Apatite Minerals Research Articles

Typochemistry and possible sources of ferrosaponite with Ce–Cu–Ni from the metabasalts of the Northern Ural

We studied metabasites from metamorphic complexes located in the northern part of the Lyapin anticlinorium of the Subpolar Urals and the Kharbey anticlinorium in the Polar Urals of the Central Ural Uplift, which are part of the Arctic zone. For the first time, ferrosaponite containing copper, nickel, and rare earth metals has been identified in these metabasites. The morphological and typochemical characteristics of ferrosaponite were examined using electron microscopy. In the Polar Urals, ferrosaponite is found in the almandine eclogite of the Marunkeu eclogite-amphibolite gneiss. The mineral is associated with garnet, quartz, pyroxene, muscovite, amphibole, and sulfides. The general formula for the mineral from almandine eclogite: (Ca0,06–0,27K0,01–0,06Се0,01)∑0,13–0,31(Fe2+ 1,67–2,21Mg0,51–0,84 Cu0,01–0,09Ni0,03–0,11)∑2,25–3,08[(Si2,84–3,08Al0,92–1,16)∑4,00O10](OH)2 ×3,55–3,83H2O. In the Subpolar Urals, this mineral was examined in a sample of garnet-amphibole-biotite-plagioclase-quartz shale, where it occurs in association with other minerals: amphibole, plagioclase, quartz, epidote, biotite, zircon, albite, titanite, apatite, and sulfides. The general formula of the mineral: (Ca0,14–0,22K0,01–0,02Се0,01)∑0,15–0,23(Fe2+ 1,24–2,22Mg0,76–0,97)∑2,17–3,15 [(Si2,86–2,96Al1,04–1,14)∑4,00O10](OH)2 ×3,41–4,47H2O. It is assumed that ferrosaponite forms through a hydrothermal-metamorphic process during the late fluid stage of rock transformation. Feldspars and biotite serve as sources of potassium and aluminum, while hornblende, pyroxenes, and epidote are the primary suppliers of magnesium and iron. In the chemical composition, alongside the main components of the mineral—potassium, calcium, magnesium, aluminum, silicon, and iron—copper, nickel, and rare earth metals were also detected. Under the influence of fluids, copper and nickel may have been derived from replaced sulfides, while cerium could have been introduced from allanite, apatite, and other minerals containing rare earth elements. Continued study of the mineragenic features of metamorphic rocks in the Arctic regions of the Urals is essential for a comprehensive assessment of their resource potential, as well as promising sources and concentrators of rare metals.

Circular economy strategies in sedimentary phosphate mine reclamation: Development of technosol from phosphate waste rock

Proper management of mine waste plays a crucial role in minimizing environmental impacts. One potential solution to tackle this problem involves transforming mine waste rock into soil to facilitate the process of mine restoration. The aim of this study was to assess the mineralogical, chemical, and physical characteristics of technosol derived from phosphate mine waste dumps. Following this evaluation, a novel rehabilitation strategy was proposed. For this purpose, a total of 32 samples were systematically collected across a 4 ha area of technosols, which had been established in accordance with the waste rock soil rehabilitation strategy involving geomorphic reshaping. According to the findings, phosphate mining left the soil with a sandy texture, resulting in a degraded soil structure with severely unfavorable crop growth conditions, notably poor stability, and low water retention. The chemistry of the studied soils was characterized by the dominance of CaO (29.02 wt%± 1.01) > SiO2 (27.61 wt% ± 0.61) > P2O5 (11.34 wt% ± 0.23) > MgO (5.97 wt%±0.16). Mineralogically, the samples were mainly formed by quartz, dolomite, calcite, apatite, and clay minerals. The prevalence of dolomite played a significant role in enhancing the accessibility of Mg as an essential nutrient and the occurrence of apatite in the soil resulted in the presence of P2O5. However, the abundance of Ca was linked to three major minerals: calcite, apatite, and dolomite. X-ray fluorescence analyses demonstrated that the concentrations of Fe2O3, K2O, and SO3 did not exceed 2 wt%.Organic matter, represented by SOC <0.2% and N < 0.02%, demonstrated an extraordinary deficiency in the study area. The analysis of element bioavailability confirmed that the soil was rich in Ca (10383,26 mg/kg), Mg (278,47 mg/kg), Zn (12,82 mg/kg), and Cu (3,7 mg/kg) but deficient in other essential nutrients such as P, K, S, Mn, and Fe. Our research results provide a set of recommendations aimed at enhancing existing mine rehabilitation practices applicable to both pre- and post-rehabilitation phases, leveraging automated mineralogy and circular economy principles. Notably, we propose a rehabilitation strategy to be implemented prior to the geomorphic reshaping phase, which is intended to reduce costs and efforts associated with soil reconstitution.

Bioactive surface modification of Ti–Nb alloy by alkaline treatment in potassium hydroxide solution

Abstract The aim of this work is to compare the responsive behaviour of titanium, niobium and titanium–niobium alloy during alkaline treatment in forming alkaline titanate layer and their resultant bioactive properties. Titanium and niobium powder mixture with composition in the beta region was pressed at 550 MPa and sintered at 1,200 °C for 2 h. The alloy was soaked in potassium hydroxide aqueous solution at 60 °C for 24 h with different concentrations of 0.5 M and 5 M. The effect of post sintering-heat treatment was investigated by annealing the treated alloy at 600 °C for 2 h. X-ray diffraction analysis and Fourier transform infrared spectroscopy analysis were used to evaluate the chemical composition and the functional group of material on the treated alloy surface respectively. Immersion in Hanks solution for 1 day resulted in traces of calcium and phosphate on alloy surfaces treated in different concentrations of alkali as well as post-heat treatment. The cell viability evaluation using MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) assay on the new beta-Ti alloy with potassium-based titanate layer demonstrated potassium hydroxide treatment with a 5 M concentration after post-heat treatment significantly improved cell proliferation, which is a prerequisite for bone mineral apatite deposition.

Coordinated microanalysis of volatiles in apatite and silicate minerals in ancient lunar basalts

Despite being essentially water-free, nominally anhydrous minerals such as plagioclase and pyroxene represent the biggest reservoir of water in most lunar rocks due to their sheer abundance. Apatite, which incorporates F, Cl, and OH into its mineral structure as essential crystal components, on the other hand, is the only other volatile-bearing phase common in lunar samples. Here, we present the first coordinated study of volatiles (e.g., H2O, Cl, F, and S) in nominally anhydrous minerals combined with isotopic measurements in apatite from the ancient lunar basalt fragments from meteorite Miller Range (MIL) 13317. Apatite in MIL 13317 basalt contains ∼ 2000 ppm H2O and has an elevated δD values (+ 523–737 ‰), similar to Apollo mare basalts, but has high δ37Cl values (+ 29–36 ‰), similar to apatite found in several KREEP-rich samples. MIL 13317 is unique compared with other lunar basalts; it has both elevated δD and δ37Cl values currently only observed in highlands sample 79215 (a granulitic impactite). Based on measurements of H2O in nominally anhydrous minerals and in apatite, the source magma of MIL 13317 basalt is estimated to contain ∼ 130–330 ppm H2O. Assuming reasonable levels of partial melting of the lunar mantle and magmatic degassing during eruption of the basalt, the Moon contained at least one reservoir with < 100 ppm H2O, a δD value of < 0 ‰ similar to carbonaceous chondrites, and extensively fractionated Cl isotopes prior to 4.332 Gyr, the crystallization age of the MIL 13317 basalt.

Petrochemistry and Tectonic Setting of the Phroa-Wiang Pa Pao Granitic Rocks, Chiang Mai, and Chiang Rai Provinces, Central Granitic Belt of Thailand

The Phrao-Wiang Pha Phao granitic rocks are crop out along Highway Number 1150 (Phrao-Wiang Pa Pao) in Chiang Mai and Chiang Rai provinces. The geologic investigation as field observation, lithology, petrography, geochemistry, and tectonic interpretation applied for this study. The least-altered 19 rock samples were collected and performed in stained rock slabs for modal analysis and standard thin sections for petrographic analysis. Based on the Quartz-Alkali Feldspar-Plagioclase diagram for plutonic rocks, the rock samples in the Phrao area are granodiorite, and one is biotite-monzogranite, while most of the rock samples in the Wiang Pa Pao area are biotite-monzogranite. The petrographic investigation for rock samples indicated that granitic samples have medium to coarse-grained and show porphyritic texture. The orthoclase phenocrysts are sitting in the groundmass and are composed of quartz, plagioclase, and orthoclase feldspar, with a minor amount of biotite, muscovite, apatite, zircon, titanite, and opaque minerals. The granitic samples can be classified as granodiorite to monzogranite, which is high-K calc-alkalic affinity and peraluminous S-type based on geochemistry. Based on the normative mineralogy calculation, the rock samples were composed mainly of normative quartz, plagioclase, and orthoclase, with minor corundum, hypersthene, magnetite, ilmenite, apatite, zircon, and chromite. The S-type granitoid supported by normative corundum and Na2O/K2O ratios less than 0.49 at Na2O ranging from 1.53 - 2.35 wt %. Their tectonic setting of formation appears to be a post-orogenic environment (post-collisional granite) of the Sibumasu and the Indochina blocks. The Phrao Phrao-Wiang Pha Phao granitic rocks are a part of the Central Granitic Belt and are related to tin-tungsten deposits with rare earth elements. HIGHLIGHTS Tectonic setting of the Phroa-Wiang Pa Pao Granitic Rocks, Thailand. Petrography and modal analysis The geochemistry analysis by XRF and CIPW normative calculation. The Central Granitic Belt in Thailand. GRAPHICAL ABSTRACT

The Ain Dibba and Ain Kissa phosphorites, Tebessa (NE Algeria): REE depletion versus shallow, open depositional environment during the Paleocene-Eocene phosphogenesis in North Africa

The Ain Dibba and Ain Kissa phosphorites, located north of Tebessa town, NE Algeria, belong to the Upper Cretaceous-Paleocene-Eocene Afro-Arabian phosphatic province that extends from Morrocco to the Middle East. These two phosphorite showings, which were partly exploited at the beginning of the 20th century, were deposited during the Late Paleocene (Thanetian) times on the northern basin of the Kasserine Paleo-Island. Although they are not yet economically very important, the present petrological and geochemical study contribute highly to the knowledge of their critical trace and REE contents as well as the understanding of their paleo-depositional environment. Petrographic and XRD data show that these phosphorites are mainly composed of pellets, coprolites, bioclasts and rare glauconite, gypsum, quartz grains and zeolites. These constituents are cemented by calcareous, siliceous or rarely clayey matrix. The pellets and coprolites are composed mainly of cryptocrystalline carbonate fluor-apatite (CFA). The XRF and ICP-MS chemical analyses of these phosphorites, show they are not as rich as those from Kef Essenoun and Bled El Hadba southern basin, neither in P2O5 nor in REE contents. P2O5 concentrations range from 14.16 to 26.57 wt% (average = 20.24 ± 4.33 wt%, n = 15), with only one sample having 31.89 wt% P2O5, whereas ΣREE contents range from 171 to 344 ppm (average = 252 ± 69 ppm, n = 9) and, therefore, considered as moderately REE-enriched phosphorites. Ce anomaly values display a decrease from the lower to the upper phosphorite sub-layers (from −0.57 down to −0.72), suggesting an increase from relatively sub-oxic to more oxic conditions. The Eu anomalies range from 0.89 to 1.35 for Ain Dibba and from 0.93 to 1.35 for Ain Kissa phosphorites. The highest Ce/Ce∗ and lowest Eu/Eu∗ anomalies are recorded in the lower layers, often enriched in both REE and glauconite contents, whereas the lowest Ce/Ce∗ and highest Eu/Eu∗ anomalies, reflecting more oxic conditions, are characteristics of the glauconite-free and REE-poor upper layers. The gradual timewise transition from relatively sub-oxic to oxic conditions (from the lower to the upper layers) is also recorded in the redox-sensitive (Cr, Ni, V, U) trace element data. This implies that during early diagenesis, the sedimentary environment became slightly reduced, which enabled intensive uptake of both REE and some trace element (e.g., Cr, V, Ni, U) mainly from pore-water through substitution and adsorption mechanisms onto apatite and glauconite minerals. This is noticed especially in the lower phosphorite layers of both Ain Dibba and Ain Kissa deposits. In a larger scale, the Ain Dibba and Ain Kissa phosphorites show lower REE contents, lower Ce and Eu anomalies, and lower redox-sensitive trace element contents than those of the southern (Kef Essenoun and Bled El Hadba) and eastern (Tunisian) basins of the Kasserine paleo-Island. These geochemical features indicate that phosphorites from the northern basin were deposited, through upwelling current, in a more open, shallower, oxygenated and agitated environment during the Paleocene-Eocene phosphogenesis in North Africa and Middle East.

Hydrothermal alteration and elemental mass balance for the Surda Copper Deposit, Singhbhum Shear Zone, Eastern India: implications for both copper and magnetite–apatite mineralization

This paper explores the geological relationships, mineralogical and geochemical characteristics, and quantitative elemental mass balance constraints of the hydrothermal alteration zones within the uraniferous Surda copper deposit in the Singhbhum Shear Zone in eastern India, which is affiliated with an iron oxide–copper–gold system. Five distinct alteration zones are identified: a proximal potassic (biotitization) zone containing magnetite–apatite; a central chloritization zone containing copper, uranium, gold and magnetite; distal silicification (quartz) and albitization zones; and a transitional chlorite–sericitization zone. Evidence suggests these zones originated from mafic precursors linked to a subduction zone. Magnetite mineralization shows both magmatic ( δ 18 O + 2.0 to +4.8‰) and hydrothermal ( δ 18 O + 0.4 to +0.6‰) signatures. Hydrothermal magnetite–apatite formed at temperatures of 440 to 550°C, with continued crystallization at lower temperatures (280 to 360°C) concurrent with copper sulfide and uranium precipitation from an Fe-rich, isotopically heavy fluid ( δ 34 S + 4.55 to +9.66‰). Major elements (Ca, Na, Mg) and some minor and rare earth elements decrease from weakly altered mafic rocks to late alteration zones, reflecting the breakdown of Ca-bearing hornblende, biotite and plagioclase. Potassium decreases from early to late alteration zones due to mineral transformations. Mass-balanced geochemical data align with hydrothermal alteration mineral assemblages, indicating processes such as mineral dissolution, element absorption and sulfide behaviour. Overall, the study highlights the complex hydrothermal alteration processes shaping the Surda copper deposit and provides insights into ore formation mechanisms.

Decoding Apatite in Volcanic Carbonatitic breccia from Mongra, Northwest of Amba Dongar Carbonatite Complex, Gujarat, India: Insights to Genesis &amp; Rare Earth Element Budgets

Chemical variations in apatite in context to carbonatites and trace element partitioning between apatites and carbonatite-rich liquids are important in assessing the petrogenesis and evolution of the carbonatites as well as the associated carbonatitic breccia due to apatite's sensitivity to surrounding magma composition. Volcanic carbonatitic breccia is one of the constituent rock types found outside the ring structure of the Amba Dongar Carbonatite Complex (ADC) situated in western India. In the present work, we report the mineral chemistry of apatites from the carbonatitic breccias of the Mongra region (ADC outer core) and compare them to apatites from ADC carbonatites. Apatite chemistry from Mongra displays a larger concentration of rare earth elements, manganese, and chlorine when compared to those of ADC carbonatites. Morphology and distinct zoning of these apatites represent late-stage magmatic processes with high heavy rare earth element concentrations (high Lutetium), followed by interaction of fluids from the surrounding alkaline rocks. Variation in sulphur concentration in the apatites of this study indicates crystallisation under mildly reducing conditions. Integrated field observations, petrography, and apatite mineral chemistry from the Mongra region allow for an understanding of the genesis of apatites in the ADC outer core, with possible implications for late-stage mineral-melt interactions.

Linking beryllium mineralization to fluid-rock reactions: A case study of the Madumeng quartz vein-type beryllium mineralization in the Southern Great Xing'an Range, Northeast China

The Southern Great Xing'an Range (SGXR) in Northeast China is a significant polymetallic mineralization belt. Although several beryllium (Be) deposits have been reported in the SGXR, the timing and mechanisms of Be mineralization are poorly understood. To determine the mechanisms of newly-discovered Be mineralization in the Madumeng area, we carried out monazite–zircon–apatite U–Pb dating, whole-rock and mineral geochemical, and monazite Nd isotopic analyses of the beryl-bearing quartz veins and host Late Permian–Early Triassic granite. Monazite from the beryl-bearing quartz veins yielded U–Pb ages of 138–137 Ma, and the host granite yielded zircon and apatite U–Pb ages of 251 ± 1 and 256 ± 27 Ma, which indicate that the Madumeng Be mineralization formed later than the host granite. Monazite in the beryl-bearing veins has similar εNd(t) values (−1.31 to +4.27) to those of Early Cretaceous highly fractionated granite related to Be mineralization in the SGXR, which suggests the ore-forming material was derived from exsolved fluids associated with Early Cretaceous, deep-seated, highly fractionated granites. Fluid-rock reactions had a key role in generating the Madumeng Be mineralization, and the intensity of these reactions was recorded by the whole-rock and mineral geochemistry. The alteration during fluid-rock reactions increased the pH and Ca contents of the fluids. Mica and beryl record the release of Ca and Fe from the granite into the fluid. The released Ca2+ ions combined with F− ions in the fluid, leading to instability of Be–F complexes and subsequent precipitation of beryl. Our findings indicate that the Early Cretaceous was an important period of Be mineralization in the SGXR and highlight the contribution of fluid-rock reactions to Be precipitation in quartz vein-type Be mineralization.

Uranium partitioning between apatite and hydrothermal fluids at 150–250 °C

This experimental study is focused on the immobilization of dissolved uranium (U) via its entrapment by apatite at hydrothermal conditions. Experiments on apatite crystallization were conducted in 0.5 M sodium chloride (NaCl) solutions at temperatures of 150, 200, and 250 °C. Uranium was introduced into the system as a solid compound (UO3), which controlled the concentration of dissolved U in the hydrothermal fluids. The results showed that U contents in apatite exceed U concentrations in co-existing fluid by 2–3 orders of magnitude. Apparent Nernst partition coefficients (DU) and exchange coefficient (KU/Ca) were evaluated. Experimentally determined DU values were consistent with DU predicted by the Lattice Strain Model at 200 and 250 °C. The obtained KU/Ca values shows dependence on temperature. The results lay the foundation for further assessment of uranium immobilization in apatite and other minerals at repository conditions.

Investigation of characteristics and application of food waste-derived bone char on plant growth

Waste bone, a by-product originating from animal husbandry and food industry, primarily ends up in landfills and may cause soil pollution if no treatment method is applied. In this article, pork bone char (PBc), a porous carbonaceous material, was manufactured by pyrolyzing waste pork bones collected from food waste sources. The investigation covered temperatures from 400 to 800 °C in limited oxygen conditions. The prepared PBc samples were characterized and applied as an alternative source of phosphorus fertilizer by evaluating the growth of Ipomoea aquatica planted on the PBc/soil mixture and assessing the properties of SPBc.As a result, the PBc materials exhibit a clear hydroxyapatite mineral structure along with an abundance of micro-mesoporous features. The SPBc samples demonstrate a significant change in phosphorus concentration (up to 1.6 %) compared to PBc non-amended soil, and the growth of the Ipomoea aquatica plant differed significantly from the plant not fertilized by PBc. The results after four weeks indicate that samples added with PBc synthesized at temperatures of 500, 600, and 700 °C promoted its vigorous growth corresponding to the ratio of Ca/P of hydroxyapatite. The specific surface area, pore volume, and average pore size by various pyrolysis temperatures can impact the release of phosphorus from the PBc into the soil, significantly influencing the growth of Ipomoea aquatica. The achieved outcome not only presents a promising substance for reducing reliance on conventional phosphorus fertilizers derived from apatite minerals but also establishes a means to pursue the objectives of sustainable development and a circular economy.

Magmatic degassing and fluid metasomatism promote compositional variation from I-type to peralkaline A-type granite in the late Cretaceous Fuzhou felsic complex, SE China

Abstract A-type granites generally have much lower water, higher temperature, and incompatible element concentrations than I-type granitoids. Yet it remains unclear why I-A-type granitic complexes occur in convergent plate margins. Here we conduct geochemical analyses on apatite and mafic minerals from the late Cretaceous I-A-type granitic complex in Fuzhou area, SE China, aiming to decipher differentiation, fluid metasomatism, and degassing that primarily control the compositional diversity of felsic magmas. Apatites in both rock types are F-rich and show large H2O and δD variations, i.e., 341–3892 ppm H2O and –325 to +336‰ δD in I-type granitoids; 67–1366 ppm H2O and –251 to +1439‰ δD in A-type granites. H2O in apatite is negatively correlated with La/Sm and Sr/Y in the I-type granitoids, whereas it is positively correlated with Ce and total rare earth element (REE) concentrations in the A-type granites. Once H2O increases up to hundreds of ppm, both rock types show a rapid decrease of H2O/Ce, an increase of F/Cl, and extensive H isotope fractionation. Arfvedsonite occurs as a late crystallizing mineral in the A-type granite and has much higher contents of Na2O, K2O, F, and high field strength elements (HFSE) than hornblende in the I-type granitoids, indicating the addition of F-HFSE-rich alkaline fluids during its magmatic evolution. The consumption of arfvedsonite and formation of aegirine further indicate the role of fluid metasomatism and H2 degassing via a reaction of 3Na3Fe5Si8O22(OH)2 + 2H2O = 9NaFeSi2O6 + 2Fe3O4 + 6SiO2+5H2. The combined geochemical data demonstrate that the systematic differences in mineral assemblage, whole-rock composition, magma temperature, H2O content, and δD of apatite between the I- and A-type granites are likely attributed to varying degrees of differentiation, fluid metasomatism and magmatic degassing. The I-type granitoids experienced hornblende, biotite, plagioclase, K-feldspar, and apatite fractionation and close-system degassing. The A-type granite was likely formed from the I-type monzogranitic magma that was metasomatized by the mantle-derived F-HFSE-rich alkaline fluids to produce the peralkaline magma, which further experienced K-feldspar + plagioclase + biotite + apatite fractionation and open-system degassing. Further numerical estimation indicates that the primary magma of Fuzhou granitic complex contained ~3.0 wt% H2O, and the lower water content of A-type granite was likely attributed to strong degassing during its emplacement. Our results indicate that some peralkaline A-type granites can be generated from relatively water-poor I-type granitic magmas by fluid metasomatism and degassing.

Uranium enrichment driven by paleomarine condition and event deposition: Insights from the lower Cambrian Niutitang Formation organic-rich shales in northeastern Guizhou, South China

Organic-rich shale related uranium (U) mineralization has attracted widespread attention as a strategic and clean alternative to fossil energy and a paleoceanic redox proxy. A comprehensive study of mineralogy, organic geochemistry and elemental geochemistry of the lower Cambrian Niutitang Formation organic-rich shales in northeastern Guizhou, South China was conducted to address this issue. SEM-EDS results showed that the U occurrence state in the Niutitang Formation shales is dominated by nanoscale U minerals, mainly including coffinite, brannerite, U-bearing apatite and U-bearing xenotime. Various states of U are closely associated with organic matter, apatite, pyrite and clay minerals. Based on geochemical indexes, paleomarine condition and event deposition jointly drove the U enrichment in the Niutitang shales, in which hydrothermal activities and/or volcanic eruptions increased U fluxes in seawater and euxinic environment with high primary productivity provided a favorable condition for U reduction. The adsorption, complexation and reduction of UO22+ by organic matter and the formation of uranyl phosphate complexes by the combination of phosphate and UO22+ accelerated U immobilization and enrichment from bottom water to sediments. The microbial activities (e.g., BSR) in this process created favorable euxinic conditions and released inorganic-phase P to provide available ligands for UO22+. The U enrichment models of the lower Cambrian Niutitang shales in northeastern Guizhou were established. This paper provides a new insight into the U enrichment mechanism in organic-rich shales, and may also have implications for the applicability of U as redox proxy and the exploration of organic-rich shale related U deposits.

Increasing control over biomineralization in conodont evolution

Vertebrates use the phosphate mineral apatite in their skeletons, which allowed them to develop tissues such as enamel, characterized by an outstanding combination of hardness and elasticity. It has been hypothesized that the evolution of the earliest vertebrate skeletal tissues, found in the teeth of the extinct group of conodonts, was driven by adaptation to dental function. We test this hypothesis quantitatively and demonstrate that the crystallographic order increased throughout the early evolution of conodont teeth in parallel with morphological adaptation to food processing. With the c-axes of apatite crystals oriented perpendicular to the functional feeding surfaces, the strongest resistance to uniaxial compressional stress is conferred along the long axes of denticles. Our results support increasing control over biomineralization in the first skeletonized vertebrates and allow us to test models of functional morphology and material properties across conodont dental diversity.

Effect of Rare Earth Ion Substitution on Phase Decomposition of Apatite Structure.

The paper describes an investigation of phase decomposition of apatite lattice doped with rare earth ions (cerium, samarium, and holmium) at temperatures ranging from 25-1200 °C. The rare-earth ion-doped apatite minerals were synthesized using the sol-gel method. In situ high-temperature powder X-ray diffraction (XRD) was used to observe the phase changes and the lattice parameters were analyzed to ascertain the crystallographic transformations. The expansion coefficient of the compounds was determined, and it was found that the c-axis was the most expandable due to relatively weak chemical bonds along the c-crystallographic axis. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to examine the decomposition properties of the materials. Due to rare earth ion doping, the produced materials had slightly variable decomposition behaviour. The cerium and samarium ions were present in multiple oxidation states (Ce3+, Ce4+, Sm3+, Sm2+), whereas only Ho3+ ions were observed. Rare earth ion substitution affects tri-calcium phosphate proportion during decomposition by regulating concentrations of vacancies. X-ray photoelectron spectroscopy (XPS) analysis indicated that cerium and samarium ion-doped apatite yielded only 25 % tricalcium phosphate during decomposition. This finding advances our understanding of apatite structures, with implications for various high-temperature processes like calcination, sintering, hydrothermal processing, and plasma spraying.

First in situ Lu–Hf garnet date for a lithium–caesium–tantalum (LCT) pegmatite from the Kietyönmäki Li deposit, Somero–Tammela pegmatite region, SW Finland

Abstract. The in situ Lu–Hf geochronology of garnet, apatite, fluorite, and carbonate minerals is a fast-developing novel analytical method. It provides an alternative technique for age dating of accessory minerals in lithium–caesium–tantalum (LCT) rare-element (RE) pegmatites where zircon is often metamict due to alteration or radiation damage. Currently most dates from Finnish LCT pegmatites are based on columbite-group minerals (CGMs), but their occurrence is restricted to mineralised zones within the pegmatites. Accessory minerals such as garnet and apatite are widespread in both mineralised and unmineralised LCT pegmatites. Lu–Hf dating of garnet and apatite provides an exceptional opportunity to better understand the geological history of these highly sought-after sources for battery and rare elements (Li, Nb, Ta, Be) that are critical for the green transition and its technology. In this paper we present the first successful in situ Lu–Hf garnet date of 1801 ± 53 Ma for an LCT pegmatite from the Kietyönmäki deposit in the Somero–Tammela pegmatite region, SW Finland. This age is consistent with previous zircon dates obtained for the region, ranging from 1815 to 1740 Ma with a weighted mean 207Pb / 206Pb age of 1786 ± 7 Ma.

Curved mineral platelets in bone

Bone is a composite material principally made up of a mineral phase (apatite) and collagen fibrils. The mineral component of bone occurs in the form of polycrystalline platelets 2–6 nm in thickness. These platelets are packed and probably glued together in stacks of two or more, ranging up to >30 platelets. Here we show that most of these stacks are curved flat sheets whose cylindrical axes are oriented parallel to the long axes of collagen fibrils. Consequently, the curvature of the platelets is not detectable in TEM sections cut parallel to the collagen fibril axes. The radius of curvature around these axes ranges from about 25 nm (the average radius of the collagen fibrils) to 100′s of nm. The shapes of these curved forms contribute to the compressive strength of bone. Statement of significanceBone, the material of which bones are made, is mainly composed of a protein, collagen, and the mineral apatite (calcium phosphate). The crystals have long been known to be flat plates about 5 nanometers (nm) thick. Here we show that the crystals are bound together in curved platelets with a radius of curvature between 25 and several hundred nm, which weave between fibrils of collagen. Some platelets wrap tightly around fibrils. The platelets form stacks of from two to up to 30. The crystals in the platelets are all oriented parallel to the cylindrical fibrils even though most crystals are not in contact with collagen. These curved structures provide greater strength to bone.

Age and composition of perovskite in ultramafic lamprophyres from the Zima alkaline-ultramafic carbonatite complex, the southern margin of the Siberian craton: Petrogenetic implications

This paper presents data on the age and trace element composition of perovskites from dykes of ultramafic lamprophyres (aillikites) of the Zima alkaline-ultramafic carbonatite complex (Bolshaya Tagna and Bushkanay) located within the Urik-Iya graben, Eastern Sayan region, southern margin of the Siberian craton. The studied samples exhibit similar textural and structural features but differ slightly in the mineral composition of the groundmass. They have a porphyritic structure, a massive texture, and consist of olivine macrocrystals embedded in a fully crystallized groundmass composed of perovskite, apatite, spinel, phlogopite, garnet, carbonates, clinopyroxene and other minerals. The macrocrystals quantity varies between 40 and 50 vol%. With the exception of a single sample from the Bushkanay dyke, olivine is entirely replaced by serpentine and/or talc.Perovskites from aillikites of the Bolshaya Tagna intrusion exhibit crystals with normal zoning showing a decrease in Na, REE, and Nb contents with center-to-rim increasing Ca content. In contrast, minerals from the aillikites of the Bushkanay dyke demonstrate reverse zoning, with an increase in Na, REE, and Sr and decrease in Ca contents from the center to the rim. We suggest that during crystallization of perovskites, the magma parental to the aillikites of the Bolshaya Tagna intrusion and the Bushkanay dyke had nearly similar trace element composition, but after crystallization of the cores of perovskite crystals each melt portion evolved independently. The samples from the Bushkanay dyke show an increase in fO2 and the residual magma enrichment in REE, Na, and Sr as evidenced by their elevated contents at the rims of perovskite grains. In the Bolshaya Tagna aillikites after crystallization of perovskite cores, the melt was depleted in REE, Na, and Nb.Based on U-Pb dating of perovskites, the age of aillikites from the Bolshaya Tagna intrusion is 583–654 Ma. Perovskite from aillikites of the Bushkanay dyke is relatively young, with an age of 575 ± 39 Ma. The obtained ages are consistent with the age of formation of Neoproterozoic alkaline-ultramafic carbonatite complexes of the Siberian craton and other occurrences of aillikites in a response to extension of the Rodinia lithosphere.

Novel self-setting cements based on tricalcium silicate/(β-tricalcium phosphate/monocalcium phosphate anhydrous)/hydroxypropyl methylcellulose: From hydration mechanism to biological evaluations

Despite the clinical success of tricalcium silicate (TCS)-based materials in endodontics, the inferior handling characteristic, poor anti-washout property and slow setting kinetics hindered their wider applications. To solve these problems, an injectable fast-setting TCS/β-tricalcium phosphate/monocalcium phosphate anhydrous (β-TCP/MCPA) cement was developed for the first time by incorporation of hydroxypropyl methylcellulose (HPMC) and β-TCP/MCPA. The physical-chemical characterization (setting time, anti-washout property, injectability, compressive strength, apatite mineralization and sealing property) of TCS/(β-TCP/MCPA) were conducted. Its hydration mechanism was also investigated. Furthermore, the cytocompatibility and osteogenic/odontogenic differentiation of stem cells isolated from human exfoliated deciduous teeth (SHED) treated with TCS/β-TCP/MCPA were studied. The results showed that HPMC could provide TCS with good anti-washout ability and injectability but slow hydration process. However, β-TCP/MCPA effectively enhanced anti-washout characteristics and reduced setting time due to faster hydration kinetics. TCS/(β-TCP/MCPA) obtained around 90 % of injection rate and high compressive strength whereas excessive additions of β-TCP/MCPA compromised its injectability and compressive strength. TCS/(β-TCP/MCPA) can induce apatite deposition and form a tight marginal sealing at the dentin-cement interface. Additionally, TCS/(β-TCP/MCPA) showed good biocompatibility and promoted osteo/odontogenic differentiation of SHED. In general, our results indicated that TCS/(β-TCP/MCPA) may be particularly promising as an injectable bioactive cements for endodontic treatment.

Integrated approach to sustainable utilization of phosphate waste rock in road embankments: Experimental insights, stability analysis, and preliminary economic evaluation

This paper highlights an issue that has not received much attention which is the use of phosphate waste rock (PWR) in road embankments. This study focuses on the valorization of marly clay and marly limestone lithologies, which are abundant but often unused or undervalued, being simply deposited around mine sites. Investigating the potential use of these materials in road embankments requires a combination of experimentation, stability analysis, and economic evaluation. The materials were collected from mining trenches in the Benguerir mine (Morocco). The samples were subjected to i) chemical and mineralogical characterization; ii) environmental characterization; and iii) geotechnical characterization. The results of the characterization show that the samples are chemically dominated by CaO (12–33 wt%), SiO2 (23–38 wt%), and MgO (7 – 9 wt%); mineralogically, the main phases are quartz, calcite, dolomite, apatite, and clay minerals. The environmental characterization classified the studied materials as non-hazardous waste. In terms of geotechnical characterization, the marly limestone and marly clay belong to the A3 and R33 categories, which means that they can be successfully used as a sustainable alternative material for the embankment. This finding supports their safe utilization. The stability analysis reveals that embankments up to 10 m in height can be constructed with marly clay without significant physical instability risks. Satisfactory safety factors (SF) were found (SF=1.97 for H=5 m and SF=1.54 for H=10 m). For marly limestone, the height limit is less than 10 m (SF=1.74 for H=5 m and SF=1.33 for H=10 m), but it can be increased to 10 m by adding a bench of rock fill with a safety factor of 1.64. Finally, an economic evaluation demonstrates that PWR can be used as embankment materials within a radius of 28 km around the mine site. It appears to be a cost-effective alternative compared to conventional materials.