Apatite Type Research Articles

U-Pb ages of apatite, sulfur isotopes of sulfides and possible origin of the Dashui hematite-rich, sulfide-deficient gold deposit in the West Qinling orogen, Central China

The Dashui gold (Au) deposit is one of the largest Au deposits in West Qinling orogenic belt and unique in that its metallic minerals are dominated by hematite but sulfides are extremely scarce. The age and genesis of the Dashui Au deposit, however, remain poorly constrained. To resolve these issues, here we present robust apatite U-Pb dating results under the context of detailed textural and compositional studies. The ore mineral assemblages at Dashui consist of fine-grained quartz, hematite, kaolinite, apatite, native Au, and trace amounts of pyrite. The presence of hematite and gold as inclusions fully enclosed in quartz and apatite suggests that the former minerals are of primary origin rather than, as generally considered, a product of supergene oxidation of Au-bearing pyrite. Cathodoluminescence imaging reveals that the ores contain two types of apatite. CL-bright apatite was likely inherited from the magmatic wall rocks, whereas CL-dark apatite precipitated coevally with the ore minerals. In-situ LA-ICP-MS U-Pb isotope analysis of the CL-dark apatite suggests that the Dashui deposit formed at 217.2 ± 4.1 Ma, contemporaneously with the main stage of regional Au mineralization in the West Qinling orogenic belt that formed under the Triassic subduction-collisional tectonic setting. Given than Au mineralization at Dashui is temporarily and spatially associated with intermediate to felsic porphyry intrusions, and that the ore sulfides have S isotopes consistent with a magmatic-hydrothermal origin, the deposit can be broadly classified as a Carlin-like Au deposit. Nevertheless, the hematite-rich rather than pyrite-rich ore assemblages indicate an ore-forming environment that was more oxidized than that of typical Carlin-type deposits.

Trace Element and In Situ O-Nd Isotope Signatures of Apatite from the Bilihe Porphyry Au-only Deposit: Magmatic Constraints on Au Mineralization

Abstract The magmatic controls on the formation of porphyry Au-only deposits are still poorly understood. The Bilihe deposit (> 30 t @ 2.7 g/t Au) located at the northern margin of the North China Craton is such an example, where apatite chemistry from a causative granodiorite intrusion constrains the physicochemical conditions and ore-forming potential of the porphyry-related magmas. Apatite can be subdivided by distinct CL intensities into early CL-bright and late CL-gray/dark sub-types both occurring in fresh (Ap-f), as well as in potassic (Ap-k) and phyllic (Ap-p) altered granodiorite. The mostly euhedral CL-bright apatite shows a homogeneous texture and is enriched in LREE and depleted in Fe, Mg, Mn, Y, and U compared to CL-gray/dark apatite, which develops patchy or oscillatory zoning. The CL-gray/dark apatite exhibits decreasing Fe and Mg contents as well as δ18O values from Ap-f to Ap-k and Ap-p due to consecutive fluid alteration during porphyry evolution, which was generally not observed in CL-bright apatite. We thus conclude that all types of CL-bright apatite but only CL-gray/dark Ap-f inherit the original magma composition. Binary O-Nd isotope mixing simulations suggest that both magmatic CL-bright apatite and CL-gray/dark Ap-f were influenced by crustal sediment assimilation. Our results further indicate that the magma parental to the Bilihe porphyry Au-only deposit was H2O-poor (< 2 wt.%), causing plagioclase fractionation in the absence of hornblende, as evidenced by relatively low Sr/Y (< 0.1) and significantly negative Eu anomalies in magmatic apatite. Pressure estimates by magmatic biotite that record the late crystallization stage yielded 48.9 ± 8.4 MPa, indicating a shallow final emplacement depth of 1.85 ± 0.32 km. The studied apatites formed under volatile-saturated from S deficient magmas at relatively reduced conditions (ΔFMQ + 0.5) compared to porphyry Cu deposits. We thus conclude that these physicochemical parameters together with the low-pressure conditions result in a fertile magmatic-hydrothermal environment for the formation of Au-only porphyry deposits.

Scheelite as a microtextural and geochemical tracer of multistage ore-forming processes in skarn mineralization: A case study from the giant Xintianling W deposit, South China

The Xintianling deposit is one of the largest skarn-type scheelite deposit in China. Recent discoveries of quartz-vein-type scheelite mineralization within the deposit have raised questions about its origin and the evolution of ore-forming fluids, hindering a comprehensive understanding of the ore-forming process. We investigate the microtextures, trace elements, and oxygen isotope compositions of scheelite from different stages in both skarn-type and quartz-vein-type W mineralizations. Combined with apatite geochemistry and U–Pb dating, we determine the timing of quartz-vein-type mineralization and the evolution of magmatic-hydrothermal system. Based on detailed petrological observation, three types (seven subtypes) of scheelite and two types of apatite are identified. The Mo contents and Eu/Eu* ratios of scheelite, along with the Ce/Ce* ratios of apatite indicate the oxygen fugacity of fluids during the skarn metallogenic episode is generally higher than that during the quartz-vein metallogenic episode. Furthermore, the Y/Ho ratios and REE patterns of scheelite indicate the presence of at least three significant stages of fluid influx and fluid-rock interactions throughout entire ore-forming process. The O isotope compositions of scheelite in the quartz-vein-type metallogenic episode reveal that the ore-forming fluids are originated from a magmatic source, and meteoric water was mixed into the system, leading to the precipitation of the latest stage of scheelite. The apatites closely coexist with scheelite, from the early and the late stages of quartz-vein metallogenic episode, yield consistent U–Pb ages within error of 160.4 ± 2.4 Ma and 158.4 ± 1.3 Ma, respectively, indicating a close genetic link between quartz-vein-type W mineralization and the fine-grained porphyritic biotite granite. Our study highlights the significance of pulsed fluid exsolution and the combined effects of multiple mechanisms, including fluid-rock interaction, fluid mixing, and physicochemical condition changes, in the formation of large W deposits.

Apatite and pyroxene as records of magmatic–hydrothermal processes and platinum-group mineral (PGM) formation in the Wengeqi mafic–ultramafic intrusion, Inner Mongolia, China: The role of oxidized, H2O-rich magmas

The Devonian Wengeqi mafic–ultramafic intrusion, situated on the northern margin of the North China Craton (NCC) — an Andean-style convergent margin during the Paleozoic — hosts many platinum-group minerals (PGMs), especially within the S-deficient, magnetite-rich clinopyroxenite zones. These PGMs occur in two distinct associations: Pt-rich PGMs (e.g., sperrylite) closely associated with primary magnetite and Pd-rich PGMs (e.g., sudburyite, kotuskite, arsenopalladinite) associated with secondary minerals (e.g., actinolite, pyrite). The mechanisms underlying the formation of PGMs in S-deficient rocks and the spatial decoupling of various PGM types remain elusive. The relationship of PGM formation and characteristics of magmas at convergent margins is also not well understood. In this contribution, we utilized apatite and clinopyroxene textures and chemistry alongside whole-rock SrNd isotopes to characterize i) the nature of the parental magma from which the Wengeqi intrusion crystallized, and ii) the magmatic–hydrothermal processes that operated to generate the Pt- and Pd-rich PGM. Based on the composition of clinopyroxene and clinopyroxene–melt partition coefficients, the parental magma of the Wengeqi intrusion is estimated to have an arc-like affinity on a primitive mantle-normalized trace-element diagram. This, together with the EMI-like SrNd isotope signature, implies that the Wengeqi magma was sourced from metasomatized SCLM beneath the NCC with an EMI-like composition. Three types of apatite (Ap1, Ap2, and Ap3) were identified within the intrusion. Ap1 and Ap2 are magmatic in origin, and appear as isolated grains, whereas Ap3 occurs as stringers or heterogeneous domains within Ap1 and Ap2, and likely resulted from hydrothermal modification of magmatic apatite. Notably, the abundant Ap2 exhibits higher VS contents and Eu/Eu* ratios than the less common Ap1, and contains S predominantly in the form of S6+, suggesting that the Wengeqi magma was relatively oxidized, with fO2 > FMQ + 1.2. Based on the chemistry of magmatic apatite, the Wengeqi magma had ∼5 wt% H2O, which, together with its high fO2, facilitated crystallization of magnetite, causing reduction of the magma by removal of Fe3+. This reduction process promoted PGM nucleation by decreasing PGE solubility in the magma, leading to the association of PGM with magnetite. Additionally, the oxidized, H2O-rich magma likely released oxidizing fluids, selectively mobilizing Pd rather than Pt, separating Pt-rich PGMs from Pd-rich PGMs. The budget of PGE in the parental magma could have been increased by i) metasomatism of the SCLM source (e.g., by carbonatitic fluids), which would have elevated the concentration of PGE in the mantle source, and ii) the high fO2 and H2O levels of the magma, which would have delayed sulfide saturation. Accordingly, mantle metasomatism and high fO2–H2O are deemed favorable for enrichment of PGE in magmas within convergent margins.

Innovative imaging of iron deposits using cross‐gradient joint inversion of potential field data with petrophysical correlation

AbstractThis study demonstrates the application of the cross‐gradient joint inversion method to investigate iron mineralization zones within a volcano‐sedimentary environment. The presence of minerals with intense contrasts in density or magnetic susceptibility, such as hematite or magnetite, facilitates modelling the distribution of ore bodies with depth. Our approach involves establishing a unified interpretation of reconstructed density and susceptibility models through both independent and joint inversion with sparsity regularization in conjunction with a petrophysical model resulting from core data. This approach provides an ideal strategy to uncover the realistic geologic setting of iron ore deposits. We initially simulated a synthetic model closely resembling real‐case scenarios to assess the efficacy of the cross‐gradient joint inversion algorithm in comparison to independent inversion. Subsequently, the inversion algorithms were implemented on gravity and magnetic data, collected over an area of 500 × 600 m2 in Shavaz iron‐bearing deposits located in the central Iranian block. The primary iron oxide–apatite type mineralization in the study area is associated with the Nain–Dehshir–Baft fault as a NW–SE trending strike‐slip fault. Although both inversion methods yield satisfactory models, incorporating the cross‐gradient constraint in joint inversion resulted in a more constrained delineation of iron–oxide ore deposits in the fault system. This improvement facilitates the differentiation between hematite and a small percentage of magnetite, providing a more accurate estimation of ore depth. Inversion results suggest that the magnetite mineralization is coated with extensive hematite mineralization and both are positioned relatively within the same depth interval, covered by approximately a 15–25 m sequence of sediments.

Structural, optical and photoluminescence characteristics of apatite type lanthanide silicates

This article reports the solid state synthesis of apatite type rare earth-transition metal silicates Nd4MnSi3O13 and Sm4MnSi3O13. These oxyapatite type lanthanide silicates were characterized through structural, micro structural, optical and photoluminescence properties. The indexed X-ray diffraction patterns and Raman analysis confirm that both the samples crystallize in single phase hexagonal symmetry with space group P63/m. Transmission electron microscopy images along with electron diffraction pattern indicate the good crystalline nature of both the samples which further support the results obtained from X-ray diffraction study. The optical band gap energies are found to be 4.1 eV and 3.9 eV for Nd4MnSi3O13 and Sm4MnSi3O13 respectively. The wide optical band gap values of these semiconductor silicates make enable them for fundamental and technological applications. The luminescent properties and CIE coordinates showed the green-yellow emission of these synthesized silicates which further indicate that these compounds may have uses in solid state lighting because of the tunable luminescence.

Apatite as a Record of Magmatic–Hydrothermal Evolution and Metallogenic Processes: The Case of the Hongshan Porphyry–Skarn Cu–Mo Deposit, SW China

Apatite, as a common accessory mineral found in magmatic–hydrothermal deposits, effectively yields geochemical insights that facilitate our understanding of the mineralization process. In this research, multiple generations of magmatic and hydrothermal apatite were observed in the Hongshan porphyry–skarn Cu–Mo deposit in the Yidun Terrane in SW China. The geochemical compositions of the apatite were studied using in situ laser ablation–inductively coupled plasma mass spectrometry and an electron probe microanalysis to understand the magmatic–hydrothermal processes leading to ore formation. The apatite (Ap1a) occurs as subhedral to euhedral inclusions hosted in the phenocrysts of the granite porphyry. The Ap1b occurs later than Ap1a in a fine-grained matrix that intersects the earlier phenocrysts. Increases in F/Cl, F/OH, and F/S and decreases in ΣREE and (La/Yb)N from Ap1a to Ap1b suggest the exsolution of a volatile-rich phase from the magma. The skarn hosts three types of hydrothermal apatite (Ap2a, Ap2b, and Ap3), marking the prograde, retrograde, and quartz–sulfide stages of mineralization, respectively. The elemental behaviors of hydrothermal apatite, including the changes in Cl, Eu, As, and REE, were utilized to reflect evolutions in salinity, pH, oxygen fugacity, and fluid compositions. The composition of Ap2a, which occurs as inclusions within garnet, indicates the presence of an early acidic magmatic fluid with high salinity and oxygen fugacity at the prograde skarn stage. The composition of Ap2b, formed by the coupled dissolution-reprecipitation of Ap2a, indicates the presence of a retrograde fluid that is characterized by lower salinity, higher pH, and a significant decrease in oxygen fugacity compared to the prograde fluid. The Ap3 coexists with quartz and sulfide minerals. Based on studies of Ap3, the fluids in the quartz–sulfide stage exhibit relatively reducing conditions, thereby accelerating the precipitation of copper and iron sulfides. This research highlights the potential of apatite geochemistry for tracing magmatic–hydrothermal evolution processes and identifying mineral exploration targets.

Continental Arc Plutonism in a Juvenile Crust: The Neoproterozoic Metagabbro-Diorite Complexes of Sinai, Northern Arabian-Nubian Shield

Based on new field, petrographic, and whole-rock geochemistry data, we investigated three discrete metagabbro-diorite complexes (MGDC) across the E-W Sinai to contribute to increasing knowledge of the evolution of the juvenile continental crust of the Neoproterozoic Arabian–Nubian Shield. The three MGDCs vary in the dominance of the gabbroic versus dioritic rock types among each of them. Gabbroids are distinguished into pyroxene-hornblende gabbros and hornblende gabbros, whereas dioritic rocks have been subdivided into diorites and quartz diorites. The studied MGDC rocks are almost metaluminous and possess prevalent calc-alkaline characteristics over subsidiary tholeiitic and alkaline affinities. The most distinctive feature in the profiles of the investigated MGDCs on the N-MORB-normalized spider diagrams is the coincidence of stout negative Nb anomalies and projecting positive Pb spikes, which is typical of igneous rocks evolved in subduction zones. The three MGDC samples exhibit variably LREE-enriched patterns [(La/Yb)N = 4.92–18.55; av. = 9.04], either lacking or possessing weak to negligible positive and negative Eu anomalies. The calculated apatite and zircon crystallization temperatures reveal the earlier separation of apatite at higher temperatures, with the obvious possibility of two genetic types of apatite and zircon in the magma (cognate vs. xenocrystic) since both accessories have yielded very wide ranges of crystallization temperatures. The investigated MGDCs were formed in a continental arc setting, particularly a thick-crust arc (>39 km). The parent magmas comprised components derived from the melting of the mantle wedge, subducting oceanic lithosphere, and subducting overlying sediments. The mantle input was from a spinel–garnet transitional mantle source at a depth of ca. 75–90 km. The impact of slab-derived fluids was much greater than that of slab-derived melts, and so subduction-related fluids had a crucial effect on metasomatizing the partially melted mantle source. The parent mantle-derived magma has been subjected to substantial crustal contamination as a dominant mechanism of differentiation.

Influence of partial replacing of CaO by SrO on structure and bioactivity of calcium-phospho-silicate glasses

New alkali-free bioglasses of the ternary 60SiO2·5P2O5·35CaO parent glass wherein Ca is partially substituted by Sr (up to 10 mol%) were prepared by sol-gel method. The replacement of Ca with Sr induced the tendency to crystallisation of an apatite type phase. The bioactivity tested in vitro depends on Ca/Sr replacement degree, despite the fact that the theoretical network connectivity does not change with Ca/Sr substitution. After seven days of incubation in simulated body fluid, only on the samples with x ≥ 5 mol% SrO was developed a layer assumed of combined Ca/Sr composition of carbonated hydroxyapatite. Bactericidal activity was observed exclusively in case of strontium containing samples, for both Gram positive and negative bacteria. Structural effects of partial replacing of CaO by SrO were investigated by X-ray diffraction and FTIR analysis both before and after samples incubation in simulated body fluid.

The origin and significance of euhedral apatite crystals on conodonts

Crystal overgrowth on fossil remains is well-documented in the literature. Attention has specifically focused on bioapatite (i.e., an apatite of biochemical origin regardless of post-mortem changes) configurations, in order to decipher any possible relation to fossilization/diagenesis. This study investigates the Rare Earth Element (REE) and other High-Field-Strength Element (HFSE) composition of euhedral crystals formed on the surface of conodont elements compared with that of crystal-free surfaces. Euhedral crystals are by definition crystals characterized by sharp faces, developing solids that, for apatite, assume the form of hexagonal prisms, reflecting its crystal symmetry. Late Ordovician (Amorphognathus ordovicicus Zone) conodonts from two localities in Sardinia and the Carnic Alps (Italy) are herein investigated. Conodont elements reveal the occurrence of smooth surfaces and surfaces partially covered with euhedral crystals. Since euhedral crystals did not reasonably grow during the organism's lifetime, the REE and HFSE analysis can provide important insights into the crystal growth process. The experimental results indicated a substantial contribution of diagenetic imprinting for all the analyzed material, although more evident on euhedral crystals that are significantly enriched in middle and, subordinately, in heavy REE with respect to smooth surfaces. The positive correlations between La + Th vs log[ΣREE] and Ce + Th vs log[ΣREE] could support the hypothesis that the neoformed euhedral crystals grew also by depleting the pristine bioapatite of the conodont elements. Nevertheless, the occurrence of two types of apatite cannot be ruled out: euhedral crystals as neoformed products of diagenetic processes and smooth surfaces as remains of the pristine conodont bioapatite after diagenesis.

CMAS corrosion behavior of a novel high entropy (Nd0.2Gd0.2Y0.2Er0.2Yb0.2)2Zr2O7 thermal barrier coating materials

The CMAS corrosion behavior of a novel high entropy material (Nd0.2Gd0.2Y0.2Er0.2Yb0.2)2Zr2O7 with thermal conductivity of 1.215 W·m−1·K−1 was investigated. Results show that a dense layer composed of apatite type RE8Ca2(SiO4)6O2 phase and RE/Ca-ZrO2 forms in front of the reaction layer, which dramatically decreases the infiltration rate of CMAS from 20 to 5.3 µm/h at 1300 °C. Moreover, the elements with a larger ion radius are easier to form apatite type phase to slow down the further infiltration of CMAS. This study reveals that the high entropy (Nd0.2Gd0.2Y0.2Er0.2Yb0.2)2Zr2O7 ceramic is a promising candidate for TBCs with extreme resistance to CMAS corrosion.

Formation of Fluorapatite in the Equilibrium System CaO–P2O5–HF–H2O at 298 K in a Nitrogen Atmosphere

The process of biomineralization of apatite in nature has been studied by scientists from various fields of science for more than a century. Unlike the volcanogenic, hydrothermal, and other types of igneous apatites, the genesis of which is entirely clear, the formation of phosphate ores of marine sedimentary origin is still debatable. Since phosphate concentrations in water bodies are too low for the spontaneous precipitation of solid phosphates, the study of different ways for their concentration is of particular interest. In this work, phase equilibria in the system CaO–P2O5–HF–H2O at 298 K, involving fluorapatite formation, have been studied. Fluorapatite is known to be the most common phosphate mineral and the main source of phosphorus on Earth, playing an important role in the mineralization process of dental tissues in vertebrates. The equilibrium in the system defined above was studied at a low mass fraction of the liquid phase components, i.e., in conditions close to natural. It has been shown that the compounds of variable composition with the fluorapatite structure containing HPO42− ions were formed in the acid region of this system. These compounds are formed at pH ≤ 7.0 and have invariant points with monetite, CaHPO4, and fluorite, CaF2. Stoichiometric fluorapatite was formed at the lowest concentrations of the liquid phase components in a neutral and weakly alkaline medium and had an invariant point with Ca(OH)2. The composition of the resulting equilibrium solid phases was found to be dependent on the Ca/P ratio of the initial components and pH of the equilibrium liquid phase. Fluorite CaF2 was present in each sample obtained in this study.

Controls on metal fertility of dioritic intrusions in the Laiwu district, North China Craton: Insights from whole-rock geochemistry and mineral compositions

Several large high-grade iron skarn deposits in the Laiwu district of Shandong Province (North China Craton) are developed along the contact zone between the Early Cretaceous Kuangshan diorite pluton and Middle Ordovician dolomitic limestone. In sharp contrast, no iron skarn mineralization has been recognized in association with other contemporaneous dioritic intrusions (Jiaoyu, Jinniushan, Tietonggou) in this district. The reason for this contrast remains elusive. Here we present a comparative study of the ore-related Kuangshan pluton and its barren equivalents using whole-rock and mineral (zircon, apatite) geochemistry combined with existing Sr-Nd isotope data to provide new insights into the critical controls on iron skarn mineralization and shed light on future mineral exploration. Geochemical and Sr-Nd isotope data suggest that both the ore-related and barren intrusions were derived from a common enriched lithospheric mantle source following variable degrees of fractional crystallization and crustal assimilation. Modeling based on whole-rock Sr-Nd isotopes implies that the magmas responsible for the Kuangshan and Jinniushan diorite plutons assimilated significant quantities of the Ordovician evaporite-bearing carbonates. Both the fertile and barren diorites show high whole-rock Sr/Y ratios, high zircon Eu/Eu* and Eu/Eu*/Y ratios, and low zircon Dy/Yb ratios. These data, combined with high magmatic water contents (4.4−8.0 wt%) calculated from amphibole compositions, indicate that those four plutons crystallized from hydrous magmas. High whole-rock Fe2O3/FeO, and high ΔFMQ values (mostly >1; fayalite-magnetite-quartz oxygen buffers) estimated from zircon, apatite, and amphibole suggest that the magmas from which the diorite intrusions crystallized were all oxidized. Using available partitioning coefficients for Cl between apatite and magma, the parental melts of the Kuangshan and Jinniushan diorite are estimated to have had higher Cl contents (0.15−0.77 wt%) than the Jiaoyu and Tietonggou diorites (0.06−0.34 wt%). Two types of apatite from the intrusions studied are recognized based on their paragenetic relations: Type 1 apatite (Ap1) is an early-formed phase enclosed in euhedral amphibole, plagioclase, and biotite, whereas type 2 (Ap2) is a late-formed variety hosted in, or intergrown with, anhedral K-feldspar (± anhedral amphibole ± subhedral to anhedral quartz). In the fertile Kuangshan diorite, Cl and OH contents of apatite decrease, but Sr contents increase from Ap1 to Ap2. However, those parameters show reverse trends or remain constant from Ap1 to Ap2 in barren diorites. Such distinctive apatite geochemical signatures are best interpreted as reflecting more efficient fluid exsolution from the parental magma of the Kuangshan diorite than from the barren intrusions. This view is supported by the presence of abundant fluid inclusions in apatite and quartz exclusively from the mineralized intrusion, indicating its crystallization from volatile oversaturated melts. The results presented here indicate that elevated magma Cl contents and efficient separation of magmatic hydrothermal fluid from cooling magmas have been the critical factors controlling iron skarn mineralization in the Laiwu district. Mass balance constraints on Cl budget indicate that a minimum of 44−60 km3 of magma was required to form the Fe deposits associated with the Kuangshan pluton. Our preliminary results suggest that decreasing OH and Cl contents from early to late apatite in intermediate rocks can be used as an indicator for efficient fluid exsolution and consequently metal fertility of those rocks.

Neoproterozoic Zn-Pb mineralization in the world-class Sichuan-Yunnan-Guizhou Zn-Pb triangle, southwest China: Insights from apatite geochemistry and in situ sericite Rb-Sr geochronology of the Daxiao deposit

The Sichuan-Yunnan-Guizhou (SYG) zinc-lead triangle, located in southwestern China, is an important producer of zinc, lead, silver, and critical raw metals such as germanium. In this region, most Zn-Pb deposits hosted in the later Ediacaran to Permian carbonate rocks are believed to be Mississippi Valley-type (MVT) deposits, while the origin of the Zn-Pb deposits found in the Mesoproterozoic basement remains controversial. To address this gap, our study conducted in situ LA-ICP-MS/MS muscovite Rb-Sr dating and apatite major, trace and Sr isotope analysis on the Daxiao deposit hosted in the Mesoproterozoic basement. The in situ Rb-Sr dating of sericite yielded a Neoproterozoic age of 766 ± 31.3 Ma, challenging the previously proposed Indosinian orogen-related MVT model. Instead, it links the formation of this deposit to an extensional setting that coincided with the breakup of the Rodinia. We identified a specific type of apatite, recognized as ore-stage apatite based on texture and analyzed composition, within the deposit. The ore-stage apatite exhibits high 87Sr/86Sr ratios (ranging from 0.78384 to 0.81082), similar to those of the Archean basement rocks.Based on our study and previous data, we proposed a new genetic model for the Daxiao Zn-Pb deposit, and possibly other basement-hosted Zn-Pb deposits in the SYG triangle. During the Neoproterozoic (∼766 Ma), the study area experienced an extensional setting characterized by crustal thinning and magmatic activity resulting from the breakup of the Rodinia. Basinal brines infiltrated the deep Archean basement along faults and were heated to high temperatures by magma and/or high geothermal gradients. These hot brines continuously extracted Pb, Zn from the Archean basement and migrated upward into the Mesoproterozoic host rock, where they precipitated lead–zinc ores in favorable structural positions. The Daxiao Zn-Pb deposit, along with the coexisting sediment-hosted stratabound copper (SSC) deposits, basement-hosted gold and uranium deposits, and late sulfide mineralization in the iron oxide-copper–gold (IOCG) deposits, suggests a Neoproterozoic regional mineralization event associated with the breakup of Rodinia. Our study also highlights the potential of using in situ sericite Rb-Sr dating to precisely determine the age of other hydrothermal ore deposits, such as Carlin-type Au deposits, which have long been a subject of uncertainty.

Distinct REY sources recorded in the Doushantuo phosphorite

During the Ediacaran period, massive marine phosphorites were deposited worldwide, which could represent a global sink of rare earth elements and yttrium (REY) in oceans. In the Doushantuo Formation of South China, the REY source has been preliminarily constrained as the mixed sources of seawater and terrigenous matter in these phosphorites. However, the REY composition of both seawater and terrigenous endmembers is still unclear; therefore, it’s difficult to identify the contributions of seawater and terrigenous sourced REY. In this work, REY and other trace elements of bulk phosphorites, in situ carbonates, and apatite grains were analyzed from a drill core (Fangmashan) of the Doushantuo Formation in South China. Combined with mineralogical observations, the REY composition of seawater and terrigenous endmembers is well-constrained. Along the investigated Fangmashan drill core, all in situ carbonates (calcites and dolomites) show a modern seawater-like REY pattern, indicating that the REY characteristics of the Doushantuo seawater could be similar to those of modern oxic seawater without significant changes. Alternatively, apatites from the lower and upper phosphorites showed distinct REY patterns. One type of apatite in the upper phosphorites showed a modern seawater-like REY pattern, indicating authigenic REE enrichment from the seawater column. However, another type of apatite in the upper phosphorites with an REE pattern that deviated from seawater showed high ΣREY (∼691.16 ± 309.78) and low Y/Ho (∼40.52 ± 4.05), probably reflecting mixed REY sources and/or the effects of early diagenesis. It is noted that most apatites in the lower phosphorites are obviously enriched in light REY (LREY: La - Nd) compared to heavy REY (HREY: Ho - Lu and Y), which may represent a significant contribution of the terrestrial REY source. This study reveals that the REY composition of paleo-seawater could be similar to modern seawater as early as the Neoproterozoic and supports a significant contribution to understanding the difference in the REY composition of phosphorites in geological history.

Geology, mineralogy and geochemistry of the Morro Preto Alkaline-carbonatite complex, Goiás, Brazil

The Morro Preto Complex, located in the northern portion of the Cretaceous Goiás Alkaline Province, is unique in the region due to the large predominance of carbonatites and phosphate mineralization. It comprises two circular intrusions (Morro Preto North and Morro Preto South) of apatite-rich magnesiocarbonatites gradually transitioning to ferrocarbonatites. The complex also hosts fenites produced by carbonatite metasomatism at the contacts with the Neoproterozoic country rocks. Kamafugite dykes with carbonate globules suggest an immiscibility link between silicate and carbonatite magma.The magnetite-apatite-dolomite carbonatites vary in texture and modal composition from cumulates to magnesiocarbonatites with variable apatite and magnetite, with minor barite and traces of pyrochlore, phlogopite, baddeleyite and zircon. In the ferrocarbonatites, magnetite and apatite are rare or absent, and the dominant carbonate varies from Fe-dolomite to ankerite and siderite, with traces of bastnaesite, monazite, thorium-rich monazite and sulfides. SiO2, Fe2O3, MnO, BaO:SrO and the sum of rare earth elements (REEs) increase from magnesiocarbonatites to ferrocarbonatites, whereas the CaO, MgO and P2O5 contents decrease.Four main apatite types are recognized in the complex: (i) high P-REE primary magmatic sub-euhedral apatites (type 1), (ii) fluorapatite associated with ferrodolomite-rich zones (type 2), (iii) fine-grained, Na-rich metasomatic apatite (type 3) and (iv) secondary fluorapatite filling veinlets and cavities (tuupe 4). In general, the apatite morphological and compositional variations correlate with carbonate evolution and with stable isotope data. Dolomite and type 1 apatite represent the primary group (+9.49 to +11.88‰ δ18O and −5.1 o −4.66‰ δ13C). Ferrodolomite, iron-rich carbonates, along with types 2 and 4 fluorapatite have heavier isotope compositions (up to +21.59‰ δ18O and −3.33‰ δ13C), indicating metasomatic reworking related to late-stage carbonatite-derived fluids.Geological, geochemical and mineral chemistry data are consistent with the evolution of the complex by crystal fractionation, liquid immiscibility, metasomatic overprinting and late hydrothermal events. The K fenitization and late-stage carbohydrothermal events suggest that the Morro Preto Alkaline-Carbonatite Complex represents the uppermost parts of a carbonatite magmatic system.

Identifying the roles of major phosphorus fractions in REY enrichment of Pacific deep-sea sediments using sequential extraction and mineralogical analysis

Bioapatite (i.e., fish teeth and debris) is considered the predominating carrier of rare earth elements (REY, including lanthanide (Ln) and yttrium (Y)) due to the positive correlation between phosphorus (P) and REY in REY-rich deep-sea sediments. Besides bioapatite, the presence of various P species such as vivianite and authigenic carbonate-fluorapatite suggests other P species may have also contributed to the enrichment of REY in the REY-rich deep-sea sediments, yet their roles in REY enrichment are still unclear. This study investigated the REY characteristics of five P species (fractions), including exchangeable and loosely adsorbed P (Ex-P), Fe oxides bound P (Fe-P), authigenic apatite, and biogenic apatite (Ca-P), detrital apatite (Detrital-P), and organic-P (Org-P), in deep-sea sediments from the Pacific Ocean by using the sedimentary extraction (SEDEX) method and micro-scale analysis. The results show that Ca-P contributes 49.42% of the total P, while Fe-P and Detrital-P comprise 45.04% of the total P. The heavy rare earth enrichment is more visible in Fe-P and Ca-P compared to insignificant trends in the other fractions. Meanwhile, multiple forms of apatite demonstrate varied sources of REY in the Ca-P fraction. For instance, the formation of new apatite on the surface of a phillipsite explains the exceptionally high REY content in the Ca-P fraction. These results suggest that all investigated P fractions in deep-sea sediments positively contribute to REY enrichment and that in addition to fish teeth, other types of biogenic and authigenic apatites may also be important REY carriers.

The Characteristics, Enrichment, and Migration Mechanism of Cadmium in Phosphate Rock and Phosphogypsum of the Qingping Phosphate Deposit, Southwest China

Sedimentary phosphate rocks are characteristically rich in organic matter, and contain sulfides and a high concentration of trace elements, including cadmium (Cd), which is harmful to the human body. The mining of phosphate rock and phosphogypsum at Qingping has expanded the release of Cd into groundwater and farmland soil. To prevent and control Cd pollution it is critical to reveal the carrier mineral phase(s) and migration mechanism of Cd and other elements in phosphate rock and phosphogypsum. The elemental and mineral composition of bulk samples were analysed by XRF, ICP-MS, and XRD, respectively. The results showed that from phosphate rock to phosphogypsum, the main constituent elements changed from CaO (49.43%) and P2O5 (36.63%) to CaO (33.65%) and SO3 (>34%), and the main mineral changed from fluorapatite to gypsum. Among all the elements, the element transfer factor (ETF) of P2O5, F, Co, U, Cd, and other elements was low; the ETF (Cd) was only 10.85%, and only a small amount of Cd entered the acidic phosphogypsum during the production process. Raman spectroscopy analysis revealed two types of apatite: the brown–black apatite with organic matter (type 1) and the yellow–light brown apatite without organic matter (type 2). LA-ICP-MS analysis showed that the Cd element content in type 2 was lower, while the organic matter and Cd element content in type 1 were higher, suggesting that Cd may be controlled by organic matter, and the relationship with apatite is not apparent. Electron probe analysis and XRD semiquantitative results show that the content of Cd in pyrite is higher (511 ppm), which is significantly higher than that of bulk rock. In addition, pyrite is rich in Co, As, Ni, Zn, and other elements. The content of Cd in phosphate ore shows a good correlation with that of pyrite. Cd in Qingping phosphate rock is mainly controlled by organic matter and pyrite, and only a small amount of Cd is transferred to phosphogypsum. Reducing the environment leads to the enrichment of Cd in phosphate rock.

Apatite in brachinites: Insights into thermal history and halogen evolution

Abstract Apatite is an important petrogenetic indicator in extraterrestrial materials. Here, we report the mineralogical features of apatite and associated phases in three brachinites Northwest Africa (NWA) 4969, NWA 10637, and NWA 11756. Two types of apatite are observed: intergranular apatite and apatite inclusion within chromite and silicate minerals. The intergranular chlorapatite is enclosed by or penetrated by irregular porous merrillite, indicating chlorapatite replacement by merrillite. The intergranular chlorapatite is closely associated with a fine-grained pyroxene-troilite intergrowth along olivine grain boundaries, which is a sulfidization product of olivine. High-Ca pyroxene is observed as a constituent phase in the intergrowth for the first time. The apatite inclusions are either monomineralic or closely associated with subhedral-euhedral pore-free merrillite. In NWA 4969, the apatite inclusions show a large compositional variation from chlorapatite to fluorapatite and are systematically more F-rich than intergranular apatite; while the apatite inclusions in NWA 10637 and NWA 11756 are chlorapatite. Most of the two apatite types in brachinites contain oriented tiny or acicular chromite grains, suggesting the exsolution of chromite from apatite. We propose that apatite replacement by merrillite, formation of pyroxene-troilite intergrowth, and exsolution of chromite in apatite were caused by a shock-induced, transient heating event (~930–1000 °C) on the brachinite parent body. This heating event resulted in halogen devolatilization during replacement of the intergranular apatite by merrillite, which probably disturbed the Mn-Cr isotopic system in brachinites as well. We also propose that the apatite inclusions could be a residual precursor material of the brachinites.

Assimilation of xenocrystic apatite in peraluminous granitic magmas

Abstract Apatite is a ubiquitous phase in granite plutons and in most adjacent country rocks, thus contamination of a granite magma with wall-rock material results in two genetic types of apatite in the magma: cognate and foreign. These two textural and chemical varieties of apatite undergo textural and compositional changes to reach physical and chemical equilibrium (perfect assimilation) in the melt. Our experiments replicate the conditions in such contaminated granites. The starting materials consist of a peraluminous synthetic SiO2-Al2O3-Na2O-K2O (SANK 1.3) granite gel with A/NK of 1.3, synthetic F-apatite, synthetic Cl-apatite, and natural Durango apatite. Initial experiments in cold-seal hydrothermal pressure vessels at magmatically realistic temperatures of 750 °C and pressures of 200 MPa produced negligible reactions, even after run times of 2000 h. Instead, we used an argon-pressurized internally heated pressure vessel with a rapid-quench setup at temperatures of 1200 °C, pressure of 200 MPa, and run durations of 192 h. An advantage of this high temperature is that it exceeds the liquidus for quartz and feldspar; therefore, apatite is the only solid phase in the run products. The starting composition of each run was 90 wt% SANK 1.3 granite gel and 10 wt% crushed apatite (consisting of one, two, or three varieties), with and without 4 wt% added H2O. Run products were examined by SEM for texture and by EMPA and LA-ICP-MS for composition. The starting synthetic granite composition contains no Ca, F, Cl, or REEs thus, in every run, apatite was initially undersaturated in the melt. In all experiments, most large apatite grains consisted of anhedral shards with rounded corners, most small apatite grains were round, and a small proportion of apatite grains developed one or more crystal faces. In experiments with two or three apatite compositions, the run-product apatite grains had compositions intermediate between those of the starting-material grains, and they were homogeneous with respect to Cl, and probably F, but not with respect to REEs. The processes to reach textural equilibrium consist of dissolution until the melt is saturated in apatite, followed by Ostwald ripening to eliminate small grains and to develop crystal faces on larger ones. The processes to reach chemical equilibrium consist of dissolution of apatite, diffusion of cations (Ca, P, REE) and anions (F, Cl, OH) through the silicate melt, and solid-state diffusion in the undissolved apatite grains. The halogens approached chemical equilibrium in all experiments, but in the experiments containing Durango apatite, the REEs have not. Models involving radial diffusion into spherical apatite grains at the temperatures of the experiments show complete re-equilibration of the halogens, but changes in the REE concentrations affecting only the outer few micrometers. We conclude that the rate of chemical equilibrium for the halogens is greater than the rate of physical equilibrium for texture, which in turn is greater the rate of chemical equilibrium for REEs. We illustrate these processes with a natural example of contaminated granite from the South Mountain Batholith in Nova Scotia. Given that all granites are contaminated rocks, we propose that future petrogenetic studies focus on developing techniques for a minerals-based quantitative estimation of contamination (QEC).