Oscillatory Zoning Research Articles

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.

Constraints of in-situ elemental compositions and U–Pb ages of cassiterite on the origin of the Cretaceous Gejiu and Dulong tin deposits, SW China: Implications for the linkage of tin belts in SE Asia

The western Yunnan tin belts in SW China and the southern Myanmar tin belt in SE Asia are traditionally thought to be part of the SE Asian tin metallogenic province. However, the tectonic setting of the Youjiang tin belt in SW China and its genetic relationship to the other tin belts are poorly documented. In this belt, the giant Gejiu and Dulong tin deposits are typical of skarn-type deposits and both contain contact and distal skarn orebodies. Tin ores of distal orebodies in these two deposits are composed of cassiterite, sulfide and calcite. In both deposits, most cassiterite grains from these ores are rich in Fe and W and depleted in Nb and Ta. They have 238U/206Pb ages between 81.4 and 84.1 Ma, similar to hosting granitic plutons. Two generations of cassiterite with distinctly different microtextures and trace elemental compositions can be recognized. The first generation (Cst-I) is compositionally and texturally homogeneous, but the second generation (Cst-II) displays distinctly oscillatory zoning. Cst-II contains Nb, W, and U lower, and Fe, Ta, Zr and chalcophile elements (Ga, Ge, In, and Sb) higher than Cst-I. These textural and compositional variations reflect the potential involvement of meteoric water in the magmatic-hydrothermal system. In this system, ore-forming fluids were evolved to more alkaline and oxidized to facilitate the precipitation of cassiterite. Our study indicates that these two deposits in the Youjiang tin belt have mineralization styles similar to those in the adjacent western Yunnan and southern Myanmar tin belts and all these tin belts belong to the SE Asian metallogenic provinces. A westward-younging trend of tin mineralization in these three belts can be explained by the rollback of the subducted Neo-Tethyan oceanic slab. This setting is different from the one related to the subduction of the Paleo-Pacific plate.

Integrated textural and geochemical analysis of igneous zircon by atom probe tomography

Mechanisms relating to growth and/or compositional modification of zircon occur at the atomic scale. For felsic igneous systems, processes responsible for growth patterns in zircon have previously remained elusive as the volume of material needed to analyze these compositional features using traditional in-situ methods is considerably larger than the typical sub-micron scale distribution of trace elements. To illuminate some of these driving forces, we characterize and quantify minor and trace element concentrations in igneous zircon grains by combining methods of cathodoluminescence (CL) imaging, electron microprobe microanalysis (EMPA) elemental maps for Hf, Y, Yb and U or Th, and atom probe tomography (APT). We focus on igneous zircon from the Chon Aike Silicic Large Igneous Province (Patagonia) that provide novel insights into (1) dissolution and re-crystallization during crustal anatexis, (2) crystallization to produce oscillatory zonation patterns that are typical of igneous zircons, and (3) the incorporation of trace element impurities (e.g., P, Be, and Al) at the nanoscale. Significantly, these APT volumes provide nanoscale sampling of boundaries between oscillatory growth zones in an igneous zircon to reveal compositional zoning of Y and, to a lesser extent P, which appear as high-angle, planar features. These concentration boundaries measured on the order of 10 to 12 nm are difficult to reconcile with proposed mechanisms for generating fine-scaled oscillations. Lastly, we fit diffusional profiles to measured Y concentrations to provide an estimate on the maximum timescales of zircon growth prior to eruption, as a function of the temperature at which diffusion occurred. When combined with known pressure-temperature-time paths for the magmatic system considered, these extremely short diffusion profiles that are resolvable by APT provide a powerful method to constrain timescales of crystal growth.

Kyanite microstructural and microchemical characteristics reveal differences in growth, deformation and chemical modification: A case study from the Paleoproterozoic suture zone of South Harris, NW Scotland

Based on petrological association, cathodoluminescence (CL), trace element signatures and orientation relationships, two generations of kyanite are distinguished in a high temperature, high pressure garnet-biotite-aluminosilicate bearing migmatite of South Harris, NW Scotland. The migmatite shows a garnet and biotite rich domain (Grt-Bt domain) which is cut at a low angle by a dominantly coarse-grained plagioclase-quartz leucosome. In addition, a fine-grained plagioclase-quartz-kyanite domain (Plag-Qtz-Ky domain) is present intercalated with the Grt-Bt domain and subparallel to the plagioclase-quartz domain. Type 1 kyanite is coarse grained and associated with Bt clusters and garnet within the Grt-Bt domain. It grew relatively early, syn- to post-garnet growth, in a suprasolidus environment resulting in crystallographically determined oscillatory CL and trace element zoning. Grains record evidence of progressive deformation in the crystal plastic regime, where deformation is accommodated by dislocation glide, climb and deformation twinning. The dominant activated slip system is (100)<001> with minor component of <100>, while deformation twins show a ∼ 180° rotation around ∼<001> axis and a twin plane near (001). Grains appear to be impervious to deformation induced diffusion with all zoning remaining sharp despite crystal plastic deformation. Grains in direct contact with the Plag-Qtz-Ky domain show late modification of the CL and trace element signature suggesting melt-mediated interface-coupled dissolution-precipitation reaction. This modification resulted in crosscutting lobate high trace element regions and irregular rims with low Cr and V content. These rims show similar CL and trace element characteristics as Type 2 kyanite which are exclusively seen within the Plag-Qtz-Ky domain suggesting that Type 2 grains are cogenetic with Type 1 rims. Type 2 grains are finer grained than Type 1 grains and show near uniform CL and trace element distributions with rare oscillatory zoned and relatively higher Cr & V bright cores. Type 2 show either no or very localized internal deformation features. However, they exhibit a clear shape preferred orientation which coincides with a crystallographic preferred orientation where the longest shape axis is parallel to <001>. We propose that Type 2 kyanite grains underwent melt-present deformation by rigid body rotation in an externally derived melt with different trace element chemistry than the host rock. This melt thus interacted chemically by melt-mediated interface-coupled dissolution-precipitation reactions with the surrounding rocks forming the Type 1 rims.Our study shows detailed analysis of kyanite is an important tool for giving constraints on the deformation, P–T and melting history of high-grade metamorphic rocks and migmatites.

Multi-stage magmatic–hydrothermal evolution of nepheline pegmatite: Insights from the mineralogy and geochronology of a zircon megacryst from the Yilanlike nepheline pegmatite, South Tianshan

Magmatic–hydrothermal evolution plays a key role in the formation of peralkaline rocks and associated zirconium and rare earth element (REE) mineralization. Zircon is a common mineral in peralkaline rocks and can record invaluable information about the magmatic–hydrothermal evolution of these systems. To help better constrain the magmatic–hydrothermal evolution of and Zr enrichment processes in peralkaline systems, we characterized the mineralogy and geochronology of a texturally complex zircon megacryst from the rare metal mineralized Yilanlike nepheline pegmatite in the South Tianshan. Here we present laser Raman spectra, in situ elemental data, and U–Pb geochronological data for the zircon megacryst to constrain the age and magmatic–hydrothermal evolution of this nepheline pegmatite. Three types of zircon domains (Zrn-I, Zrn-II, and Zrn-III) are distinguished based on their morphological and geochemical characteristics. Zrn-I has well-developed oscillatory zoning, REE patterns similar to magmatic zircon, high Th/U ratios (0.09–0.47), and concordant U–Pb ages, indicative of a magmatic origin. Zrn-II is characterized by weak oscillatory and patchy zoning, low full width at half maximum (FWHM) values (6.58–14.86 cm−1), and low trace-element contents (e.g., Nb = 0.16–0.92 ppm, Ta = 0.13–0.54 ppm, U = 195.77–812.92 ppm, Th = 15.85–158.95 ppm, and total REE = 13.00–187.75 ppm), indicative of a recrystallized origin as this process generates heterogeneous zoning, heals the zircon crystal lattice, and lowers trace-element contents. Concordant U–Pb ages and low Th/U ratios (0.05–0.26), combined with moderate Ce/Ce* and (Sm/La)N ratios (0.38–33.96 and 1.34–27.73, respectively), which are characteristic of the magmatic–hydrothermal transition, indicate that Zrn-II recrystallized in the presence of hydrothermal fluids. Zrn-III is characterized by “spongy” textures, thorite inclusions, high FWHM values (6.58–47.87), relatively high contents of total REE (14.79–962.05 ppm), and discordant U–Pb ages, suggestive of an origin related to the hydrothermal alteration of earlier zircons. Results of U–Pb dating of Zrn-I and -II yield weighted concordant ages of 286.9 ± 1.9 Ma (MSWD = 1.5, n = 23) and 279.3 ± 2.3 Ma (MSWD = 0.24, n = 20), respectively, whereas the U–Pb results for Zrn-III are largely discordant. Based on these textural, geochemical, and geochronological results, a multi-stage process for the formation of the zircon megacryst and nepheline pegmatite is proposed. First, the parent magma of the nepheline pegmatite was emplaced and the zircon megacryst crystallized at ca. 286.9 Ma (represented by Zrn-I). As the magma differentiated, hydrothermal fluids derived from the evolved magma recrystallized Zrn-I to Zrn-II at ca. 279.3 Ma. Finally, a second hydrothermal event altered Zrn-I and -II to form Zrn-III. Given the low concentrations of UO2, ThO2, and Y2O3 in Zrn-II, and the CHARAC behavior of Zr and Hf, the fluid that formed this zircon variety likely had relatively low F contents. This multi-stage magmatic–hydrothermal evolution likely played an essential role in concentrating Zr and generating the Zr mineralization. Zirconium is primarily enriched via magmatic crystallization, as illustrated by the high abundances of Zrn-I in the Yilanlike nepheline pegmatite. The presence of hydrothermal zircon (Zrn-II and Zrn-III) suggests that hydrothermal recrystallizatio nay have also facilitated the enrichment of Zr. It is, therefore, suggested that both magmatic and hydrothermal processes contributed to the enrichment of Zr in the Yilanlike nepheline pegmatite.

In-situ Lu-Hf garnet dating of Archean deep crust granulites from the polymetamorphic Grenville Front Tectonic Zone

Abstract Recent advances in geochronological techniques now allow the ability to efficiently decipher the timing and duration of geological processes in complex high-grade polymetamorphosed orogenic terranes. This is the case of the Grenville Front Tectonic Zone, which truncates the Superior Craton to the southeast. The zone exposes parautochtonous Archean rocks that underwent mid- to high-pressure granulite facies metamorphism of uncertain age. The metamorphic assemblages have been either interpreted as Archean and associated with the final stages of the Superior craton assembly, or as the result of Mesoproterozoic Grenvillian metamorphism, based on cross-cutting relationships and traditional geochronology methods such as U-Pb zircon and 40Ar-39Ar mica dating. Herein, we revisit the extent of the Grenvillian metamorphic overprint in the parautochtonous domain and provide new age constraints for granulite-facies metamorphic assemblages through in-situ garnet dating within migmatitic paragneiss, migmatitic orthogneiss, and mafic granulites, combined with in-situ trace element mapping. Six samples, which show bell-shaped and occasionally sharp and oscillatory lutetium growth zoning in garnet, yield garnet Lu-Hf isochrons with identical Archean dates of c. 2.6 Ga. Sparce analyses of material trend toward Grenvillian ages (c. 1 Ga) in one sample from which garnet shows lutetium zoning consistent with post-growth fluid-assisted disturbance. Overall, our results indicate that the widespread granulite-facies metamorphism within the Grenville Front Tectonic Zone is dominantly late Neoarchean in age, unveiling a rare exposure of Archean lower crust in the southeastern Superior Craton. Our results also point towards a limited Grenvillian metamorphic overprint though the spatial extent and precise thermal conditions of this metamorphism are still unknown. The results presented herein demonstrate the potential of in-situ isotopic geochronology on rock-forming minerals like garnet in polymetamorphic terranes.

Mixed sources and complicated petrogenetic processes of the Himalayan granites recorded by apatite in-situ geochemistry of the Eocene Yardoi-Lhunze complex, southeast Tibet

The Cenozoic Himalayan granites are widely accepted as the anatectic products of crustal rocks. However, previous geochemical studies on their petrogenesis are mainly based on whole-rock analyses. Here we conducted a detailed petrographic, trace elemental and Sr isotopic investigations of apatite from the Middle Eocene (44–40 Ma) two-mica granites and subvolcanic porphyritic leucogranites of the Yardoi-Lhunze complex from the Tethyan Himalayan Sequence in the southeast Tibet, with the aim to constrain their magma sources and petrogenetic processes. The results show that apatites from the Quedang and Dala two-mica granites are characterized by euhedral to subhedral crystal shape, and have a wide range of initial 87Sr/86Sr ratios (0.7016–1.0088). They show significant negative Eu anomaly and varied concentrations of Sr and Y, indicating they are typical magmatic apatites. Apatites from the Qiaga porphyritic leucogranites can be divided into two groups based on Eu anomaly. Group-I apatites with positive Eu anomaly mainly display euhedral to subhedral crystal shape but with alteration rim, suggesting from the influence of hydrothermal fluids. Group-II apatites with negative Eu anomaly also have euhedral to subhedral crystal shape but they exhibit patchy or oscillatory zones, consistent with a magmatic origin. However, both group-I and II apatites have comparable initial 87Sr/86Sr ratios, 0.7198–0.9966 and 0.7174–0.9999, respectively. Previous studies based on whole-rock petrology and geochemistry have suggested that the Quedang and Dala two-mica granites and the Qiaga porphyritic leucogranites represent cumulates and fractionated melt-rich magmas, respectively. This is evidenced by systematic variations between Sr, Y, (La/Sm)N and Eu/Eu* in magmatic apatites from Quedang and Dala, consistent with the fractionation crystallization of plagioclase and monazite.Apatite has a wide range of initial 87Sr/86Sr ratios (0.7016–1.0088), far exceeding the range of whole-rock records (0.7011–0.7204). Notably, most of the analyzed apatites show lower range of initial 87Sr/86Sr ratios consistent with locally exposed amphibolites (0.7109–0.7332). The remaining small portion of apatites have initial 87Sr/86Sr ratios falling within the data range of the locally exposed metapelites (0.8517–0.9527). Therefore, the investigated granites have mixed magma sources dominated by amphibolites with subordinate metapelites. This can be inferred by apatite Sr isotopes alone, but not by whole-rock Sr isotopes alone. Our investigations highlight that in-situ geochemistry of apatite can provide a powerful means to unravel the mixed magma sources and complicated magmatic processes for granites.

Extent and survival of zoned pyroxene within intrusions hosting magmatic sulfides: Implications for zoned pyroxene as a prospectivity indicator

AbstractChromium-zoning patterns in pyroxene from the economically significant Ni-Cu sulfide deposits at Nova-Bollinger (Western Australia) and Kevitsa (Northern Finland) were investigated using XRF mapping, automated mineralogy, and EPMA analyses. At Nova-Bollinger, complex Cr-zoning patterns are found widely throughout the cumulus orthopyroxene and clinopyroxene within the Lower Intrusion, a small chonolith that hosts the vast extent of the sulfide mineralisation. Cumulus pyroxenes with visible sector and abrupt zonation patterns have been found up to 150 m vertically away from the massive sulfide ore. Complex zoning patterns are observed throughout the Kevitsa intrusion, in the form of strong oscillatory zoning in cumulus clinopyroxene and sector zoning in idiomorphic orthopyroxene oikocrysts. Kevitsa pyroxenes show varying degrees of hydration, leading to epitaxial replacement by amphibole. Cr zonation is visible through the early stages of this alteration, with preservation enabled by the presence of Cr-rich epitaxial amphibole; however, the remnant zoning is lost as the amphibole alteration progresses. Results suggest that Cr zonation in pyroxene may be an effective indicator of dynamic recharged conduits and therefore an indicator of favourable conditions for metal enriched magmatic sulfide ore formation. Such indicators have significant vertical extent from the ore body and can survive partial alteration, which makes them a useful tool for prospectivity assessment of drilled intrusions. Furthermore, our data show that there is potential for complexly zoned pyroxene to be used as an ex-situ prospectivity indicator in glacial till.

Characteristics of Dioritic Intrusion at Kaligono Area, Kulon Progo Mountains, Indonesia: A Preliminary Study for Petrogenesis Implications

Abstract This study defines the characteristics of dioritic rock intrusion in the Kaligono area, Kulonprogo Mountains, Indonesia. Previous studies suggest the existence of porphyry deposit system in the mentioned area, hosted by the dioritic intrusion. According to the Geologic Map of Yogyakarta Quadrangle, age of the dioritic intrusion is the Miocene. Study of the intrusion characteristics is very important to gain a better understanding of the geological model associated with the deposit system. This preliminary study focused on determining petrogenesis of the dioritic intrusion. Methods carried out in this study were field data collection, petrographic analysis, and geochemical analysis using ICP-AES (Inductive Coupled Plasma-Atomic Emission Spectrometry) and ICP-MS (Inductively Coupled Plasma Mass Spectrometry) analysis. Petrography analysis showed that igneous rocks in this research area consist of dioritic rock with phorphyritic texture and oscillatory zoning. Based on its geochemical composition, the rock samples can be classified as diorite and granodiorite and calc-alkaline suites. These rocks are enriched in LILEs (Rb, Ba, Sr, and K) and depleted in HFSEs (Nb, Ti, Zr). In addition, REE shows a slight enrichment of light-REE and depletion of HREE. These patterns of the trace elements including REE show a typical pattern of calc alkaline arc. Petrographic observation and geochemical variation indicate that the magma has undergone fractional crystallization.

Quartz texture and the chemical composition fingerprint of ore-forming fluid evolution at the Bilihe porphyry Au deposit, NE China

Abstract Quartz is widely distributed in various magmatic-hydrothermal systems and shows variable textures and trace element contents in multiple generations, enabling quartz to serve as a robust tracer for monitoring hydrothermal fluid evolution. This study demonstrates that integrated high-resolution SEM-CL textures and trace element data of quartz can be used to constrain physicochemical fluid conditions and trace the genesis of quartz in porphyry ore-forming systems. The Bilihe deposit is a gold-only porphyry deposit located in the Central Asian orogenic belt, NE China. Four quartz generations were distinguished following a temporal sequence from early-stage dendritic quartz, unidirectional solidification textured quartz (UST quartz), gray banded vein quartz (BQ), to late-stage white calcite vein quartz (CQ), with the Au precipitation being mostly related to dendritic quartz, UST quartz, and BQ. The well-preserved dendritic quartz with sector-zoned CL intensities and euhedral oscillatory growth zones crystallized rapidly during the late magmatic stage. The relatively low Al contents of dendritic quartz were interpreted to be related to contemporaneous feldspar or mica crystallization, while the high-Ti contents indicate high-crystallization temperatures (~750 °C). The comb-layered UST quartz displays heterogeneous, patchy luminescence with weak zoning, hosts coeval melt and fluid inclusions, and retains the chemical characteristics of magmatic dendritic quartz. High-Ti and low-Al contents of UST quartz suggest a formation at relatively high temperatures (~700 °C) and high-pH conditions. Three sub-types can be defined for hydrothermal BQ (BQ1, BQ2, and BQ3) based on contrasting CL features and trace element contents. The Al contents increase from BQ1 to BQ2 followed by a drop in BQ3, corresponding to an initial decrease and subsequent increase in fluid acidity. Temperature estimates of BQ decrease from BQ1 (635 °C) to BQ3 (575 °C), which may, however, be disturbed by high growth rates and/or high-TiO2 activities. The CQ typically displays a CL-bright core and CL-dark rim with oscillating CL intensities and is characterized by the lowest Ti and highest Al, Li, and Sb contents compared to the other quartz types, which suggests a deposition from more acidic and lower temperature fluids (~250 °C). Trace element patterns indicate that a coupled Si4+ ↔ (Al3+) + (K+) element exchange vector is applicable to dendritic quartz, UST quartz, and BQ. By contrast, charge-compensated cation substitution of Si4+ ↔ (Al3+, Sb3+) + (Li+, Rb+) is favored for CQ. The comparison with compiled trace element data of quartz from other porphyry Au, Cu, and Mo deposits worldwide suggests that Ti, Al, Li, K, and Ge concentrations, as well as Al/Ti and Ge/Ti ratios, have the potential to discriminate the metal fertility of porphyry mineralization.

Cobalt remobilization during tectonic–hydrothermal overprinting: A case from the Tuolugou Co(–Au) deposit in East Kunlun Orogenic Belt, China

Stratiform Cu-Co deposits hosted in (meta-) sedimentary and volcaniclastic rocks contribute two-thirds of the global Co supply. However, the mechanisms driving Co remobilization during tectonic-hydrothermal overprinting events remain poorly understood. As a dominant Co repository, pyrite can provide valuable insights into mineralization history due to its refractory nature. Here, we present the first micro-analytical investigation of pyrite from the Tuolugou Co(–Au) deposit in East Kunlun Orogenic Belt. Ore textures indicate that Co mineralization is attributed to two distinct stages: primary enrichment and subsequent overprinting processes. The former is characterized by pyrite (PyI with up to 3.92 wt% Co) remnants exhibiting oscillatory zones, while the latter is marked by deformation of pyrite (PyII) ores. Three overprinting episodes, namely Da, Db, and Dc, are further distinguished according to varying extents of deformation and mineral assemblages. The Da is characterized by synkinematic PyIIa (up to 4.18 wt% Co) augens, which were most likely formed via pressure–solution mechanism. The Db is represented by polygonal PyIIb (up to 4.75 wt% Co) and siegenite with 120° triple–point junctions. The random orientation and rare intragrain misorientation of cobaltiferous sulfides at Db suggest their formation by recrystallization without plastic strains. The Dc resulted in the formation of Co ± As–rich PyIIc (up to 5.36 wt% Co) along with minor occurrence of cobaltite–gersdorffite, pyrrhotite (up to 1.25 wt% Co), and marcasite (up to 1.28 wt% Co). The PyIIc replacing PyI underscores the role of fluid-coupled dissolution and precipitation during fluid–rock interactions in the formation of these cobaltiferous sulfide assemblages at Dc. The presence of PyIIc infilling within the PyI fissures, in conjunction with the transition from siegenite to cobaltite–gersdorffite, suggests a shift towards low fO2 and low temperature conditions under relatively brittle setting. There is a discernible disparity in sulfur isotope compositions between the two mineralization stages. The PyI exhibits a narrow range of δ34SV–CDT values from –2.14 to 1.35 ‰, indicating a magmatic sulfur origin. In contrast, PyII displays a wide δ34SV–CDT range of –5.22 to 6.16 ‰, suggesting an involvement of strata sulfur during the overprinting stage. Monazite U-Pb dating has effectively constrained two mineralization events. The ca. 453 Ma age implies a potential correlation of the primary Co mineralization with the Late Ordovician to Early Silurian exhalative-syngenetic processes in a Proto–Tethyan-related post–collisional extension setting. Conversely, the ca. 190 Ma age indicates that Co remobilization was instigated by the early Mesozoic ductile–brittle deformation associated with the Paleo-Tethyan orogenesis. Finally, geochemical modeling was performed by simulating the interaction of a Co-rich acidic, reducing fluid with typical quartz-albitite rocks. The simulations demonstrate the appearance of independent Co minerals such as Co-pentlandite during the reaction progression, greatly supporting ore upgrading via tectonic-hydrothermal overprinting.

New Research Results on U-Pb Zircon Isotope Age of Ta Cu Granodiorite in Dalat Zone and Geological Significance

Ta Cu granodiorites from the Dalat Zone, Southern Vietnam, have typical composition of granodiorite, coinciding with the Dinh Quan complex. The granodiorites are composed of plagioclase (45–50%), quartz (20–25%), orthoclase (15–20%), hornblende (5–7%), and biotite (5–7%). Geochemically, they are met aluminous with an average A/CNK value of 0.89- 0.96, low SiO2 (61.68-62.14) and high Na2O/K2O&gt; 1. Petrographical and geochemical characteristics of Ta Cu granodiorites are classified as I-type granite generated from arc-related magmas. Zircons selected from these rocks are characterized by prismatic shape, oscillatory zoning, no luminescent rim, and have high ratio Th/U (0.35–1.11) that are indications of the magmatic origin. We report the first LA-ICP-MS 206Pb/238U zircon ages of 116 Ma for the Ta Cu granodiorite in the Southeastern Dalat Zone in Southern Vietnam. This age value is temporally coeval with Early Cretaceous magmatism previously reported in the Dalat Zone. Zircon ꜪHf(t) values +4.0 to+13.0, whole-rock ꜪNd(t) values -2.0 to +0.2, and average model ages (TDM2) 652 Ma to 957 Ma indicate that the Ta Cu granodiorites were derived from the remelting of Neoproterozoic mantle-derived melt with a minor input of crustal materials. Together with other Late Mesozoic magmatic complexes along the Dalat Zone, the Ta Cu granodiorites are a representative of magmatism linked to Pacific Ocean subduction beneath the Indochina block during the Early Cretaceous.

Ore-forming process of the Xiaoyuzan gold deposit in the Western Tianshan, Northwest China: Constraints from mineralogy and S isotopes of sulfides

The Xiaoyuzan deposit is a typical intermediate-sulfidation epithermal Au deposit in the Boluokenu metallogenetic belt. The orebodies are hosted by the Lower Carboniferous Dahalajunshan Formation volcanic rocks and controlled by the NW- and NNW-striking faults. The metal minerals present in the ores mainly include pyrite, sphalerite, galena, chalcopyrite, and tetrahedrite. The non-metallic minerals are primarily composed of quartz, calcite, and sericite. Three ore-forming stages are distinguished based on mineral assemblages, wall-rock alteration, and vein crosscutting relationships, including the quartz-pyrite stage (I) with silicification and propylitization, quartz-sulfide stage (II) with phyllic alteration, and quartz-carbonate stage (Ⅲ) with carbonatization. Three different types of pyrite are classified: coarse-grained PyI with cubic from the wall rock, fine-grained PyII with a crystal form of pentagonal dodecahedron in the quartz-sulfide veins, and coarse-grained cubic PyⅢ in the quartz-carbonate veins. The in-situ δ34S value range of sulfides from stage I, stage II and stage Ⅲ are 5.0 ‰ to 5.5 ‰, 4.3 ‰ to 6.5 ‰ and 5.7 ‰ to 6.2 ‰, respectively. The composition of S isotopes indicates that the source of the sulfur is magmatic in origin, with main contribution from the host rock. All the types of pyrite are relatively enriched with Sb, Cu, Ag, Pb, Bi, and As. The composition of pyrite suggests that the Au in the pyrite present as lattice gold (Au+1). The gradual decrease in Co contents from in PyⅠ, PyⅡ to PyⅢ indicates a gradual decrease in temperature during fluid evolution. The contents of trace elements in sphalerite are relatively low, with Fe, Mn, Cd, and Cu being relatively enriched. Using the sphalerite geothermometer (GGIMFis), the calculated temperature falls within the range of 303.0 to 334.3 °C. Pyrite II is characterized by the occurrence of oscillatory zones, suggesting rhythmic changes in fluid physicochemical conditions and compositions. Although coexisting of liquid-rich and vapor-rich aqueous inclusions were locally observed in stage II quartz according to previous studies, the absence of crustiform/colloidal/lattice bladed quartz in the main stage suggests that slight or gentle fluid boiling has occurred. In summary, it is proposed that fluid-rock reactions made great contribution for the precipitation of gold and sulfides in the Xiaoyuzan deposit.

Origin of discordant U[sbnd]Pb dates in non-metamict zircons in intrusives deformed at granulite facies: Grain scale processes, and relevance to Cambrian orogeny, Eastern Ghats Belt, India

Interpreting the origin of UPb discordance in zircons in intrusives that experience high-T metamorphic-deformation events is challenging. We investigate in depth the origin of UPb dates obtained from garnet-bearing border zone granitoids and a sheared ferrodiorite dyke bordering the Balangir anorthosite pluton, eastern India. The crustal domain is known for discordant ages resulting in disputes regarding the age of intrusion and multiple granulite facies events. We shed light on the origin of the discordant dates utilizing CL imaging, electron backscatter diffraction analysis, trace element mapping in zircons, and Ti-in-zircon thermometry.Zircons in the foliated border zone granitoids (BZG) comprise (a) embayed cores with varying Y, U and Hf oscillatory zones, and (b) well-faceted chemically-homogeneous mantles crystallographically continuous with the cores, which truncate the oscillatory zones. In the intensely sheared ferrodiorite, cauliflower-shaped zircons possess profuse micropores and micro-fractures. Ti-in-zircon temperatures (700–950 °C) overlap in the texturally-distinct zircons, but are somewhat lower in the mantles/cauliflower-shaped zircons relative to the oscillatory-zoned cores in BZGs.LA-ICP-MS dates of zircons in four samples constitute a near-unique discordia line with the upper and lower intercepts at ca. 980 Ma and 495 Ma. Interestingly, dates from the mantles are highly variable with no correlation between age decrease and distance to the cores. The lack of concordant dates at the two intercepts, and the increase in discordance away from the intercepts preclude episodic zircon growth, and suggests a single-stage granulite facies event (ca. 495 Ma) that modified the ∼980 Ma zircon xenocrysts entrained from protoliths into the intrusives. We propose the age discordance was caused by melt-mediated high-T interface coupled dissolution-precipitation processes at ∼495 Ma. Variable inheritance of isotopic signatures of ∼980 Ma zircon xenocrysts in the younger zircons contributed to discordance in UPb systematics; the effect of variable inheritance of ∼980 Ma isotope signatures is less pronounced in the cauliflower-shaped zircons from the HFSE enriched ferrodiorite residual melts from high degree of plagioclase fractionation.Our results are consistent with a distinct Cambrian (∼495 Ma) orogeny involving emplacement of anorthosite pluton and related intrusives and high-T granulite-facies deformation-metamorphism in the ∼980 Ma Eastern Ghats Province, and are a direct record of Cambrian collision between the Eastern Ghats Province and the Archean cratonic nucleus.

Oscillatory zoning of minerals as a fingerprint of impurity-mediated growth

We propose a kinetic mathematical model of the oscillatory compositional zoning profile recorded in minerals based on the crystal growth suppression induced by impurities. Notably, the presence of a small amount of impurities significantly inhibits crystal growth, and a growth inhibition mechanism called the pinning effect is widely accepted. Here we show that a model that considers the pinning effect and adsorption/desorption kinetics of impurities on the crystal surface can reproduce the oscillatory compositional zoning. As impurities are common in nature, this model suggests the existence of a universal mechanism that can occur in the growth processes of various crystals.

Recognition of Neogene tin mineralization in the Southeast Asian tin belt

The Southeast (SE) Asian tin belt is a major tin producer globally, with a prolonged mineralization history from the Permian to Paleogene (ca. 285−45 Ma). Tin deposits in this region are typically associated with tectonic settings that involve subduction and collision of the Paleo-, Meso-, and Neo-Tethys slabs. Ca. 40 Ma, a notable transition occurred in the tectonic regime of SE Tibet, with the Neo-Tethys subduction giving way to lateral extrusion of the Indochina block along major strike-slip faults. Previously, it was believed that this shift had brought tin mineralization to a halt. In this study, we present in situ laser ablation−inductively coupled plasma−mass spectrometry U-Pb cassiterite ages of 21−19 Ma from the Yunling tin deposit located in western Yunnan, China. Yunling produces gem-quality cassiterite that is transparent but contains low U contents, which renders usual U-Pb dating techniques unusable. To address this, a customized dating protocol involving cathodoluminescence (CL) imaging and testing of U distribution on crystallographically well-defined cassiterite crystals was applied. The study revealed two types of primary microstructures in cassiterite: volumetrically dominant concentric oscillatory growth zones and subordinate CL-dark sector zones. The U content shows a preferential enrichment in the CL-dark sector zones, typically tens of parts per million (ppm), which is two orders of magnitude greater than the U content in the concentric zone. This is significant, as the dating results (21−19 Ma) obtained through the targeted selection of CL-dark sector zones represent the youngest tin mineralization event in the SE Asian tin belt. Additionally, these results challenge the established belief that the ore-hosting Indosinian granite, dated to ca. 215 Ma, was related to Sn mineralization in the Yunling area. We suggest that emplacement of the early Neogene Sn mineralization at Yunling may be genetically connected to extensive delamination of the lithosphere in southeastern Tibet. The lithospheric delamination led to the upwelling and decompression partial melting of the asthenosphere, which provides a plausible explanation for the high temperature required for the release of Sn from biotite-dehydration melting of sedimentary protolith. The study also highlights the potential of Oligocene−Miocene-aged granites situated in the Sanjiang Tethys and adjacent areas of western Yunnan as prospective exploration targets for tin mineralization.

Geology and genesis of the Aqishan Pb-Zn deposit, NW China: Insights from mineralogy, geochemistry, and in situ U-Pb geochronology

The unique ore-forming processes and the key factors responsible for formation of skarn deposits are still obscure, and challenges exist in the determination of timing of Pb-Zn skarns owing to lacking suitable mineral chronometers. Here we present detailed paragenesis, bulk geochemistry, in situ U-Pb dating of zircon and garnet, and garnet oxygen isotopes together with in situ zircon Hf-O isotopes from the newly discovered Aqishan Pb-Zn deposit in the southern Central Asian Orogenic Belt (CAOB), northwest China. This comprehensive data set revealed a Late Carboniferous subduction-related distal Pb-Zn skarn system associated with the granitic magmatism. Pre-ore stage garnets are generally subhedral to euhedral with oscillatory zoning and show slightly fractionated rare earth element patterns with positive Eu anomalies that point to an infiltration metasomatism origin under high water/rock ratios. The syn-ore stage sphalerite is typically enriched in Mn and Cd and has moderate Zn/Cd ratios (337–482), with a formation temperature of 265 °C to 383 °C, which indicate magmatic-hydrothermal signatures. The isocons defined by P2O5 decipher that the principal factors for skarn formation were elevated activities of Fe, Ca, and Si species, where remobilization of Pb metals, meanwhile, contributed to ore-forming budgets to mineralizing fluids. SIMS U-Pb dating of zircons from granite porphyry that occurs distal to the skarns and Pb-Zn orebodies shows that these intrusions emplaced at ca. 311.3–310.6 Ma, recording the subduction of the Paleo-Tianshan oceanic plate. Hydrothermal garnets in close textural association with Pb-Zn sulfides yield indistinguishable in situ LA-ICP-MS U-Pb ages of 310.5 ± 4.1 Ma. Whole-rock geochemistry and in situ zircon Hf-O isotopes (δ18O = 4.6‰–6.0‰) indicate that the granite porphyry was derived from partial melting of juvenile crust and influenced by subducted oceanic crust. Oxygen isotope compositions of garnets (δ18O = 8.0‰–9.0‰) demonstrate that the equilibrated ore fluids were inherited from fluid-rock interactions between a primary magmatic water and host tuff rocks. Our study highlights the application of garnets as a potential robust U-Pb geochronometer and isotopic tracer of ore fluids in skarn mineralizing systems in subduction-related arc environments.

Zircon compositional systematics from Devonian oxidized I-type granitoids: examination of porphyry Cu fertility indices in the New Brunswick Appalachians, Canada

Zircon is a common, widely distributed accessory mineral in most igneous rocks and its refractory nature records magmatic evolution in terms of oxygen and U-Th-Pb isotopes, and trace-element contents all of which reflect the intrinsic physio-chemical evolution of the magmatic systems in which it crystallized. Zircon compositions can be used as an indicator of relative fertility of hypabyssal intrusions in terms Cu ± Mo ± Au porphyry mineralization. To further characterize syn- to post-collisional adakitic Devonian oxidized I-type granitoids in the New Brunswick (specifically, those with Cu ± Mo ± Au porphyry-style mineralization), LA-ICP-MS analyses (guided by µXRF-EDS mapping and SEM-BSE imaging of polished thin sections) of zircons from 13 granitoids was conducted. The zircons studied were similar in terms of their textures (homogenous cores, patchy zoning, oscillatory zoning, and some unzoned zircon); however, they have a wide range of trace- and minor-element (Hf, HREE, Y, Th, U) compositions. Specifically, Zr/Hf ranges between 24–60, whereas Th/U ranges between 0.15 and 5.37. The presence of inherited zircon affects the concentrations of Th and U, as well as other key elements. Estimated crystallization temperatures of granitoids, ranging from 737 to 899°C, were calculated via Ti-in-zircon geothermometry assuming reduced TiO2 and SiO2 activities. The calculated log fO2 values for zircons from some of these granitoids indicate a highly oxidized magmatic signature. Zr/Hf, Eu/Eu⁎, and (Eu/Eu⁎)/Y in zircon, as well as zircon (Ce/Nd)/Y are some of the best indicators of porphyry fertility. The Ce/Ce* in zircon exhibit a large range (1.1–590), with higher Ce/Ce* reflecting more metallogenically favourable oxidizing conditions. If Eu/Eu⁎ in zircon is ≥0.4 (relatively oxidized conditions), it indicates a high potential for an ore-forming porphyry Cu mineralizing system. Lower Eu contents reflect relatively reducing conditions, as Eu anomalies vary with oxygen fugacity as well, and the relative abundance of Eu2+ is higher, but does not substitute into the zircon lattice. The evidence extracted from analyzing the zircon composition within New Brunswick’s I-type granitoids indicates the fertility of these hypabyssal intrusions.

Mineral Textures and Chemistry Trace the Origin and Transcrustal Evolution of the Sanyuangou Syenite in Southern North China Craton

Abstract Alkaline rocks are widely distributed in various geological environments and are important carriers for exploring the formation and compositional diversity of continental crust. Extensive studies have investigated the processes of mantle melting and crustal differentiation that produced such rocks. However, the potential interaction processes between mantle-derived magma and crust during their formation are poorly constrained. In this study, we focus on a Paleoproterozoic garnet-bearing syenite in the Xiong'er large igneous province (LIP) on the southern margin of the North China Craton through detailed whole-rock and mineral analyses. The high K2O (7.4–8.8 wt %) syenite emplaced at ~1772 Ma with ancient inherited zircon (1800–2800 Ma). The dominant mineral assemblage is composed of clinopyroxene, garnet, and K-feldspar with a small amount of titanite. Complex compositional oscillatory zoning of clinopyroxene and garnet indicates that magma mixing played a significant role in the formation of the syenite. We estimated the major elements composition for melts in equilibrium with clinopyroxene and calculated the clinopyroxene/melt partition coefficients by crystal lattice strain model, thus calculating the trace elements of the equilibrated melts. The equilibrium melts of high Mg# (&amp;gt;85) clinopyroxene have high CaO/Al2O3 (&amp;gt;0.6) and low Hf/Sm (&amp;lt;0.4), which suggests a role for carbonatitic metasomatism of the mantle. The variables La/Yb (24.4–56.1), Dy/Yb (0.8–5.9), and Yb (0.6–10.3 μg/g) indicate that the initial melts were formed by 1% to 2% partial melting of spinel-garnet phlogopite lherzolite. An REE-based model for melts in equilibrium with low Mg# (&amp;lt;85) clinopyroxene indicates that 10% to 30% felsic magma from ancient crust participated in hybridization. In addition to well-documented magma mixing, the oscillatory zoning of garnet is also related to competition with titanite. The initial alkaline magmas have a high water content (~4 wt %), which delays the crystallization of K-feldspar, leading to the enrichment of K2O, until the K-feldspar accumulates in the shallow crust to form the syenite. Magma mixing under an open system further leads to alkalinity enrichment. Magma source and crustal evolution jointly determine the potassium-rich characteristics of syenite. Multiple episodes of magma mixing and fractional crystallization occur in the crust (700–300 MPa), suggesting complex and vertically extensive magma chambers. This study represents the first identification of carbonatitic metasomatism as a mantle source in the Xiong'er LIP. Furthermore, it offers a new perspective on magma mixing between the mantle and crust in transcrustal magmatic systems, contributing to the formation of alkaline rocks.

W-rich zircons from the granite in the Hukeng tungsten deposit, South China: Genesis and exploration significance

South China is endowed with copious hydrothermal tungsten ore deposits, which are generally suggested to be associated with highly fractionated granites. However, the mechanism of tungsten enrichment and mineralization during magmatic-hydrothermal processes is not clear. Here, we clearly identified W-rich zircons (up to several thousand ppm) from the granite in the Hukeng tungsten deposit in South China. W-rich zircons are generally dark in cathodoluminescence images with irregular cracks, cavities and blurry oscillatory zones. They also show high contents of U, Nb, REEs, and high W/Gd ratios, which are not possible to be produced only by magma differentiation. Raman spectra of zircons indicate that these W-rich zircons have experienced different degrees of metamictization. Thus, these W-rich zircons should be crystallized from the late magma and subsequently altered by W-rich magmatic-hydrothermal fluids. W-rich zircons record the activity of W-rich ore-forming fluids which were exsolved from the granitic magma. We suggested that the W/Gd ratios of > 0.2 of zircons can be used as an indicator to estimate the W mineralization potential of a granite. This study provides a new pathway for using zircon to record tungsten mineralization processes and to guide tungsten ore prospecting.