Variation of Cl and SO3 Contents of Microphenocrystic Apatite in Intermediate to Silicic Igneous Rocks of Cenozoic Japanese Island Arcs: Implications for Porphyry Cu Metallogenesis in the Western Pacific Island Arcs

Abstract. Determinations of SO₃ and Cl contents of igneous accessory apatite were carried out on Late Cenozoic intermediate to silicic intrusive and volcanic rocks in the Japanese island arcs of the western Pacific rim including the southwestern Kuril arc (eastern Hokkaido), Northeast Japan arc (southwestern Hokkaido through northeastern Honshu to central Honshu), Izu‐Bonin arc, Kyushu‐Palau ridge, Southwest Japan arc (northern Kyushu) and northern Ryukyu arc (southern Kyushu). These were compared to those from the Western Luzon arc, Philippines, to better understand the metallogenesis of porphyry Cu deposits in the western Pacific island arcs. In addition, SO₃ and Cl contents of accessory apatite in the Cretaceous magnetite‐series granitic rocks in the Kitakami belt (northeastern Honshu) and the Miocene ilmenite‐series granitic rocks in the Outer Zone of Southwest Japan (southern Kyushu) were also examined. Microphenocrystic apatites in shallow intrusions associated with porphyry Cu deposits in the Western Luzon arc contain >0.1 wt% S as SO₃. Such high SO₃ contents of microphenocrystic apatite are a common characteristic of hydrous mag‐matism in the Western Luzon arc, from 15 Ma old tonalitic plutonic rocks of the Luzon Central Cordillera to present‐day volcanism at Mount Pinatubo. The accessory apatite in intrusive rocks associated with porphyry Cu deposits, especially those at the Santo Tomas II deposit, show significantly high Cl contents (>2 wt%). The SO₃ contents of microphenocrystic apatite in most of the hydrous silicic rocks along the volcanic front, in andesites related to native sulfur deposits, and in Miocene and younger shallow granitic intrusions in northeastern Honshu, are generally <0.1 wt%. On the other hand, the SO₃ contents of apatite in such rocks from eastern Hokkaido, southwestern Hokkaido, Izu, northern Kyushu and southern Kyushu are similar to those from the Western Luzon arc. The SO₃ contents of accessory apatite in the Cretaceous magnetite‐series granitic rocks in the Kitakami belt are variable, whereas those of the Miocene ilmenite‐series granitic rocks in southern Kyushu are extremely low. The Cl contents of accessory apatite in some rocks of the Northeast Japan arc, Izu‐Bonin arc and Southwest Japan arc are significantly high. In terms of the Cl and SO₃ contents of microphenocrystic apatite, Cenozoic Japanese arc magmatism show similarities with arc magmatism associated elsewhere with porphyry Cu mineralization, except for the most of northeastern Honshu of the Northeast Japan arc. Apatite commonly occurs as inclusions in other phenocrystic phases. Thus the variation in SO₃ contents of apatite is a feature of early stage magmatic differentiation. The SO₃ contents of microphenocrystic apatite are considered to reflect the redox state of the magma source region or fluids encountered during magma generation.     

Duluth Complex apatites: Age reference material for LA–ICP–MS‐based fission‐track dating

Anorthositic series apatites of the Duluth Complex, Minnesota, USA, have high spontaneous fission‐track densities of up to ~10⁷ cm^–2 and a homogeneous age of ~900 Ma, allowing high‐precision fission‐track dating based on LA–ICP–MS U analysis. Absolute fission‐track dating, track‐length measurement and chemical composition analysis were performed to evaluate a cooling history, which is essential for age reference materials. Preliminary inverse modelling for a sample with a shortened track‐length distribution yielded a monotonic cooling history from ~100°C at 925 Ma. The apatites incur an over‐etching problem when employing the commonly used etching protocol involving 5.5 M HNO₃.     

Major and Trace Element Characteristics of Apatites in Granitoids from Central Kazakhstan: Implications for Petrogenesis and Mineralization

This paper presents abundances of major and trace elements of apatites in granitic rocks associated with different types of ore deposits in Central Kazakhstan on the basis of electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. Our results demonstrate that the concentrations and ratios of elements in apatites from different granitoid rocks show distinct features, and are sensitive to magma evolution, petrogenetic and metallogenetic processes. Apatites in the rocks associated with Mo‐W deposits have high content of F and MnO, low content of Cl, which may be indicative of sedimentary sources, while apatites from a Pb‐Zn deposit show relatively high content of Cl and low F content, which possibly suggest a high water content. In these apatites, Sr contents decrease, while Mn and Y contents increase with magma evolution. This relationship reflects that these elements in apatites are related with the degree of magmatic differentiation. Four types of REE patterns in apatites are identified. Type 1 character of highest (La/Yb)_N in apatites of Aktogai porphyry Cu‐Mo deposit, Sayak‐I skarn Cu deposit and Akzhal skarn Pb‐Zn depposit is likely produced by the crystallization of heavy REE‐enriched minerals. Type 2 character of upward‐convex light REE in apatite of Aktogai porphyries likely results from La‐enriched mineral crystallization. Type 3 feature of Nd depletion in apatites of East Kounrad and Zhanet deposits both from Mo‐W deposits primarily inherits the character of host‐rock. Type 4 apatites of Aktogai deposit and Akshatau W‐Mo deposit with wide range of REE contents may suggest that apatites crystallize under a wide temperature range. Three types of apatite with distinct redox states are identified based on Eu anomaly. The Aktogai apatite with slight negative Eu anomaly displays the most oxidized state of the magma, and the apatites of other samples at Aktogai, East Kounrad and Akzhal with moderate negative Eu anomaly show moderate oxidizing condition of these rocks, while the remaining apatites with strong En anomaly indicate a moderate reductive state of these rocks.     

Investigations of the Stillwater Complex: Part V. Apatites as indicators of evolving fluid composition

Variations in the F, Cl and OH contents of apatite are not constrained by crystal-chemical factors (in contrast to micas and amphiboles), and thus changes in the abundance of these components provide an indicator of halogen fugacity variations and insights into the degassing history of igneous rocks. Microprobe analysis of intercumulus apatites from the Stillwater Complex reveal that Cl-rich apatites, typically containing <0.4 wt % F and >6.0 wt % Cl, occur throughout the lower 1/3 of the complex excluding the Basal series. A change from Cl-rich to more F-rich apatite occurs within olivine-bearing zone I (OB I) of the Banded series, the host zone of the platiniferous J-M Reef. Although apatite compositions are somewhat variable above the J-M Reef, more F-rich apatites predominante and typically contain >1.2 wt % F and <3.0 wt % Cl. The most F-rich apatites occur in the uppermost exposed cumulates. Pristine apatites from coeval sills and dikes from below the complex and from the Basal series are similarly F-rich. In all apatites, the Cl and F contents are lower in rocks affected by later metamorphic fluids. Rare earth element (REE) concentrations in chlorapatites show a marked peak in the olivine-rich rocks of the J-M Reef, and contain up to 2 wt % Ce₂O₃ + La₂O₃. The trend of first increasing, then decreasing Cl/F ratios with stratigraphic height is modeled by a vapor-driven zone refining process occurring within the cumulate pile causing Cl-enrichment in the interstitial melt accompanied by degassing at the top of the magma chamber causing overall loss of Cl from the magma as crystallization proceeded. The abrupt change from Cl-rich to more F-rich apatites within OB I is interpreted as the result of a breakdown of the Cl-rich zone refining front and mixing with Cl-poor supernatant melt. Any high temperature fluids that exsolved and circulated through the lower 1/3 of the complex must have been enriched in Cl and could have transported REE and trace metals.     

Some Pertinent Features of Mo‐Mineralized Granitoids in the Circum‐Pacific Region

Petrological characteristics of granitic rocks related to the world large molybdenum deposits are studied. The granitoids are evaluated by Fe₂O₃+TiO₂‐FeO+MnO‐MgO diagrams, and found to all plot to the magnetite‐series field. They are all high silica and high‐K series, but not A‐type, except for the Climax‐type porphyries and some others in the Colorado mineral belt. By‐product molybdenum contained in porphyry copper deposits, lower grade but huge tonnage, occurs with calc‐alkaline I‐type magnetite‐series granodiorite and monzogranite. Felsic intrusive rocks of the Climax mine are A‐type and are exceptionally high in trace elements such as F and Rb, which are generally enriched with W and Sn‐related granitoids that originated in crustal source rocks. The by‐product molybdenites in porphyry copper deposits appear to originate in adakitic granodiorite or monzogranite, having deep origins with the subducted slab or thickened juvenile mafic lower crust. Therefore, there is no single magma type but the magnetite series, which concentrates a large volume of molybdenum in the ore deposits.     

Granitoids and Their Magnetic Susceptibility in South Korea

Abstract: Magnetic susceptibility (MS) measurements were carried out for 1,120 samples in the Middle Proterozoic to Early Tertiary granitoids so far recognized in South Korea, and the lateral and spatial variation of their magnetic susceptibility, i.e., content of magnetite, is studied. The Middle Proterozoic two mica granitoids related to cassiterite (Sn) deposits in northeastern part of the Sobaegsan Massif show very low MS (less than 0.3 A‐ 10^‐3 SI unit), and the Permo‐Triassic tonalitic to granodioritic and monzonitic rocks which are barren in mineralization, distributed in the middle part of South Korea also show low MS (less than 1 A‐ 10^‐3 SI unit). On the contrary the Late Triassic to Jurassic granitoids (= Daebo granitoids) which were evolved from tonalite through granodiorite to granite, and are most widely distributed in South Korea, show a wide variation on MS. Particularly in the Andong, Igsan, Gimcheon and Geochang areas, the granitoids which are barren in mineralization, are characterized by high MS (more than 10 A‐ 10^‐3 SI unit). The Chuncheon, Jecheon, Namyang and Geumsan plutons related to molybdenite (Mo) and/or wolframite or scheelite (W), and fluorite (F) mineralizations show a little high MS (more than 3 A‐ 10^‐3 SI unit). However, more than 60% of the Daebo granitoids show low MS (less than 3 A‐ 10^‐3 SI unit) and the rest show a little high MS (more than 3 A‐ 10^‐3 SI unit). Heterogeneous distribution of magnetite content in the Daebo granitoids is considered to reflect heterogeneity of redox state of the source materials for these granitoids. The Cretaceous to Early Tertiary granitoids (= Bulgugsa granitoids) in the Gyeongsang Basin had been generally evolved in the order of tonalite, diorite, granodiorite, granite and alkali‐feldspar granites, which are closely related to base metal ore deposits, and mostly show higher MS (more than 3 A‐ 10^‐3 SI unit) than other granitoids mentioned above, although some exceptions are recognized in highly evolved alkali‐feldspar granites (SiO₂ > 76%). In contrast, as most of the highly oxidized or evolved Cretaceous granitoids distributed in areas other than the Gyeongsang Basin show lower MS than those of the Gyeongsang Basin, and appear to be magnetite free, ilmenite‐series granites, but they might be hematite bearing magnetite‐series granitoids. Highly oxidized nature of the Bulgugsa granitoids may be due to high Fe₂O₃/FeO ratio of the source materials and also high level intrusion style of the granitic magma activities. Most of the granitic rocks of the Middle Proterozoic, Permo‐Triassic and more than 60% of the Late Triassic to Jurassic (Daebo granitoids) belong to ilmenite–series, however less than 40% of the Daebo granitoids and most Cretaceous ones are magnetite–series. Thus, the granitic magma intruded in Korean Peninsula became oxidized while the intrusive ages become younger.     

Halogen Geochemistry of the Stillwater and Bushveld Complexes: Evidence for Transport of the Platinum-Group Elements by Cl-Rich Fluids

Compositional data on apatite, phlogopite, and amphibole indicatethat the high-temperature hydrothermal fluids which affectedthe lower portions of the Stillwater and Bushveld Complexeswere Cl-rich. Apatites from the platinum-group element (PGE)ore zones from both complexes are enriched in Cl relative toother cumulus and noncumulus apatites in these intrusions andto apatites from the Skaergaard and Kiglapait Intrusions andthe Great Dyke. Apatites from all five intrusions can be groupedinto three distinct compositional fields: (a) Cumulus apatitesare essentially fluorapatites with molar Cl/(Cl+OH+F) <0?03;(b) noncumulus apatites, with the exception of those from thePGE ore zones of the Stillwater and Bushveld Complexes, haveCl/(Cl+OH+F) <0?20; (c) Cl-rich apatites associated withPGE-rich zones have Cl/(Cl+OH+F) between 0?45 and 1?0. The REEcontent of noncumulus and Cl-rich apatites also show a positivecorrelation with Cl concentration. It is argued that becauseCl is less soluble in silicate melts than F and because meltswith extremely high Cl/F ratios are unknown, the Cl-rich apatitesequilibrated with Cl-rich hydrothermal fluids exsolved duringsolidification of the cumulate sequence. The Cl, F, and OH contents of phlogopites and amphiboles aremore variable. Compositional heterogeneity is due to crystal-chemicalcontrols on halogen contents, variation in the halogen contentof the original melt/fluid phase and subsolidus re-equilibrationduring cooling with both surrounding mineral phases and lowtemperature fluids. However, both the Stillwater and Bushveldphlogopites are enriched in Cl compared to those from the Skaergaardand Kiglapait Intrusions. The compositions of coexisting minerals from the platinum depositof Olivine-Bearing Subzone I of the Stillwater Complex are usedto compute a fluid composition. The fluid is rich in alkalisand iron as well as HCl, and the solution composition is consistentwith fluid compositions deduced for the PGE-bearing secondaryhortonolite pipes of the Bushveld Complex. The high (Pt+Pd)/Irratios of these deposits are also consistent with a hydrothermalorigin, as both Pt and Pd are more soluble in Cl-complexingfluids than Ir.     

Oxide and sulphide isograds along a Late Archean, deep-crustal profile in Tamil Nadu, south India

Oxide–sulphide–Fe–Mg–silicate and titanite–ilmenite textures as well as their mineral compositions have been studied in felsic and intermediate orthogneisses across an amphibolite (north) to granulite facies (south) traverse of lower Archean crust, Tamil Nadu, south India. Titanite is limited to the amphibolite facies terrane where it rims ilmenite or occurs as independent grains. Pyrite is widespread throughout the traverse increasing in abundance with increasing metamorphic grade. Pyrrhotite is confined to the high‐grade granulites. Ilmenite is widespread throughout the traverse increasing in abundance with increasing metamorphic grade and occurring primarily as hemo‐ilmenite in the high‐grade granulite facies rocks. Magnetite is widespread throughout the traverse and is commonly associated with ilmenite. It decreases in abundance with increasing metamorphic grade. In the granulite facies zone, reaction rims of magnetite + quartz occur along Fe–Mg silicate grain boundaries. Magnetite also commonly rims or is associated with pyrite. Both types of reaction rims represent an oxidation effect resulting from the partial subsolidus reduction of the hematite component in ilmenite to magnetite. This is confirmed by the presence of composite three oxide grains consisting of hematite, magnetite and ilmenite. Magnetite and magnetite–pyrite micro‐veins along silicate grain boundaries formed over a wide range of post‐peak metamorphic temperatures and pressures ranging from high‐grade SO₂ to low‐grade H₂S‐dominated conditions. Oxygen fugacities estimated from the orthopyroxene–magnetite–quartz, orthopyroxene–hematite–quartz, and magnetite–hematite buffers average 2.5 log units above QFM. It is proposed that the trends in mineral assemblages, textures and composition are the result of an external, infiltrating concentrated brine containing an oxidizing component such as CaSO₄ during high‐grade metamorphism later acted upon by prograde and retrograde mineral reactions that do not involve an externally derived fluid phase.     

Geochemie des Apatits in Tiefengesteinen am Beispiel des Odenwaldes

Summary The apatite in various igneous rocks (from quartzmonzonitic to gabbroic composition) in one and the same area of differentiation was geochemically examined. The samples were taken from 24 different localities in the Odenwald (Germany) and the thin sections were determined petrographically with a point counter. 25 kg of each sample were dressed and the apatite separated from the heavy mineral concentrates. The pure apatite was analysed quantitative chemically. The variable components of the apatite are represented diagrammatically as functions of the rockchemistry, the physical- and the X-ray constants and their relationships are discussed. The following relations were established: The F-content of magmatic apatites increases in the acidic rocks without showing a stringent lawfulness to the rockchemistry. F remains in all apatites, compared with Cl, OR and 0, alwavs in predominance.With increase in the content of F the refractive index, as well as the lattice constants of the apatites, decrease.The Cl-content of magmatic apatites increases towards the basic rocks, but here too it remains much less than the amount of F. Further more all other statements refering to F can be applied to Cl, but with opposite meaning.A comparison of the chemical analyses of apatites from the newer literature and these of the author reveals in all probability that there is only a limited miscibility between F- and Cl-apatites. The limit being 20 atom per cent Cl. The relation of F : Cl as 1:1 in some apatites might be attributed to an orderly arranged state of the F- and Cl-apatites.OH behaves in a similar manner as Cl, except that the results have wider dispersion effect.According to the chemical equivalence calculations there is generally a small excess of cations. This means that Oxygen must fill up free halogen-places in the lattice.The content of SiO₂ of the apatites shows an increasing tendency towards in the basic rocks and the content of P₂O₅ a decreasing one.The contents of the rare earths of magmatic apatites increase in acidic rocks and only those ones with even numbers (with the exception of La) appear.Only apatites from rocks with metamorphic characteristics had an amount of SO₃.By means of a comparison between the exploit of apatite and P₂O₅-contents of the rocks can be supposed with probability that the principal quantity of the P₂O₅ in the magmatic rocks is not bound to the apatite but to the silicates. This supposition will shortly be further examined.The relative increasing of the intensity of the line (0002) and (0004) in the X-ray-graphs (X-ray-goniometer) in the F-rich apatites suggests a better (0001)-cleavage as in the Cl-rich apatites. This observation can be explained easily with the different structures of the F- and the Cl-apatites.     

Mineralogy and Mineral Chemistry of the Cretaceous Duolong Gold‐Rich Porphyry Copper Deposit in the Bangongco Arc,Northern Tibet

The Early Cretaceous Duolong gold‐rich porphyry copper deposit is a newly discovered deposit with proven 5.38 Mt Cu resources of 0.72% Cu and 41 t gold of 0.23 g t^?1 in northern Tibet. Granodiorite porphyry and quartz diorite porphyrite are the main ore‐bearing porphyries. A wide range of hydrothermal alteration associated with these porphyries is divided into potassic, argillic and propylitic zones from the ore‐bearing porphyry center outward and upward. In the hydrothermal alteration zones, secondary albite (91.5–99.7% Ab) occurs along the rim of plagioclase phenocryst and fissures. Secondary K‐feldspar (75.1–96.9% Or) replaces plagioclase phenocryst and matrix or occurs in veinlets. Biotite occurs mainly as matrix and veinlet in addition to phenocryst in the potassic zone. The biotite are Mg‐rich and formed under a highly oxidized condition at temperatures ranging from 400°C to 430°C. All the biotites are absent in F, and have high Cl content (0.19–0.26%), with log (X_Cl/X_OH) values of ?2.74 to ?2.88 and IV (Cl) values of ?3.48 to ?3.35, suggesting a significant role of chloride complexes (CuCl₂^‐ and AuCl₂^‐) in transporting and precipitating copper and gold. Chlorites are present in all alteration zones and correspond mainly to pycnochlorite. They have similar Fe/(Fe+Mg), Mn/(Mn+Mg) ratios, and a formation temperature range of 280–360°C. However, the formation temperature of chlorite in the quartz‐gypsum‐carbonate‐chlorite vein is between 190°C and 220°C, indicating that it may have resulted from a later stage of hydrothermal activity. Fe³⁺/Fe²⁺ ratios of chlorites have negative correlation with Al^IV, suggesting oxygen fugacity of fluids increases with decreasing temperature. Apatite mineral inclusions in the biotite phenocrysts show high SO₃ content (0.44–0.82%) and high Cl content (1–1.37%), indicating the host magma had a high oxidation state and was enriched in S and Cl. The highest Cl content of apatite in the propylitic zone may have resulted from pressure decrease, and the lowest Cl content of apatite in the argillic zone may have been caused by a low Cl content in the fluids. The low concentration of SO₃ content in the hydrothermal apatite compared to the magmatic one may have resulted from the decrease of oxygen fugacity and S content in the hydrothermal fluid, which are caused by the abundant precipitation of magnetite.     

The significance of Mn‐rich ilmenite and the determination of P–T paths from zoned garnet in metasedimentary rocks from the western Cape Breton Highlands,Nova Scotia

The Jumping Brook Metamorphic Suite in the western Cape Breton Highlands of Nova Scotia is part of an inverted Barrovian sequence that formed during a Late Silurian–Early Devonian promontory–promontory collision in the Canadian Appalachians. In this study, systematic discrepancies between geochemical observations and thermodynamic model predictions led to the discovery of a systematic relationship linking the style of garnet core isopleth intersection (GCII) to the pyrophanite (MnTiO₃) component of co‐existing ilmenite. Samples that yielded tight GCIIs at or near the garnet‐in curve were found to contain ilmenite with negligible pyrophanite components, whereas samples yielding GCIIs far removed (up to 105°C) from the garnet‐in curve were found to contain ilmenite with significant pyrophanite and/or ecandrewsite (ZnTiO₃) components. Based on petrographic and geochemical observations, Mn(±Zn)‐rich ilmenite are interpreted to have sequestered Mn throughout prograde metamorphism due to sluggish intracrystalline diffusion. The amount of reactive Mn input into the thermodynamic models from whole‐rock analyses were, in some cases, overestimated, resulting in garnet‐in curve topologies that extend to erroneously low P–T conditions. Modifications to the whole‐rock chemistry that account for Mn sequestration into ilmenite, however, yielded robust model results. Our results show that, in addition to uncertainties in thermodynamic data sets and phenomenon related to reaction kinetics, Mn‐rich ilmenite may superimpose additional complexities related to the interpretation of predicted equilibria involving garnet. Numerical simulations of garnet crystallization were used to infer P–T paths of metamorphism for one sample from the garnet zone (Mn corrected) and two samples from the staurolite zone (Mn uncorrected) of the inverted sequence. Model results are remarkably similar among the three samples and indicate that garnet crystallization occurred along relatively steep (31–37°C/km) clockwise P–T paths. The peak conditions of garnet crystallization and metamorphism (560–590°C, 7.4–8.0 kbar) are interpreted to have been attained approximately simultaneously, such that the paths are characterized by tight prograde‐to‐retrograde transitions. The hairpin nature of the P–T paths is interpreted to represent the onset of thrust‐related exhumation and isograd inversion along ductile shear zones, consistent with available field and geochronological constraints.     

Comparative Studies of the Petrochemistry of Sn–W‐Mineralized Granitoids: Continent vs. Island Arc

Granitic rocks obtained during field excursions of the famed mineralized regions of the Erzgebirge, Germany (mainly tin‐bearing), and South China (mainly tungsten‐bearing) have been geochemically analyzed and their results are compared with similar (mainly tungsten‐bearing) granites in the island‐arc setting of Southwest Japan. The studied granitoids all belong to the ilmenite‐series. The collision‐related Erzgebirge granitoids are rich in K₂O and P₂O_5, have high A/CNK ratios (1.11–1.24, i.e. S type), but are also high in Ga/Al ratio (i.e., having some A‐type characteristics). In South China, the Xihuashan granites, in contrast, are very low in P₂O₅, and have A/CNK slightly above 1.0 (1.01–1.05), indicative of I type granites. The (Sn‐) W‐related granites of southwest Japan have similarly low P₂O₅ and A/CNK ratios, indicative also of I‐type. Both in the Xihuashan and southwest Japan, the tungsten‐related granites have high whole‐rock δ¹⁸O values implying involvement of W‐rich crustal rocks. Sn and W contents of the unaltered granites are lowest in the island‐arc setting where the related Sn–W deposits are smallest in size relative to the collision and continental margin settings of the Erzgebirge and South China.     

Trace element and Nd isotope analyses of apatite in granitoids and metamorphosed granitoids from the eastern Central Asian Orogenic Belt: Implications for petrogenesis and post-magmatic alteration

We present in situ trace element and Nd isotopic data of apatites from metamorphosed and metasomatized (i.e., altered) and unaltered granitoids in the Songnen and Jiamusi massifs in the eastern Central Asian Orogenic Belt, with the aim of fingerprinting granitoid petrogenesis, including both the magmatic and post-magmatic evolution processes. Apatites from altered granitoids (AG) and unaltered granitoids (UG) are characterized by distinct textures and geochemical compositions. Apatites from AG have irregular rim overgrowths and complex internal textures, along with low contents of rare earth elements (REEs), suggesting the re-precipitation of apatite during epidote crystallization and/or leaching of REEs from apatite by metasomatic fluids. ε_Nd(t) values of the these apatites are decoupled from zircon ε_Hf(t) values for most samples, which can be attributed to the higher mobility of Nd as compared to Sm in certain fluids. Apatites from UG are of igneous origin based on their homogeneous or concentric zoned textures and coupled Nd-Hf isotopic compositions. Trace element variations in igneous apatite are controlled primarily by the geochemical composition of the parental melt, fractional crystallization of other REE-bearing minerals, and changes in partition coefficients. Sr contents and Eu/Eu* values of apatites from UG correlate with whole-rock Sr and SiO₂ contents, highlighting the effects of plagioclase fractionation during magma evolution. Apatites from UG can be subdivided into four groups based on REE contents. Group 1 apatites have REE patterns similar to the host granitoids, but are slightly enriched in middle REEs, reflecting the influence of the parental melt composition and REE partitioning. Group 2 apatites exhibit strong light REE depletions, whereas Group 3 apatites are depleted in middle and heavy REEs, indicative of the crystallization of epidote-group minerals and hornblende before and/or during apatite crystallization, respectively. Group 4 apatites are depleted in heavy REEs, but enriched in Sr, which are features of adakites. Some unusual geochemical features of the apatites, including the REE patterns, Sr contents, Eu anomalies, and Nd isotopic compositions, indicate that inherited apatites are likely to retain the geochemical features of their parental magmas, and thus provide a record of small-scale crustal assimilation during magma evolution that is not evident from the whole-rock geochemistry.     

Low‐P and high‐T metamorphism of basalts: Insights from the Sudbury impact melt sheet aureole and thermodynamic modelling

Low‐pressure and high‐temperature (LP–HT) metamorphism of basaltic rocks, which occurs globally and throughout geological time, is rarely constrained by forward phase equilibrium modelling, yet such calculations provide valuable supplementary thermometric information and constraints on anatexis that are not possible to obtain from conventional thermometry. Metabasalts along the southern margin of the Sudbury Igneous Complex (SIC) record evidence of high‐grade contact metamorphism involving partial melting and melt segregation. Peak metamorphic temperatures reached at least ~925°C at ~1–3 kbar near the SIC contact. Preservation of the peak mineral assemblage indicates that most of the generated melt escaped from these rocks leaving a residuum characterized by a plagioclase–orthopyroxene–clinopyroxene–ilmenite‐magnetite±melt assemblage. Peak temperatures reached ~875°C up to 500 m from the SIC lower contact, which marks the transition to metabasalts that only experienced incipient partial melting without melt loss. Metabasalts ~500 to 750 m from the SIC contact are characterized by a similar two‐pyroxene mineral assemblage, but typically contain abundant hornblende that overgrew clino‐ and orthopyroxene along an isobaric cooling path. Metabasalts ~750 to 1,000 m from the SIC contact are characterized by a hornblende–plagioclase–quartz–ilmenite assemblage indicating temperatures up to ~680°C. Mass balance and phase equilibria calculations indicate that anatexis resulted in 10–20% melt generation in the inner ~500 m of the aureole, with even higher degrees of melting towards the contact. Comparison of multiple models, experiments, and natural samples indicates that modelling in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCFMASHTO) system results in the most reliable predictions for the temperature of the solidus. Incorporation of K₂O in the most recent amphibole solution model now successfully predicts dehydration melting by the coexistence of high‐Ca amphibole and silicate melt at relatively low pressures (~1.5 kbar). However, inclusion of K₂O as a system component results in prediction of the solidus at too low a temperature. Although there are discrepancies between modelling predictions and experimental results, this study demonstrates that the pseudosection approach to mafic rocks is an invaluable tool to constrain metamorphic processes at LP–HT conditions.     

Implication of Apatite and Anhydrite for Formation of an Iron‐Oxide‐Apatite (IOA) Rare Earth Element Prospect,Benjamin River,Canada

The Benjamin River apatite prospect in northern New Brunswick, Canada, is hosted by the Late Silurian Dickie Brook plutonic complex, which is made up of intrusive units represented by monzogranite, diorite and gabbro. The IOA ores, composed mainly of apatite, augite, and magnetite at Benjamin River form pegmatitic pods and lenses in the host igneous rocks, the largest of which is 100 m long and 10–20 m wide in the diorite and gabbro units. In this study, 28 IOA ore and rock samples were collected from the diorite and gabbro units. Mineralogical observations show that the apatite–augite–magnetite ores are variable in the amounts of apatite, augite, and magnetite and are associated with minor amounts of epidote‐group minerals (allanite, REE‐rich epidote and epidte) and trace amounts of albite, titanite, ilmenite, titanomagnetite, pyrite, chlorite, calcite, and quartz. Apatite and augite grains contain small anhydrite inclusions. This suggests that the magma that crystallized apatite and augite had high oxygen fugacity. In back scattered electron (BSE) images, apatite grains in the ores have two zones of different appearance: (i) primary REE‐rich zone; and (ii) porous REE‐poor zone. The porous REE‐poor zones mainly appear in rims and/or inside of the apatite grains, in addition to the presence of apatite grains which totally consist of a porous REE‐poor apatite. This porous REE‐poor apatite is characterized by low REE (<0.84 wt%), Si (<0.28 wt%), and Cl (<0.17 wt%) contents. Epidote‐group minerals mainly occur in grain boundary between the porous REE‐poor apatite and augite. These indicate that REE leached from primary REE‐rich apatite crystallized as allanite and REE‐rich epidote. Magnetite in the ores often occurs as veinlets that cut apatite grains or as anhedral grains that replace a part of augite. These textures suggest that magnetite crystallized in the late stage. Pyrite veins occur in the ores, including a large amount of quartz and calcite veins. Pyrite veins mainly occur with quartz veins in augite. These textures indicate pyrite veins are the latest phase. Apatite–augite–magnetite ore, gabbro–quartz diorite and feldspar dike collected from the Benjamin River prospect contain dirty pure albite (Ab₉₈Or₂–Ab₁₀₀) under the microscope. The feldspar dikes mainly consist of dirty pure albite. Occurrences of the dirty pure albite suggest remarkable albitization (sodic alteration) of original plagioclase (An_25.3–An₆₀ in Pilote et al., 2012) associating with intrusion of monzogranite into gabbro and diorite. SO₄^2? bearing magma crystallized primary REE‐rich apatite, augite and anhydrite reacted with Fe in the sodic fluids, which result in oxidation of Fe²⁺ and release of S^2? into the sodic fluids. REE, Ca and Fe from primary REE‐rich apatite, augite and plagioclase altered by the sodic fluids were released into the fluids. Then Fe³⁺ in the sodic fluids precipitated as Fe oxides and epidote‐group minerals in apatite–augite–magnetite ores. Finally, residual S^2? in sodic fluids crystallized as latest pyrite veins. In conclusion, mineralization in Benjamin River IOA prospect are divided into four stages: (1) oxidized magmatic stage that crystallized apatite, augite and anhydrite; (2) sodic metasomatic stage accompanying alteration of magmatic minerals; (3) oxidized fluid stage (magnetite–epidote group minerals mineralization); and (4) reduced fluid stage (pyrite mineralization).     

Composition and assemblage characteristics of magnetic minerals in layer S<Subscript>5-1</Subscript> of Xifeng and Duanjiapo sections

Relatively strongly magnetic fine components (< 30μm, XS-4J and DS-4J) which are most environmentally sensitive were separated from layer S_5-1 in the Xifeng and Duanjiapo loess sections and analyzed by MPV-3 for their morphometric characteristics and reflectance, SEM-ESD for their element contents and XRD for their mineral phases, respectively. The results showed that minerals in both samples are dominated by detrial Fe-Ti oxides of aeolian origin. In sample XS-4J the reflectance and iron contents of magnetic minerals are usually high. In addition to magnetite (Fe₃O₄), maghemite (γFe₂O₃) and hematite (Fe₂O₃), some Fe-high oxide (72.25 wt%–86.67 wt%), ilmenite (FeTiO₃), and magnetite-ulvöspinel [Fe(FeCr)O₄, Fe (FeNi)O₄] were also detected. In sample DS-4J obvious negative linear correlations were found between Ti and Fe, and the contents of Mn, Si, Al and Ca are usually high and the minerals are dominated by magnetite (maghemite), goethite (FeOOH) and limonite (containing Si and OH). In addition, the signs of corrosion of magnetic minerals and newly crystallized magnetite (maghemite) were recognized. Differences in the composition and assemblage characteristics of magnetite minerals between XS and DS reflect significant differences in source rocks and preserving conditions.     

Geochemistry of apatites in the granitic rocks of the Molybdenum, Tungsten, and Barren provinces of Southwest Japan

Recognition of the importance of chlorine complexing in enhancing the solubility of metal sulfides in aqueous solutions has led to the view that the chlorine content of intrusive rock could govern the ability of a magma to separate a metal-rich hydrothermal phase. This article presents the chlorine and fluorine contents of apatites in the granitic rocks of the Barren, Tungsten, and Molybdenum provinces of Southwest Japan.The abundance of Cl in apatites correlates negatively with rock D.I. (differentiation indices), and the abundance of F in apatites correlates positively with rock D.I. The abundance of Cl in apatites of the Molybdenum province is generally higher than that of the Tungsten and Barren provinces, and the abundance of F in apatites in the Molybdenum province is generally lower than that of F in apatites of the Tungsten and Barren provinces.Apatites in the granitic rocks associated with tungsten and fluorite mineralization and granite pegmatite formation, and from the Barren province are mostly F-OH apatites     

Fluid inclusion studies in apatite from carbonatites of the Wasaki area of western Kenya

Apatites from the carbonatites contain relatively large (up to 120μ), aqueous, CO₂-rich, saline inclusions. Homogenisation temperature determinations show that the minimum formation temperature of these apatites ranged from 200°C to 484°C. The mode of homogenisation of inclusion in the Wasaki sövite apatites indicates that these apatites crystallised from a supercritical fluid. A higher estimate of the formation temperature of the apatites from this sample (500°C–590°C) was obtained from the solution temperature of a transient phase (probably Na₂CO₃) precipitated from the inclusion-fluid at elevated temperatures. These fluids are considered to represent trapped portions of a fluid carbonatite magma.     

The P–T–X(fluid) evolution of meta‐anorthosites in the Eastern Granulites,Tanzania

Meta‐anorthosite bodies are typical constituents of the Neoproterozoic Eastern Granulites in Tanzania. The mineral assemblage (and accessory components) is made up of clinopyroxene, garnet, amphibole; scapolite, epidote, biotite, rutile, titanite, ilmenite and quartz. Within the feldspar‐rich matrix (70–90% plagioclase), mafic domains with metamorphic corona textures were used for P–T calculations. Central parts of these textures constitute high‐Al clinopyroxene – which is a common magmatic mineral in anorthosites – and is therefore assumed to be a magmatic relict. The clinopyroxene rims have a diopsidic composition and are surrounded by a garnet corona. Locally the pyroxene is surrounded by amphibole and scapolite suggesting that a mixed CO₂–H₂O fluid was present during their formation. Thermobarometric calculations give the following conditions for the metamorphic peak of the individual meta‐anorthosite bodies: Mwega: 11–13 kbar, 850–900 °C; Pare Mountains: 12–14 kbar, 850–900 °C; Uluguru Mountains: 12–14 kbar, 850–900 °C. The P–T evolution of these bodies was modelled using pseudosections. The amount and composition of the metamorphic fluid and <0.5 mol.% fluid in the bulk composition is sufficient to produce fluid‐saturated assemblages at 10 kbar and 800 °C. Pseudosection analysis shows that the corona textures most likely formed under fluid undersaturated conditions or close to the boundary of fluid saturation. The stabilities of garnet and amphibole are dependent on the amount of fluid present during their formation. Mode isopleths of these minerals change their geometry drastically between fluid‐saturated and fluid‐undersaturated assemblages. The garnet coronae developed during isobaric cooling following the metamorphic peak. The cooling segment is followed by decompression as indicated by the growth of amphibole and plagioclase. The estimated of the metamorphic fluid is ～0.3–0.5. Although the meta‐anorthosites have different formation ages (Archean and Proterozoic) they experienced the same Pan‐African metamorphic overprint with a retrograde isobaric cooling path. Similar P–T evolutionary paths are known from the hosting granulites. The presented data are best explained by a tectonic model of hot fold nappes that brought the different aged anorthosites and surrounding rocks together in the deep crust followed by an isobaric cooling history.     

Apatite Chlorine Concentration Measurements by LA‐ICP‐MS

Apatite incorporates variable and significant amounts of halogens (mainly F and Cl) in its crystal structure, which can be used to determine the initial F and Cl concentrations of magmas. The amount of chlorine in the apatite lattice also exerts an important compositional control on the degree of fission‐track annealing. Chlorine measurements in apatite have conventionally required electron probe microanalysis (EPMA). Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) is increasingly used in apatite fission‐track dating to determine U concentrations and also in simultaneous U‐Pb dating and trace element measurements of apatite. Apatite Cl measurements by ICP‐MS would remove the need for EPMA but the high (12.97 eV) first ionisation potential makes analysis challenging. Apatite Cl data were acquired using two analytical set‐ups: a Resonetics M‐50 193 nm ArF Excimer laser coupled to an Agilent 7700× quadrupole ICP‐MS (using a 26 μm spot with an 8 Hz repetition rate) and a Photon Machines Analyte Excite 193 nm ArF Excimer laser coupled to a Thermo Scientific iCAP Qc (using a 30 μm spot with a 4 Hz repetition rate). Chlorine concentrations were determined by LA‐ICP‐MS (1140 analyses in total) for nineteen apatite occurrences, and there is a comprehensive EPMA Cl and F data set for 13 of the apatite samples. The apatite sample suite includes different compositions representative of the range likely to be encountered in natural apatites, along with extreme variants including two end‐member chlorapatites. Between twenty‐six and thirty‐nine isotopes were determined in each apatite sample corresponding to a typical analytical protocol for integrated apatite fission track (U and Cl contents) and U‐Pb dating, along with REE and trace element measurements. ³⁵Cl backgrounds (present mainly in the argon gas) were ~ 45–65 kcps in the first set‐up and ~ 4 kcps in the second set‐up. ³⁵Cl background‐corrected signals ranged from ~ 0 cps in end‐member fluorapatite to up to ~ 90 kcps in end‐member chlorapatite. Use of a collision cell in both analytical set‐ups decreased the low mass sensitivity by approximately an order of magnitude without improving the ³⁵Cl signal‐to‐background ratio. A minor Ca isotope was used as the internal standard to correct for drift in instrument sensitivity and variations in ablation volume during sessions. The ³⁵Cl/⁴³Ca values for each apatite (10–20 analyses each) when plotted against the EPMA Cl concentrations yield excellently constrained calibration relationships, demonstrating the suitability of the analytical protocol and that routine apatite Cl measurements by ICP‐MS are achievable.