Mineralogy and major-element geochemistry of the lower Permian Greta Seam,Sydney Basin,Australia

The mineralogy of the high-volatile bituminous coals and associated strata from the Greta seam, Sydney Basin, Australia, has been evaluated in this study. Although the seam is not immediately overlain by marine strata, percolation of marine water into the original peat bed is indicated by the petrological, mineralogical and geochemical characteristics, which resemble those of coals with marine roof strata. The upper and lower sections of the seam have contrasting mineralogy. Pyrite typically comprises 40 to 56 wt% of the mineral assemblage in the marine-influenced upper part of the seam section. The lower part contains much less pyrite (typically <5 wt%, organic-free basis), and also relatively abundant dawsonite (up to 14 wt%, organic-free basis). The minerals within most coal plies are largely of authigenic origin. These include pyrite, siderite, clay minerals (mainly kaolinite and Na-rich mixed-layer illite/smectite), and quartz, most of which have a relatively early, syngenetic origin. Minor Ti-bearing minerals, anatase or rutile, and phosphate minerals, fluorapatite and goyazite, were probably also formed during early diagenesis. Other minerals have features that indicate late-stage precipitation. These include abundant cleat- and fracture-filling dawsonite, which may be the result of reactions between earlier-precipitated kaolinite and Na₂CO₃- or NaHCO₃-bearing fluids. Minor albite may also be epigenetic, possibly precipitated from the same Ca–Al bearing fluids that formed the dawsonite. The most abundant detrital minerals in the Greta coals are quartz, poorly ordered kaolinite, illite and mixed-layer illite/smectite (I/S). These occur mainly in the floor, roof and other epiclastic horizons of the seam, reflecting periods of greater clastic influx into those parts of the original peat-forming environment. Detrital minerals are rare in the coals away from the epiclastic horizons, probably owing to almost complete sediment bypassing in the depositional system. Alternatively, any detrital minerals that were originally present may have been leached from the peat bed by diagenetic or post-diagenetic processes.     

Phosphorus and the rare earth elements in felsic magmas: an assessment of the role of apatite

The solubility of fluorapatite in 17 silica-rich melts in the system Na₂O-K₂O-Al₂O₃-SiO₂ (with and without CaO or CaF₂) was determined at 1 kbar water pressure and 750 900°C. Apatite saturation occurs at levels of dissolved P₂O₅ ranging between 0.04 (± 0.02) and 0.28 (± 0.13) wt%. with only 4 values outside the 0.09–0.20 wt% range.The results demonstrate not only that apatite is a common liquidus phase in felsic melts, but also that, under most circumstances, it remains in the residue during episodes of partial fusion of the crust. Given a solubility limit of 0.14 wt% dissolved P₂O₅ (the mean of the experimental values) a source containing as little as 0.05% P₂O₅ must be 35% melted before apatite is lost from the residue and no longer buffers the melt P₂O₅ concentration at the saturation value. Higher abundances of P₂O₅ in the source postpone the loss of residual apatite to still higher degrees of melting, and if the source P₂O₅ content exceeds 0.14 wt%, apatite must be residual for all degrees of melting, increasing in abundance as melting proceeds.The generally secondary influence of apatite on the rare earth element (REE) patterns of melt and residue is most apparent when garnet and/or amphibole is minor or lacking in the residue. Fractional crystallization of intermediate (e.g. andesitic) magmas toward felsic compositions invariably results in saturation in apatite and some consequent depletion of REE in the melt.     

Differentiation of nelsonitic magmas in the formation of the ~1.74 Ga Damiao Fe–Ti–P ore deposit, North China

The ~1.74 Ga Damiao anorthosite complex, North China, is composed of anorthosite and leuconorite with subordinate melanorite, mangerite, oxide-apatite gabbronorite, perthite noritic (i.e., jotunitic) and ferrodioritic dykes. The complex hosts abundant vein-, pod- and lens-like Fe–Ti–P ores containing variable amounts of apatite (10–60 modal%) and Fe–Ti oxides. In addition to Fe–Ti–P ores, there are also abundant Fe–Ti ores which are closely associated with Fe–Ti–P ores in the deposit. Most of Fe–Ti–P ores are dominated by Fe–Ti oxides and apatite, devoid of silicate minerals, mineralogically similar to the common nelsonites elsewhere. In contrast, Fe–Ti ores are dominated by Fe–Ti oxides with minor apatite (<5 modal %). The parental magma of these ores, estimated from olivine and apatite compositions using mineral-melt partition coefficients, has composition similar to the ferrodioritic dykes. Fe–Ti–P ores have variable Fe–Ti oxides and apatite proportions, indicating that they are cumulates. Their simple assemblage of Fe–Ti oxides and apatite and local net-texture suggest that the Fe–Ti–P ores in Damiao have formed from nelsonitic melts immiscibly separated from the ferrodioritic magma during late-stage differentiation. Fe–Ti ores are also cumulates and have mineral compositions similar to Fe–Ti–P ores. The close association between Fe–Ti and Fe–Ti–P ores indicates that the Fe–Ti ores may have also formed from the nelsonitic melts. We proposed that differentiation of nelsonitic melts accompanied by gravity settling is responsible for the formation of Fe–Ti and Fe–Ti–P ores. Such a differentiation process in nelsonitic melts is well supported by variations of Sr, Y, Th, U, REE and Eu/Eu* of apatite in Fe–Ti–P ores. Using oxides/apatite ratio of 2:1 and compositions of apatite and calculated primary oxides, we estimate the composition of the nelsonitic melt as ~52.0 wt% Fe₂O₃t, ~18.5 wt% CaO, ~14.2 wt% P₂O₅, ~8.7 wt% TiO₂, ~4.0 wt% Al₂O₃ and ~1.1 wt% MgO with minor SiO₂, K₂O, Na₂O and F. Such a nelsonitic melt is suggested to be possibly conjugated with Si-rich melts compositionally similar to the Damiao jotunitic dykes (~50 wt% SiO₂ and ~15 wt% Fe₂O₃t) which may subsequently evolve to mangeritic rocks in Damiao. Our modeling also indicates that the onset of immiscibility occurs at a time when the evolved melt has ~44 wt% SiO₂, ~21 wt% Fe₂O₃t, ~3.0 wt% TiO₂ and ~2.6 wt% P₂O₅. High oxygen fugacity and phosphorous content in magmas may play important roles in the immiscibility of nelsonitic magmas, including promoting iron enrichments and widening the two-liquid field.     

Petrogenesis and metallogenic implications of Late Mesozoic intrusive rocks in the Tongling region,eastern China: a case study and perspective review

ABSTRACT

Large-scale Cu–Au mineralization is associated with Late Mesozoic intrusive rocks in the Tongling region of eastern China, which mainly comprise pyroxene monzodiorite, quartz monzodiorite, and granodiorite. To constrain the petrogenesis of the intrusive rocks and Cu–Au mineralization, detailed analyses of the geochronology, apatite in situ geochemistry, whole-rock geochemistry, and zircon Hf isotopic compositions were performed. Magmatic zircons from pyroxene monzodiorites, quartz monzodiorites, and granodiorites yield U–Pb ages of 136–149 Ma, 136–146 Ma, and 138–152 Ma, respectively, indicating that their formation ages are contemporaneous. Quartz monzodiorites and granodiorites (SiO₂ = 57.9–69.5 wt.%) are highly potassic calc-alkaline rocks with adakitic affinity and have low MgO and Y contents, low zircon ε_Hf(t) values (?11.7 to ?39.0), high apatite Cl contents (>0.2 wt.%), and log fO₂ values (?23.2 to ?8.23), indicating that they may have formed when metasomatized mantle-derived magmas mixed with slab-derived magmas before undergoing crustal assimilation and fractional crystallization. Pyroxene monzodiorites (SiO₂ = 48.4–53.0 wt.%) are shoshonitic and record high MgO, P₂O₅, and Y contents, high zircon ε_Hf(t) values (1.55 to ?7.87), high oxygen fugacity, low Nb and Ta contents, and low apatite Cl contents (mainly <0.2 wt.%), suggesting that they were primarily derived from a metasomatized lithospheric mantle-derived magma that experienced the assimilation of lower crustal materials. The results indicate that the intrusive rocks and associated large-scale Cu–Au mineralization of the Tongling region resulted from the partial melting of the subducted oceanic slab in an oxidizing environment.     

Uranium (U) concentration and its genetic significance in the phosphorites of the Paleoproterozoic Bijawar Group of the Lalitpur district,Uttar Pradesh,India

The paper presents the uranium (U) concentration and distribution pattern in the Paleoproterozoic phosphorites of Lalitpur district of Uttar Pradesh. The study of thin sections, SEM and XRD reveal that apatite is the essential phosphate mineral while quartz and feldspars are the dominant gangue in the phosphorites of the investigated area. The collophane is observed to be mostly oolitic in form and microspherulitic in texture. The major element geochemistry indicated that the phosphorite samples are rich in P₂O₅, CaO, SiO₂ and Fe₂O₃ whereas depletion of MgO, MnO, K₂O and Al₂O₃ was observed. The CaO/P₂O₅ ratio ranges from 1.13 to 1.46 which is slightly lower than that of cations and anions substituted francolite (1.621) and close to that of carbonate-fluorapatite (1.318). The trace element geochemistry indicates that the phosphorites of Lalitpur have the significant range of U concentration (1.67 to 129.67 μg/g) which is more than that of Th (0.69 to 0.09 μg/g) among the analysed trace elements in the phosphorite samples of the area. The positive correlation of U with P₂O₅, CaO and U/P₂O₅ indicates a close association of U with phosphate minerals like collophane (apatite), whereas negative correlation of U with SiO₂ and Fe₂O₃ may be due to mutual replacement. The antipathetic relationship of U with Ni may be an indication of high oxidizing conditions, whereas sympathetic relationship of U with K₂O points towards higher alkaline conditions of the basin of deposition during phosphatization. The variable concentration of U and its relationship with significant major and trace elements in most of the phosphorite samples lead one to believe that the deposition of these phosphorites might have taken place in highly alkaline medium during fairly oxidizing to weakly reducing environmental conditions of geosynclinal basin.     

Mineralogy and geochemistry of Al-hydroxide/oxyhydroxide mineral-bearing coals of Late Paleozoic age from the Weibei coalfield, southeastern Ordos Basin, North China

This paper mainly describes mineralogy and geochemistry of coals from the Weibei coalfield in the southeastern Ordos Basin, North China. A number of Al-hydroxide/oxyhydroxide minerals were detected in the Late Carboniferous coals (Nos. 5, 10 and 11 coals), especially in the No. 10 coal. Aluminum-hydroxide/oxyhydroxide minerals (nordstrandite, boehmite and diaspore) in the No. 10 coal are associated with kaolinite, suggesting that these minerals are derived from the breakdown of kaolinite. A model in which Al-hydroxide/oxyhydroxide minerals form from the incongruent dissolution of kaolinite is presented. Nordstrandite and boehmite mainly occur as massive lenses (<500 μm in length). Diaspore appears as massive aggregates and as single euhedral crystals (<50 μm in length) in a kaolinite matrix. The presence of high temperature quartz, and zircon indicates that there was input of felsic volcanic debris during accumulation of the Late Carboniferous coals. These volcanic materials have also had a significant influence on the enrichment of certain trace elements including Li, Be, Ga, Zr, Nb, Mo, Sn, W and U in the Late Carboniferous coals (Nos. 5, 10, and 11 coals). SEM-EDX results show that Ga in the No. 10 coal (whole coal average 33.4 μg/g; n = 2) mainly occurs within Al-hydroxide/oxyhydroxide minerals (nordstrandite, boehmite, and diaspore), kaolinite and organic matter.     

Geochemical Characteristics of Apatite in Heavy REE‐rich Deep‐Sea Mud from Minami‐Torishima Area,Southeastern Japan

We have conducted geochemical and mineralogical investigations of the rare earth and yttrium (REY)‐rich mud from the Minami‐Torishima area in the Pacific in order to clarify the concentration of REY and their host‐phase in the mud. X‐ray diffraction analysis shows that the mud is mainly composed of phillipsite, fluorapatite, quartz, albite, illite and montmorillonite. Whole‐rock CaO, P₂O₅ and total REY contents of the mud are positively correlated. Relative abundance of apatite is also positively correlated to P₂O₅ and total REY contents. These correlations suggest that apatite is the main host of the P₂O₅ and REY in the mud. We make in situ compositional analyses of constituent minerals in the REY mud. The results show that the apatite is abundant in REY (9300–32,000 ppm) and is characterized by a negative Ce anomaly and enrichment in heavy rare‐earth elements. This abundance and composition of REY of the mud is similar those of fish debris apatites. In contrast, phillipsite is less abundant in REY (60–170 ppm). Therefore we conclude that the main REY host phase of the mud is apatite.     

The petrogenesis of granitoid rocks unusually rich in apatite in the Western Tatra Mts. (S-Poland, Western Carpathians)

In the bottom part of the tongue-shaped, layered granitoid intrusion, exposed in the Western Tatra Mts., apatite-rich granitic rocks occur as pseudo-layers and pockets between I-type hybrid mafic precursors and homogeneous S-type felsic granitoids. The apatite-rich rocks are peraluminous (ASI?=?1.12–1.61), with P₂O₅ contents ranging from 0.05 to 3.41 wt.% (<7.5 vol.% apatite), shoshonitic to high-K calc-alkaline. Apatite is present as long-prismatic zoned crystals (Ap₁) and as large xenomorphic unzoned crystals (Ap₂). Ap₁ apatite and biotite represent an early cumulate. Feldspar and Ap₂ textural relations may reflect the interaction of the crystal faces of both minerals and support a model based on local saturation of (P, Ca, F) versus (K, Na, Al, Si, Ba) in the border zones. Chondrite-normalized REE patterns for the apatite rocks and for pure apatite suggest apatite was a main REE carrier in these rocks. Minerals characteristics and the whole rock chemistry suggest both reduced S-type and I-type magma influenced the apatite-rich rocks. The field observations, mineral and rock chemistry as well as mass-balance calculations point out that the presence of apatite-rich rocks may be linked to the continuous mixing of felsic and mafic magmas, creating unique phosphorus- and aluminium-rich magma portions. Formation of these rocks was initially dominated by the complex flowage-controlled and to some extent also gravity-driven separation of early-formed zoned minerals and, subsequently, by local saturation in the border zones of growing feldspar and apatite crystals. Slow diffusion in the phosphorus-rich magma pockets favoured the local saturation and simultaneous crystallization of apatite and feldspars in a crystal-ladden melt.     

Petrology of Late Jurassic allochthonous ultramafic lamprophyres within the Batain Nappes,Northeastern Oman

ABSTRACT

Late Jurassic ultramafic lamprophyre (UML) sills and dikes occur as 3 km-long intrusions within the allochthonous Whara Formation of the Batain nappes, eastern Oman. The sills and dikes comprise macrocrystic phlogopite and spinel-bearing aillikite and damtjernite. Aillikite is a light grey, massive fine-grained tuffaceous rock with euhedral laths of mica, while damtjernite is a dark grey, medium- to coarse-grained rock with abundant pelletal lapilli and globular segregationary textures. Both lithologies are composed of calcite, phlogopite, apatite, magnetite, spinel, diopside, and richterite. Orthoclase occurs only within damtjernite. The rocks are strongly silica undersaturated (17.6–33.7 wt.% SiO₂), with low MgO (4.7–10.2 wt. %) and high Al₂O₃ (3.5–8.6 wt.%). The aillikites are distinguished from the damtjernites by their lower SiO₂, Al₂O₃, and Na₂O abundances, and their higher MgO, CaO, and P₂O₅ contents. The rare earth element (REE) patterns of both rock types are similar and show strong light REE (LREE) enrichment. Both are enriched in Ba, Th, U, Nb, and Ta, with normalized concentrations of up to 1000 times those of primitive mantle. Relative depletions are apparent for high REE (HREE), K, Rb, Pb, Sr, P, Zr, and Hf. The rocks have initial ⁸⁷Sr/⁸⁶Sr ratios of 0.70435–0.70646, whereas initial ¹⁴³Nd/¹⁴⁴Nd ratios vary between 0 · 512603 and 0 · 512716 (εNd_i 2.6–3.2). Pb isotopic ratios are more varied among the aillikites and damtjernites: ²⁰⁸Pb/²⁰⁴Pb_i = 38.97–39.39 and ²⁰⁷Pb/²⁰⁴Pb_i = 15.35–15.58, ²⁰⁶Pb/²⁰⁴Pb_i = 18.08–18.96. The abundance of phlogopite, apatite, and rutile and enrichment in LREEs, Ba, Th, U, Nb, and Ta in the Sal UMLs suggest metasomatic enrichment of these rocks following a low degree of partial melting of a depleted source region. Ar–Ar age dating of phlogopite macrocrysts from the aillikites and damtjernites (154 and162 Ma, respectively) correlates with large-scale tectonic events recorded in the proto-Indian Ocean at 140–160 Ma.     

Diagenetic trends of fluorine concentration in Negev phosphorites, Israel: implications for carbonate fluorapatite composition during phosphogenesis

An electron probe and chemical study of bulk phosphorite samples and separated constituents from various Negev deposits was carried out together with XRD, FTIR spectroscopy and textural analysis. The results allow a better understanding of the distribution of fluorine in these Upper Cretaceous phosphorite sequences and shed light on variations in the composition of the carbonate fluorapatite (CFA) phase during phosphogenesis. Two facies are recognized: (1) a pristine, microbially generated phosphorite facies; (2) a recycled, peloidal and biodetrital facies. Fluorine distribution in the Negev phosphorites is facies controlled: F/P₂O₅ is much lower in the pristine facies (0·090–0·107) than in the recycled facies (0·107–0·120). In addition, F/P₂O₅ varies considerably between the various constituents of the phosphate fraction; F‐poor francolites (F/P₂O₅ as low as 0·080) co‐exist with F‐rich francolites (F/P₂O₅ as high as 0·135) in the same phosphorite bulk sample. A lower F/P₂O₅ in francolite is associated with higher Cd and Zn concentrations in the phosphorite, an increase in Fe‐rich smectites in the clay fraction and the presence of structural OH in the francolite. The lower F/P₂O₅ ratios in the pristine facies are attributed to high organic deposition rates during the formation of these matted sediments, leading to rapid burial of the in situ‐forming CFA. This is possibly coupled with diffusion of F from sea water into bottom sediments being hampered by microbial mat coatings. These conditions resulted in O₂‐depleted porefluids, inducing the precipitation of Cd‐rich Zn sulphides and the formation of Fe‐rich smectites. F‐enrichment probably takes place when the earlier formed F‐poor ‘primary’ CFA is relocated close to the sea floor and bathed with interstitial sea water solutions of higher F concentrations. Oxidation and removal of the sulphide‐bound Cd and Zn apparently occurred together with enrichment in F of the francolite. Combining chemical data with XRD and FTIR results suggests a multistage growth for the Negev phosphate constituents in shifting formational sites and porefluids of varying F concentrations. This multiphase growth is reflected in the patchy distribution of F in the Negev constituents and might explain the inverse correlation between mean CO₂/F and F/P₂O₅ ratios of the analysed phosphorites in the two facies. It also suggests that CFA (or an amorphous precursor) initially formed with some OH groups in the apatite structure, which were subsequently substituted by F ions in recycled francolite through re‐equilibration with porefluids of higher F concentrations.     

Crystallization of apatite in natural magmas under high pressure,hydrous conditions,with particular reference to ‘Orogenic’ rock series

Two separate series of hydrous experiments involving (1) imposing apatite saturation on a series of igneous rock compositions from basanite to rhyolite, and (2) crystallizing similar natural rock compositions progressively until apatite appears, demonstrate a close dependence between apatite saturation and silica content of the magma, and determine P₂O₅ levels at a given silica value and temperature at which that composition may be expected to crystallize apatite. The effect of pressure on apatite solubility is not great, and is most significant for silicic compositions.P₂O₅ vs SiO₂ relationships of the low-K island arc suite, calcalkaline suite and high-K calc-alkaline suite, appear regular and characteristic for each suite, and when linked with the experimental work on apatite solubility, indicate the following: (1) the low-K and calc-alkaline series have low P₂O₅ contents (0.1–0.2 wt.%) and relatively flat P₂O₅-SiO₂ patterns; they do not show evidence of reaching apatite saturation until rhyodacite-rhyolite compositions are obtained for the low-K suite, and andesite-dacite compositions for the calc-alkaline suite; (2) the high-K calc-alkaline series has higher P₂O₅ contents (0.4–0.6 wt.%) in mafic compositions, and achieves apatite saturation over a wide compositional range for the series; (3) the calc-alkaline and high-K calc-alkaline series are probably lower temperature, and more hydrous than the low-K series; (4) anomalous P₂O₅-SiO₂ distributions may indicate non-equilibrium crystallization of apatite, magma-mixing and crystal accumulation processes active in generation of the orogenic volcanic series.     

Pétrographie et géochimie comparées des pellets phosphatés et de leur gangue dans le gisement phosphaté de Ras-Draâ (Tunisie). Implications sur la genèse des pellets phosphatés

Paléocène-Early Eocene phosphate outcrop in the Ras-Draâ deposit (Tunisia) comprises alternances of P-rich strata (P₂O₅ ≥ 18%) and P-poor ones (P₂O₅ ≤ 2%). In phosphate rich strata, P is concentrated in rounded grains—so-called pellets—(28% ≤ P₂O₅ ≤ 38%) embedded in a matrix—so-called exogangue—much poorer in P (P₂O₅ # 7%) than pellets. The study of pellets (whose size lies mainly between 100 and 500 μm), of their surrounding matrix and of poorly phosphatic sediments, interlayered between the phosphatic strata, has been performed by optical microscopy and various chemical analyses, ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy) and punctual chemical analyses by EDS (Energy Dispersive Spectroscopy). Mineralogical and chemical studies of the Tunisian phosphatic pellets show that the basic mineralogical component of these grains is carbonate-fluor-apatite, or francolite. The structural formula of a representative specimen of francolite in the basin is as follows: (Ca_4.63Mg_0.13Na_0.22)(PO₄)_2.51(CO₃)_0.48(OH_0.77F_0.23). The mineralogy of the constituents of the sediment surrounding pellets comprises carbonates, clays, silica (opal, quartz). Microscopic observations of Ras-Draâ phosphorites, added to geochemical results, establish that pellets are small bodies, allochtonous to their matrix and whose composition is independent of that of this matrix. Fecal cylindrical bodies and subspherical pellets, the latest being supposed to proceed from the fecal bodies by fragmentation, are considered to have been formed by fishes, as P-rich and organic matter-rich faeces. These faeces turn out to be resistant to mechanical dispersion and to chemical diffusion of soluble elements from and in direction of sea water. This closeness is responsible for the strong reducing conditions having prevailed inside and during the pellets diagenesis.     

Carbonatite melts and genesis of apatite mineralization in the Guli pluton (northern East Siberia)

Inclusions of mineral-forming environments in apatite-containing ijolites and magnetite–phlogopite–apatite ores in carbonatites were studied to elucidate the genesis of apatite mineralization in the Guli alkaline ultramafic carbonatite massif. Primary inclusions of carbonate–salt and carbonate melts have been discovered and studied. The carbonate–salt melt inclusions are of alkaline high-Ca composition and are enriched in P, Sr, SO₃, and F (wt.%): CaO—30–40, Na₂O—5–12, K₂O—2–4, P₂O₅—1–3, SO₃—1.5–3, and SrO—1–3. They also contain minor MgO, FeO, BaO, and SiO₂ (tenths and hundredths of percent). The homogenization temperature of these inclusions is 850–970 °C. The carbonate inclusions contain predominant CaO (54–67 wt.%) and minor MgO, FeO, SrO, Na₂O, and P₂O₅ (tenths of percent). Their homogenization temperature is 840–860 °C. Similar primary carbonate–salt and carbonate inclusions were found in garnet, and secondary ones were detected in silicate minerals (clinopyroxene and nepheline) of ijolites. Clinopyroxenes of ijolites also contain primary inclusions of alkaline ultramafic high-Ca melts similar in composition to melilitite-melanephelinites highly enriched in P, SO₃, and CO₂ (wt.%): SiO₂—41–46, Al₂O₃—8–16, FeO—2–8, MgO—3–6, CaO—12–20, Na₂O—2–9, K₂O—1–6, P₂O₅—0.4–2.1, SO₃—0.2–2.3, and Cl—0.02–0.35. According to the obtained data, apatite of the magnetite–phlogopite–apatite ores and ijolites of the Guli pluton crystallized from phosphorus-rich alkaline carbonate–salt melts at 850–970 °C. The generation of these melts was, most likely, due to the silicate–salt immiscibility in melilitite-melanephelinite melts highly enriched in salts, which occurred either at the final stages of clinopyroxene crystallization or during the formation of melilite. The presence of alkalies, S, F, and CO₂ in spatially separated carbonate–salt melts contributed to the concentration and preservation of phosphorus in them at low temperatures, which led to the formation of apatite mineralization in ijolites and ore deposit in carbonatites.© 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.     

New insights on pressure,temperature, and chemical stability of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

A Cs-bearing polyphase aggregate with composition (in wt%): 76(1)_CsAlSi5O12 + 7(1)_CsAlSi2O6 + 17(1)_amorphous, was obtained from a clinoptilolite-rich epiclastic rock after a beneficiation process of the starting material (aimed to increase the fraction of zeolite to 90 wt%), cation exchange and then thermal treatment. CsAlSi₅O₁₂ is an open-framework compound with CAS topology; CsAlSi₂O₆ is a pollucite-like material with ANA topology. The thermal stability of this polyphase material was investigated by in situ high-T X-ray powder diffraction, the combined P–T effects by a series of runs with a single-stage piston cylinder apparatus, and its chemical stability following the “availability test” (“AVA test”) protocol. A series of additional investigations were performed by WDS–electron microprobe analysis in order to describe the P–T-induced modification of the material texture, and to chemically characterize the starting material and the run products. The “AVA tests” of the polyphase aggregate show an extremely modest release of Cs⁺: 0.05 mg/g. In response to applied temperature and at room P, CsAlSi₅O₁₂ experiences an unquenchable and displacive Ama2-to-Amam phase transition at about 770 K, and the Amam polymorph is stable in its crystalline form up to 1600 K; a crystalline-to-amorphous phase transition occurs between 1600 and 1650 K. In response to the applied P = 0.5 GPa, the crystalline-to-amorphous transition of CsAlSi₅O₁₂ occurs between 1670 and 1770 K. This leads to a positive Clapeyron slope (i.e., dP/dT > 0) of the crystalline-to-amorphous transition. When the polyphase aggregate is subjected at P = 0.5 GPa and T > 1770 K, CsAlSi₅O₁₂ melts and only CsAlSi₂O₆ (pollucite-like; dominant) and Cs-rich glass (subordinate) are observed in the quenched sample. Based on its thermo-elastic behavior, P–T phase stability fields, and Cs⁺ retention capacity, CsAlSi₅O₁₂ is a possible candidate for use in the immobilization of radioactive isotopes of Cs, or as potential solid hosts for ¹³⁷Cs γ-radiation source in sterilization applications. More in general, even the CsAlSi₅O₁₂-rich aggregate obtained by a clinoptilolite-rich epiclastic rock appears to be suitable for this type of utilizations.     

Structure and properties of rare earth silicates with the apatite structure at high pressure

The pressure-induced structural transformation of rare earth, non-stoichiometric silicates, (REE_9.33(SiO₄)₆O₂, RE = La, Ce, Nd, Eu, and Gd) with the apatite structure type, were investigated by X-ray diffraction, photoluminescence, far-infrared spectroscopy, and DFT calculations. A pressure-induced degradation of symmetry from P6 ₃ /m to P6 ₃ occurs with increasing pressure. The transition is due to the tilting of SiO₄ tetrahedra and reduced symmetry constraints on one of the O atoms in the tetrahedron. The critical transition pressure increased from ~13 GPa in La_9.33(SiO₄)₆O₂ to ~25 GPa in Gd_9.33(SiO₄)₆O₂ with the decrease in lanthanide cation size. The high-pressure phase shows an unexpectedly low value for the bulk modulus over a narrow pressure range (below ~30 GPa), as compared with the low-pressure phase, especially for the structure with larger rare earth elements. High-pressure studies of alkaline earth-doped samples (Nd₈ A ₂(SiO₄)₆O₂ where A = Ca, Sr) showed that the pressure for the phase transition is mainly related to the size of lanthanides that occupy the large channels along the c axis of the apatite structure type.     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

Chloritoid stability in very iron-rich altered pillow lavas

Conclusions Our major conclusions are that the strong correlation of P₂O₅ and light REE abundances in basalts does not (a) require residual apatite or whitlockite during partial melting, or (b) imply that P₂O₅ and REE-rich magmas are derived from more refractory sources than the source of magmas with lower P₂O₅ and REE contents.     

Mineral processing and extraction of rare earth elements from the Wadi Khamal Nelsonite Ore, Northwestern Saudi Arabia

A technological sample (50 kg) from Wadi Khamal Nelsonite ore was subjected to magnetic and flotation concentration techniques. Excellent recovery percentages of 72.95% and 71.22% were achieved by the dry/wet magnetic and flotation concentration techniques, respectively. The weight of the apatite concentrate reached a reasonable percentage of approximately 23.5% with an overall 40.23% P₂O₅ total content. Analytical data of the apatite concentrate after digestion in concentrated sulfuric acid revealed that the total content of the rare earth elements (REE) constitutes about 0.2% of the total apatite content. The REE content (0.2%) was partitioned between phosphoric acid liquor (65%) and gypsum precipitate (36%). The extraction of the REEs from the phosphoric acid liquor using oxalic acid and sodium carbonate–bicarbonate mixture (1:10?w/w) yielded the RE oxide cake which constitute about 1.2% (w/w). The produced rare earth oxide cake contains traces of various metal oxides, e.g., SrO, Na₂O, etc. in addition to rare earth oxides. Attempts to determine quantitatively the constituents of the cake will be considered in future work.     

沉积磷灰石形成中的生物有机质因素

本文研究了黔中磷块岩中磷灰石的化学成分、红外光谱、碳和硫同位素组成以及伴生微量元素和稀土元素地球化学特征,获得了若干生物有机质成因的证据.磷灰石红外光谱特征表明CO₃^2-和SO₄^2-以类质同象部分替代PO₄^2-而进入磷灰石晶格,而碳、硫同位素特征表明,这CO₃^2-及SO₄^2-的相当部分是由生物有机质分解演化而来;叠层石磷灰石的P₂O₅含量与亲生物微量元素关系非常密切,而非叠层石者关系不甚密切;稀土元素地球化学特征表明,磷灰石的形成具有两种既有联系又各不相同的作用机制,即直接的生物作用和间接的有机质作用.     

Dispersion of niobium and phosphorus in soil overlying the Qaqarssuk Carbonatite Complex, Southern West Greenland

Rocks and soils overlying the Qaqarssuk Carbonatite Complex, southern West Greenland, were analyzed for major and trace elements by various analytical methods. The carbonatitic rocks contain up to 5% P₂O₅ and up to 0.2% Nb. The soils are relatively depleted in Ca due probably to dissolution of calcite by CO₂-rich waters. Apatite is not affected by this mechanism so that P₂O₅ tends to be enriched in the soils. A CaO/MgO ratio of less than about 1.5 is indicative of apatite accumulation in the soils. The dominant carbonate mineral in soils is dolomite and secondary apatite was not observed. Soil grains are angular and not seriously affected by mechanical transport. The investigations show that soil sampling for geochemical exploration in the arctic environment is suitable for mapping and prospecting for carbonatites.