Apatite-group Minerals Research Articles

Fluorpyromorphite, Pb5(PO4)3F, a new apatite-group mineral from Sukhovyaz Mountain, Southern Urals, and Tolbachik volcano, Kamchatka

Fluorpyromorphite, Pb5(PO4)3F, a new apatite-group mineral from Sukhovyaz Mountain, Southern Urals, and Tolbachik volcano, Kamchatka

Geological and Mineralogical Analysis of Phosphorites in the Jebel Dhyr Syncline, Eastern Algerian Atlas

Abstract The characterization of phosphorite features within specific North African sedimentary series remains incomplete. Hence, the primary aim of this research is to determine the composition of powder patterns and phosphatic allochem fragments within the Jebel Dhyr syncline, situated in northeastern Algeria. By focusing on this region, the study endeavors to investigate the mineralogical properties and geochemical aspects of Paleocene-Eocene phosphorites in the broader context of North Africa. The methodology employed encompasses geological, petrographic, geochemical, and mineralogical analyses of the rocks. To achieve this objective, we have employed various techniques including thin section analysis, atomic absorption spectrometry, and X-ray diffraction (XRD). The geological section across the Jebel Dhyr area has revealed a succession of horizontally layered rocks. These rocks consist of eight prominent phosphorite layers interspersed with carbonate formations. Additionally, occasional thin layers of flint can be observed within these carbonate layers. XRD analysis of the whole rock established the presence of apatite group minerals such as hydroxylapatite, fluroapatite, francolite, and dahllite. Other minerals identified include carbonates, quartz, zeolites, feldspar, clays, sulphides, and gypsum. XRD recordings on the phosphatic allochem grains (pellets, coprolites, intraclasts, and shark teeth) identified different mineral phases, with coprolites and pellets showing hydroxylapatite and fluorapatite, sometimes associated with dahllite, while granules of different forms revealed hydroxylapatite associated with fluorapatite or francolite. Teeth from the Jebel Dhyr phosphate beam showed the systematic presence of fluorapatite. This study provides valuable information for the comprehensive utilization of phosphorus resources in the Algeria-Tunisia border.

Geodynamic seawater-sediment porewater evolution of the east central Atlantic Paleogene ocean margin revealed by U-Pb dating of sedimentary phosphates

Emerging evidence suggests that U-Pb and Lu-Hf ages of sedimentary apatite group minerals are often younger than their biostratigraphic ages. However, U-Pb dating of exquisitely preserved carbonate fluorapatite (CFA) is rare. The Upper Cretaceous/Paleogene marine sedimentary rocks of the Moroccan High Atlas host phosphate-rich sediments bracketed by calcareous nannofossil Zones (NP4-NP9) of late Danian to Thanetian age. Here, we use a laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to decipher whether CFA minerals are suitable for U-Pb chronostratigraphy and whether they can reveal the sedimentary and seawater history from which they formed. U-Pb dating of the CFA grains yields ages of 42.9 ± 1.3 Ma (MSWD = 2.3) and 35.7 ± 2.8 Ma (MSWD = 1.3) from three distinct phosphate-rich beds, being >15 million years younger than the expected biostratigraphic age. Combined scanning electron microscopy, X-ray diffraction, and infrared spectroscopy analyses, associate the Mg-rich clay minerals sepiolite and palygorskite, with micro-CFA crystals, while LA-ICP-MS trace element, rare earth element, and yttrium content for primary CFA grains, collectively point to long-term early diagenetic adsorption from oxygenated seawater-dominated porewater fluids. Authigenic clay minerals display a seawater-like pattern, with negligible U concentrations suggesting limited clay mineral influence on U-Pb dating of the CFA crystals. Considering the absence of extensive post-depositional alteration, we propose that because of their large surface area, the µm-sized CFA crystallites facilitated real-time surface adsorption and desorption of elements and diffusion processes. These conditions generated long-term open system connection of sediments with overlying seawater, enabling continuous U-Pb exchange for 15–25 Myr after phosphate precipitation. The data suggest that system closure was potentially associated with sediment lithification and the Atlas orogeny, pointing to stable oxygenation of shallow marine waters along the eastern passive margin of the central Atlantic Ocean in the Paleogene.

Trace Element Content and Partition in Apatite Group Minerals in Phosphate Ore from Catalão, Brazil

Trace Element Content and Partition in Apatite Group Minerals in Phosphate Ore from Catalão, Brazil

Origin of the subduction-related Tieli nephrite deposit in Northeast China: Constraints from halogens, trace elements, and Sr isotopes in apatite group minerals

Apatite, which is an excellent tracer of geological processes and magma evolution, can record a variety of information about melt and/or ore-fluid evolution by incorporating large amounts of trace elements. In this study, we conducted an in situ geochemical analysis of apatite from the Tieli nephrite deposit in Northeast China and evaluated the genetic mechanism along with the source. The apatite from the Tieli nephrite deposit in Northeast China is magmatic apatite characterized by positive Ce anomalies, negative or positive Eu anomalies, enrichment in light rare earth elements, depletion in heavy rare earth elements, and high F content. The apatite coincides with plagioclase crystallization with positive Sr-(La/Yb)N/(Sm/Yb)N correlations. The geochemical characteristics of the redox-sensitive elements (Eu, V, As, and Mn) in apatite indicate that the parental magma has a high oxygen fugacity between HM (Hematite–Magnetite) and NNO (Ni-NiO). The estimated F and Cl contents of the source area (average values of 1694 and 2328 ppm, respectively) are higher than the average values of the continental crust and primitive mantle, indicating a convergence process of halogens in the source area. The non-chondritic Y/Ho ratios of the apatite (3.34–53.64) imply that the magma interacted with a high volume of fluids. Combined with the findings of previous studies, the 87Sr/86Sr values in apatite suggest contributions from crust and mantle materials. Moreover, the positive correlation between Sr and 87Sr/86Sr may indicate that the subducted sediments altered by seawater were added into the magma chamber. Based on the above findings, the subduction of the Pacific Plate may supply source material and power for magmatism and mineralization in the Tieli nephrite deposit.

Pliniusite, Ca5(VO4)3F, a new apatite-group mineral and the novel natural ternary solid-solution system pliniusite–svabite–fluorapatite

Abstract The new apatite-group mineral pliniusite, ideally Ca5(VO4)3F, was found in fumarole deposits at the Tolbachik volcano, Kamchatka, Russia, and in a pyrometamorphic rock of the Hatrurim Complex, Israel. Pliniusite, together with fluorapatite and svabite, forms a novel and almost continuous ternary solid-solution system characterized by wide variations of T5+ = P, As, and V. In paleo-fumarolic deposits at Mountain 1004 (Tolbachik), members of this system, including the holotype pliniusite, are associated with hematite, tenorite, diopside, andradite, kainotropite, baryte and supergene volborthite, brochantite, gypsum and opal. In sublimates of the active Arsenatnaya fumarole (Tolbachik), pliniusite–svabite–fluorapatite minerals coexist with anhydrite, diopside, hematite, berzeliite, schäferite, calciojohillerite, forsterite, enstatite, magnesioferrite, ludwigite, rhabdoborite-group fluoroborates, powellite, baryte, udinaite, arsenudinaite, paraberzeliite, and spinel. At Nahal Morag, Negev Desert, Israel, the pliniusite cotype and V-bearing fluorapatite occur in schorlomite-gehlenite paralava with rankinite, walstromite, zadovite-aradite series minerals, magnesioferrite, hematite, khesinite, barioferrite, perovskite, gurimite, baryte, tenorite, delafos-site, wollastonite, and cuspidine. Pliniusite forms hexagonal prismatic crystals up to 0.3 × 0.1 mm and open-work aggregates up to 2 mm across (Mountain 1004) or grains up to 0.02 mm (Nahal Morag and Arsenatnaya fumarole). Pliniusite is transparent to semitransparent, colorless or whitish, with a vitreous luster. The calculated density is 3.402 g/cm−3. Pliniusite is optically uniaxial (–), ω = 1.763(5), ε = 1.738(5). The empirical formulas of pliniusite type specimens calculated based on 13 anions (O+F+Cl) per formula unit are (Ca4.87Na0.06Sr0.03Fe0.02)Σ4.98(V1.69As0.66P0.45S0.12Si0.09)Σ3.01O11.97F1.03 (Mountain 1004) and (Ca4.81Sr0.12Ba0.08Na0.05)Σ5.06(V2.64P0.27S0.07Si0.03)Σ3.01O12.15F0.51Cl0.34 (Nahal Morag). Pliniusite has a hexagonal structure with space group P63/m, a = b = 9.5777(7), c = 6.9659(5) Å, V = 553.39(7) Å3, and Z = 2. The structure was solved using single-crystal (holotype) X-ray diffraction, R = 0.0254. The mineral was named in honor of the famous Roman naturalist Pliny the Elder, born Gaius Plinius Secundus (AD 23–79). It is suggested that the combination of high temperature, low pressure, and high oxygen fugacity favors the incorporation of V5+ into calcium apatite-type compounds, leading to the formation of fluorovanadates.

Uranium–lead phosphate chronostratigraphy: A proof of concept from the mid-Carboniferous boundary

Sedimentary phosphates, chiefly composed of apatite group minerals, contain exceptionally high concentrations (10–200 ppm) of U relative to other sedimentary precipitates, making them an attractive target for U–Pb dating. Phosphate-rich sedimentary rocks are common from the Neoproterozoic onwards and commonly occur at key points in the geological record, often coinciding with periods of significant environmental flux or facies change. There is thus a clear rationale for dating phosphatic rocks. In this study, we demonstrate how spatially-resolved U–Pb dating of sedimentary apatite by laser-ablation quadrupole inductively-coupled-plasma mass-spectrometry (LA-Q-ICPMS) can provide constraints on early phosphate diagenesis and reworking in ancient rocks. Our samples are from two locations in a well-characterized stratigraphic sequence containing phosphorites, and phosphate-rich carbonates and shales in western Ireland, which span the Mississippian–Pennsylvanian (mid-Carboniferous) boundary. Sedimentary phosphate preserves precise (<0.7% uncertainty) U–Pb ages that record early diagenesis, or sediment reworking, depending upon the facies sampled. These ages are consistent with age constraints derived from Carboniferous conodont biostratigraphy from the same sections. Phosphorite deposition, occurring on the sediment-starved margin of an epeiric basin, is constrained by U–Pb dating of apatite to the lower part of the Bashkirian stage at 320.7 ± 2.0 Ma (MSWD = 1). However, we identify a significant time-gap between the phosphorite and the immediately underlying carbonate stratigraphy, and thus attribute phosphorite accumulation to forced regression accompanying a widely recognized and significant glacial advance in Gondwana that took place at the mid-Carboniferous boundary. Our two sampling sites are several kilometers apart, broadly along strike of the basin margin, but preserve U–Pb isotopic and trace element compositional information that is strikingly consistent at the same stratigraphic levels. If used appropriately, integrated phosphate U–Pb dating and trace element analysis could provide age constraints for key parts of the Neoproterozoic and Phanerozoic, aiding reconstruction of evolutionary and paleoenvironmental records.

Chlorine isotope fractionation during serpentinization and hydrothermal mineralization: A density functional theory study

Because of the large-scale recycling of volatile chlorine from the interior to the surface of the Earth, it is possible to use the isotopic composition of this element (δ37Cl) in serpentinite to study mantle-crust interactions in subduction zones. It is also possible to use chlorine isotopes to track the evolution of fluids (through fluid inclusions/minerals) in hydrothermal ore-forming systems. Here, we report the results of a study of equilibrium chlorine isotope fractionation during serpentinization and hydrothermal mineralization based on density functional theory (DFT) and ab initio molecular dynamics simulations (AIMD). The chlorine isotope fractionation between lizardite and brine under variable thermodynamic conditions is described by the relationship 1000lnαlizardite-fluid = 0.4170 × (1000/T)2–0.0281 × (1000/T) + 0.0582, which yielded Δ37Cllizardite-fluid values of +0.49 to +4.46‰, +0.41 to +0.59‰ and + 0.49 to +3.57‰ for conditions at the seafloor, in the mantle wedge and in subduction zones. As a proxy for the diversity of metal-chloride complexes in hydrothermal fluids, the stable configurations of ferrous chloride complexes were acquired from long trajectories of AIMD simulation. Using this information, the chlorine isotope fractionation between minerals (i.e., apatite-group minerals, muscovite, phlogopite, tremolite, lizardite, marialite and metal halides) and ore-forming fluid was estimated. The relatively large chlorine isotope fractionation (Δ37Cl minerals-hydrothermal fluid values from −1.99 to +2.18‰) might partly explain the large variation of δ37Cl in individual fluid inclusions observed in hydrothermal ore deposits. Because of the limited chlorine isotope fractionation between apatite and hydrothermal fluid (i.e., Δ37Cl apatite-ore-forming fluid of 0.06‰–0.69‰), apatite-group minerals might be an alternative to fluid inclusions for constraining the origin and evolution of hydrothermal fluids using δ37Cl values. The theoretical constraints provided in this paper will facilitate the use of chlorine isotopes in tracking the sources of chloride in subduction zones and the origin of mineralizing fluids in ore deposits.

Chlorine isotope mantle heterogeneity: Constraints from theoretical first-principles calculations

The processes that caused the heterogeneity of δ37Cl in the Earth's mantle are unclear. Here we report theoretical estimates of equilibrium chlorine isotope fractionation among common chlorine-bearing minerals, namely apatite-group minerals (Cl-Ap, F-Cl-Ap, OH-Cl-Ap), muscovite, phlogopite, tremolite, lizardite, marialite and metal halides, based on first-principles calculations, and use them to provide an explanation for this heterogeneity. Our results show that at ambient P-T conditions, the reduced isotopic partition function ratio (β-factor) is strongly correlated with the metal-Cl bond length/bond strength of the above minerals and that phlogopite and muscovite are more enriched in 37Cl than other minerals. As a result of a number of factors, including the adjacent atomic environment, the sites occupied by chlorine atoms in crystals, the Cl-metal coordination and the crystal density, the sensitivity of 103lnβ to pressure follows the sequence: halite > fluoro-chlorapatite > chlorapatite > marialite > hydroxyl-chlorapatite > lizardite > tremolite > muscovite > phlogopite. Estimates of the chlorine isotope fractionation between chlorine-bearing minerals and aqueous fluid at the pressure and temperature prevailing during subduction indicate that the δ37Cl values of mantle minerals could vary between −6‰ and + 3‰, assuming equilibrium. In contrast, the average δ37Cl value of the bulk mantle is −0.53 ± 0.16‰. Thus, large-scale recycling of volatile Cl from the deep mantle to the continental/oceanic crust and ocean, and the isotopic fractionation of chlorine with increasing metamorphic grade during subduction, could explain the heterogeneity of δ37Cl values observed in mantle materials.

Trace Element Geochemistry and Mineral Inclusions Constraints on the Petrogenesis of a Marble–Hosted Ruby Deposit in Yunnan Province, China

ABSTRACT Primary rubies in the Ailao Shan of Yunnan Province, China, are found in three layers of marble. However, the origin and source rocks of placer rubies in the Yuanjiang area remains unclear. Trace element geochemistry and inclusion mineralogy within these materials can provide information on their petrogenesis and original source. Zircon, rutile, mica group minerals, titanite, and apatite group minerals were the main solid inclusions identified within the placer Yuanjiang rubies, along with other mineral inclusions such as pyrite, pyrrhotite, plagioclase group minerals, and scapolite group minerals. Laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) measurements showed that the placer rubies are characterized by average values of Mg (31 ppmw), Ti (97 ppmw), V (77 ppmw), Cr (3326 ppmw), Fe (71 ppmw), and Ga (66ppmw). A trace-element oxide diagram, Fe values (&amp;lt;350 ppmw), and the mineral inclusion assemblage suggest marble sources for the placer ruby. Therefore, the Yuanjiang rubies (both primary and placer) are metamorphic, and this fits well with the observations that skarn and related minerals are mostly absent in this deposit. Yuanjiang rubies can be readily separated from the high-iron rubies of different geological types by their Fe content (&amp;lt;1000 ppmw). The discriminators Mg, Ga, Cr, V, Fe, and Ti have potential in separating Yuanjiang rubies from some other marble-hosted deposits, such as Snezhnoe. Nevertheless, geographic origin determination remains a challenge when considering the similarities in compositional features between the Yuanjiang rubies and rubies from some other marble-hosted deposits worldwide (e.g., Luc Yen). The presence of kaolinite group minerals and clusters of euhedral, prismatic zircon crystals in ruby suggest a Yuanjiang origin.

The Phosphate mineral assemblages from La Viquita Pegmatite, San Luis, Argentina

ABSTRACT La Viquita is a rare-element pegmatite of LCT signature, REL-Li subclass, spodumene subtype, that shows Fe &amp;gt; Mn mineral paragenesis instead of Mn &amp;gt; Fe, which is more common in the rare-element pegmatite population of the San Luis ranges. The phosphate mineral association of this pegmatite can be subdivided into (1) primary, with dendritic triphylite [(Fe/(Fe + Mn) = 0.72] and montebrasite–amblygonite as main phases; (2) metasomatic, with subsolidus replacement of triphylite by ferrisicklerite and heterosite; and (3) hydrothermal, with secondary growth of alluaudite at the expense of heterosite and wardite from montebrasite caused by Na-metasomatism. A Ca-rich influx under oxidizing conditions produced childrenite–eosphorite–ernstite, jahnsite-(CaMnFe), and kingsmountite. Apatite-group minerals are present throughout the processes. Very late-stage solutions formed millimetric crystals of hydroxylherderite associated with hydroxylapatite in cavities in K-feldspar.

Automated mineralogy for quantification and partitioning of metal(loid)s in particulates from mining/smelting-polluted soils

Topsoils near active and abandoned mining and smelting sites are highly polluted by metal(loid) contaminants, which are often bound to particulates emitted from ore processing facilities and/or windblown from waste disposal sites. To quantitatively determine the contaminant partitioning in the soil particulates, we tested an automated mineralogy approach on the heavy mineral fraction extracted from the mining- and smelting-polluted topsoils exhibiting up to 1920 mg/kg As, 5840 mg/kg Cu, 4880 mg/kg Pb and 3310 mg/kg Zn. A new generation of automated scanning electron microscopy (autoSEM) was combined and optimized with conventional mineralogical techniques (XRD, SEM/EDS, EPMA). Parallel digestions and bulk chemical analyses were used as an independent control of the autoSEM-calculated concentrations of the key elements. This method provides faster data acquisition, the full integration of the quantitative EDS data and better detection limits for the elements of interest. We found that As was mainly bound to the apatite group minerals, slag glass and metal arsenates. Copper was predominantly hosted by the sulfides/sulfosalts and the Cu-bearing secondary carbonates. The deportment of Pb is relatively complex: slag glass, Fe and Mn (oxyhydr)oxides, metal arsenates/vanadates and cerussite were the most important carriers for Pb. Zinc is mainly bound to the slag glass, Fe (oxyhydr)oxides, smithsonite and sphalerite. Limitations exist for the less abundant contaminants, which cannot be fully quantified by autoSEM due to spectral overlaps with some major elements (e.g., Sb vs. Ca, Cd vs. K and Ca in the studied soils). AutoSEM was found to be a useful tool for the determination of the modal phase distribution and element partitioning in the metal(loid)-bearing soil particulates and will definitely find more applications in environmental soil sciences in the future.

Alkalinity generation from weathering of accessory calcite and apatite and acid drainage neutralization in an Archean granitoid waste rock

Formation of acid rock drainage is a temporal balance of acid-generating and alkalinity-generating reactions during mineral weathering. Accessory calcite and apatite are commonly present in granitoid rocks, and their weathering can be a source of net alkalinity. To evaluate the acid-consuming capability of the calcite and apatite group minerals in a granitoid waste rock, a humidity cell experiment was conducted with a mix of a high carbonate tonalite and a low carbonate pegmatite representative of the country rock surrounding a kimberlite pipe at the Diavik Diamond Mine in Canada. The alkalinity generated from the tonalite + pegmatite was evaluated through release of Ca and Sr, which indicated a primary alkalinity-generating period during the first 25 weeks of the 80-week experiment. This period represents decomposition of readily available carbonates (infillings) and phosphates (euhedral grains) that release acid-consuming CO3 and PO4 into solution. The total alkalinity—represented by the release of Ca—produced during the first 25 weeks was compared to the total acidity—represented by the release of SO4—produced during the first 25 weeks of a previous humidity cell experiment with an acid-generating (Type III) waste rock from the same site. The easily weathered carbonates and phosphates of the tonalite + pegmatite have the potential to produce sufficient net alkalinity to consume the net acid generated from the early weathering of sulfides in the Type III waste rock. Aqueous extractions performed on post-experiment samples of the tonalite + pegmatite indicate remaining carbonate and phosphate minerals that were not readily available at the experimental ≤6.3 mm size. The heterogeneity of carbonate content and availability in granitic country rock at the mine site are reflective of the variability of accessory calcite in granitoids and indicate a continued need for site-specific determination of alkalinity-generating reactions with the weathering of waste rock.

Corundum Anorthosites-Kyshtymites from the South Urals, Russia: A Combined Mineralogical, Geochemical, and U-Pb Zircon Geochronological Study

Kyshtymites are the unique corundum-blue sapphire-bearing variety of anorthosites of debatable geological origin found in the Ilmenogorsky-Vishnevogorsky complex (IVC) in the South Urals, Russia. Their mineral association includes corundum-sapphire, plagioclase (An61–93), muscovite, clinochlore, and clinozoisite. Zircon, churchite-(Y), monazite-(Ce), and apatite group minerals are found as accessory phases. Besides, churchite-(Y) and zircon are also identified as syngenetic solid inclusions within the sapphires. In situ Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) U-Pb zircon geochronology showed the ages at about 290–330 Ma linked to the Hercynian orogeny in IVC. These ages are close to those of the syenitic and carbonatitic magmas of the IVC, pointing to their syngenetic origin, which is in agreement with the trace element geochemistry of the zircons demonstrating clear magmatic signature. However, the trace element composition of sapphires shows mostly metamorphic signature with metasomatic overprints in contrast to the geochemistry of zircons. The reason for this discrepancy can be the fact that the discrimination diagrams for sapphires are not as universal as assumed. Hence, they cannot provide an unambiguous determination of sapphire origin. If it is true and zircons can be used as traces of anorthosite genesis, then it can be suggested that kyshtymites are formed in a magmatic process at 440–420 Ma ago, most probably as plagioclase cumulates in a magma chamber. This cumulate rock was affected by a second magmatic event at 290–330 Ma as recorded in zircon and sapphire zoning. On the other hand, Ti-in-zircon thermometer indicates that processes operated at relatively lower temperature (&lt;900 °C), which is not enough to re-melt the anorthosites. Hence, zircons in kyshtymites can be magmatic but inherited from another rock, which was re-worked during metamorphism. The most probable candidate for the anorthosite protolith is carbonatites assuming that metamorphic fluids could likely leave Al- and Si-rich residue, but removed Ca and CO2. Further, Si is consumed by the silicification of ultramafic host rocks. However, kyshtymites do not show clear evidence of pronounced metasomatic zonation and evidence for large volume changes due to metamorphic alteration of carbonatites. Thus, the obtained data still do not allow for univocal reconstruction of the kyshtymite origin and further investigations are required.

Show me your yttrium, and I will tell you who you are: implications for fossil imaging

AbstractThe development of X‐ray tomography in the last decade has led to a revolution in palaeontology by providing a means of imaging 3D fossils. In turn, imaging of flat fossils has strongly benefitted from critical improvement of synchrotron X‐ray fluorescence (XRF). The latter, which allows the mapping of 2D distributions of major‐to‐trace elements over decimetre‐scale objects, usually targets metals with atomic number (Z) up to strontium (K‐shell emission lines); in the same energy domain, L‐shell emission lines of heavier elements (particularly lead) can also be analysed. A fluorescence signal from strontium can escape from a depth of a few 100 μm in fossils, thereby revealing, due to its substitution for calcium in calcium phosphates (apatite group minerals and bone), hidden fossil bone or phosphatized remains. Nonetheless, strontium similarly substitutes for calcium in calcium carbonates, resulting in the absence of contrast when fossils are preserved in limestone. Here, we show that this issue can easily be overcome by using X‐rays slightly higher in energy (17.2 keV and above) to excite and detect yttrium fluorescence. Together with lanthanides (collectively known as the rare earth elements), yttrium preferentially substitutes for calcium in calcium phosphates, offering anatomical contrasts for a wider range of fossils. This is demonstrated here for three fossils (vertebrate and invertebrate) from different ages and depositional environments. We then discuss the different chemical behaviours of strontium and yttrium in calcium phosphates and carbonates. Although yttrium is also found in other (rarer) minerals, its mapping using synchrotron XRF could be used as a proxy to pinpoint calcium phosphates in fossils and other geological materials.

Trace element inventory of meteoritic Ca-phosphates

Most extraterrestrial samples feature the two accessory Ca-phosphates (apatite-group minerals and merrillite), which are important carrier phases of the rare earth elements (REE). The trace-element concentrations (REE, Sc, Ti, V, Cr, Mn, Co, As, Rb, Sr, Y, Zr, Nb, Ba, Hf, Ta, Pb, Th, and U) of selected grains were analyzed by LA-ICP-MS and/or SIMS (REE only). This systematic investigation includes 99 apatite and 149 merrillite analyses from meteorites deriving from various asteroidal bodies including 1 carbonaceous chondrite, 8 ordinary chondrites, 3 acapulcoites, 1 winonaite, 2 eucrites, 5 shergottites, 1 ureilitic trachyandesite, 2 mesosiderites, and 1 silicate-bearing IAB iron meteorite. Although Ca-phosphates predominantly form in metamorphic and/or metasomatic reactions, some are of igneous origin. As late-stage phases that often incorporate the vast majority of their host’s bulk REE budget, the investigated Ca-phosphates have REE enrichments of up to two orders of magnitude compared to the host rock’s bulk concentrations. Within a single sample, each phosphate species displays a uniform REE-pattern, and variations are mainly restricted to their enrichment, therefore indicating similar formation conditions. Exceptions are brecciated samples, i.e., the Adzhi-Bogdo (LL3-6) ordinary chondrite. Despite this uniformity within single samples, distinct meteorite groups do not necessarily have unique REE-patterns. Four basic shapes dominate the REE patterns of meteoritic Ca-phosphates: (1) flat patterns, smoothly decreasing from La-Lu with prominent negative Eu anomalies (acapulcoites, eucrites, apatite from the winonaite and the ureilitic trachyandesite, merrillite from ordinary chondrites); (2) unfractionated patterns, with only minor or no anomalies (mesosiderites, enriched shergottites, IAB-iron meteorite); (3) LREE-enriched patterns, with either positive or slightly negative Eu anomalies (chondritic apatite); and (4) strongly LREE-depleted patterns, with negative Eu anomalies (depleted shergottites). The patterns do not correlate with the grade of metamorphism (petrologic type), specific adjacent mineral assemblages or with Ca-phosphate grain size. Neither the proportions of different REE, nor particular REE patterns themselves are universally correlated to a specific formation mechanism yet Eu (i.e., magnitude of the Eu anomaly) is a sensitive indicator to evaluate the timing of plagioclase and phosphate crystallization. Based on our data, U and Th abundances in apatite increase (almost linearly) with the grade of metamorphism, as well as with the differentiation of their host rock.

Apatite in carbonatitic rocks: Compositional variation, zoning, element partitioning and petrogenetic significance

Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data (~600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥0.3apfu F) with 0.2–2.7wt.% SrO, 0–4.5wt.% LREE2O3, 0–0.8wt.% Na2O, and low levels of other cations accommodated in the Ca site (up to 1000ppm Mn, 2300ppm Fe, 200ppm Ba, 150ppm Pb, 700ppm Th and 150ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO4)2− and (VO4)3− anions, substituting for (PO4)3−, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2wt.% SiO2, 1.5wt.% SO3 and 660ppm V). Although (CO3)2− groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8–1.3, 0.8–1.1 and 0.6–0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb)cn≤25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated.

Darwin's Warm Little Pond: A One-Pot Reaction for Prebiotic Phosphorylation and the Mobilization of Phosphate from Minerals in a Urea-Based Solvent.

The poor reactivity of insoluble phosphates, such as apatite-group minerals, has been a long-appreciated obstacle for proposed models of prebiotic organophosphate formation. This obstacle presents a significant challenge to the nascent development of an RNA world and other models for the origins of life on Earth. Herein, we demonstrate that a scenario based on the formation of a urea/ammonium formate/water (UAFW) eutectic solution leads to an increase in phosphorylation when compared to urea alone for phosphate sources of varying solubility. In addition, under evaporative conditions and in the presence of MgSO4 , the UAFW eutectic mobilizes the phosphate sequestered in water-insoluble hydroxyapatite, giving rise to a marked increase in phosphorylation. These results suggest that the prebiotic concentrations of urea in a geologically plausible evaporitic environment could solve the problem of organic phosphorylation on a prebiotic Earth.

The miaskitic-to-agpaitic transition in peralkaline nepheline syenite (white foyaite) from the Pilanesberg Complex, South Africa

The Mesoproterozoic Pilanesberg Complex, South Africa, is built up by several distinct, ring-shaped intrusions of syenite and peralkaline nepheline syenite. A mildly peralkaline ((Na+K)/Al=1.04–1.09), medium-to coarse grained nepheline syenite makes up the outermost ring in the southwestern part of the complex (“Matooster type white foyaite”). In this rock, mafic silicate minerals (amphibole, biotite, aegirine) and Ti-bearing minerals (ilmenite, astrophyllite, aenigmatite, lorenzenite, bafertisite, jinshajiangite) are interstitial to feldspar and nepheline, and define a series of mineral assemblages reflecting a change from a miaskitic crystallization regime (with Na-Ca amphibole, titanite and ilmenite) to increasingly agpaitic conditions (with arfvedsonite, aegirine, astrophyllite, aenigmatite, lorenzenite). The main driving force behind the evolution was an increase in peralkalinity of the trapped liquid, mainly by adcumulus growth of alkali feldspar and nepheline, which in the later stages of evolution was combined with increases in oxygen fugacity and water activity. Unlike in most other agpaitic rock complexes, Zr remained compatible in aegirine (and to some extent in amphibole) almost to the end of the process, when a hydrous zirconium silicate mineral (hilairite) crystallized as the only mineral in the rock having essential zirconium. The presence of minerals such as hilairite, bafertisite, jinshajiangite and a Na-REE-Sr rich apatite group mineral (fluorcaphite ?) in the latest assemblages suggests that the last remaining interstitial melt or fluid approached a hyperagpaitic composition. The isolated melt pockets in the Pilanesberg white foyaite follow a pattern of evolution that can be seen as a miniature analogue of the fractional crystallization processes controlling magma evolution in large, alkaline igneous rock complexes.

Hypothesis of Lithocoding: Origin of the Genetic Code as a "Double Jigsaw Puzzle" of Nucleobase-Containing Molecules and Amino Acids Assembled by Sequential Filling of Apatite Mineral Cellules.

The hypothesis of direct coding, assuming the direct contact of pairs of coding molecules with amino acid side chains in hollow unit cells (cellules) of a regular crystal-structure mineral is proposed. The coding nucleobase-containing molecules in each cellule (named "lithocodon") partially shield each other; the remaining free space determines the stereochemical character of the filling side chain. Apatite-group minerals are considered as the most preferable for this type of coding (named "lithocoding"). A scheme of the cellule with certain stereometric parameters, providing for the isomeric selection of contacting molecules is proposed. We modelled the filling of cellules with molecules involved in direct coding, with the possibility of coding by their single combination for a group of stereochemically similar amino acids. The regular ordered arrangement of cellules enables the polymerization of amino acids and nucleobase-containing molecules in the same direction (named "lithotranslation") preventing the shift of coding. A table of the presumed "LithoCode" (possible and optimal lithocodon assignments for abiogenically synthesized α-amino acids involved in lithocoding and lithotranslation) is proposed. The magmatic nature of the mineral, abiogenic synthesis of organic molecules and polymerization events are considered within the framework of the proposed "volcanic scenario".