагается методика проведения измерений Lowered ADCP и обработки первичной информации. При последующей обработке данных широко использовался опыт МГИ НАНУ с аналогичными акустическими измерителями течений в 80-е гг. В результате обобщен опыт применения Lowered ADCP в условиях Черного моря, даны алгоритмы обработки данных, приведены профили абсолютной скорости течений на ряде станций и показано, что предлагаемый подход дает более адекватную качественную и количественную оценку профиля скорости течения, чем известные методы.The methods of measurements with Lowered ADCP and processing of the initial information are presented. During the following data processing the experience of Marine Hydrophysical Institute of NAS of Ukraine with the similar acoustic currents meters in the 80-ies was widely applied. As a result the experience of Lowered ADCP application under the Black Sea conditions is generalized, the algorithms of data processing are given, the profiles of absolute speed of currents are given on the series of stations. It is shown that the proposed approach provides more adequate qualitative and quantitative estimation of the current velocity profile than the known methods do