Oscillatory Zoning Research Articles

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# (>85) clinopyroxene have high CaO/Al2O3 (>0.6) and low Hf/Sm (<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# (<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.

Genesis of W mineralization in the Yangla Cu-polymetallic deposit (NW Yunnan, China): Constraints from scheelite microstructure, trace element, U-Pb dating and Sr isotope geochemistry

The Yangla Cu-polymetallic deposit is the largest skarn Cu deposit in the Jinshajiang suture zone. Recently, an new W orebody was identified in the depths of the Cu orebodies. However, the genetic relationship between W and Cu orebodies, along with the tungsten ore-forming processes, remains unclear. This study delves into the careful investigation of three types of scheelites focusing on microstructure, trace element compositions and Sr isotope geochemistry. The aim is to elucidate the source and evolution of ore-forming fluids and ore genesis in the multi-episodic metallogenic systems. Primary scheelite (Sch-I) generally displays oscillatory zoning in CL images with the lowest REE (3.8–142 ppm) and highest Sr (604–1480 ppm) contents. Secondary scheelite (Sch-III), commonly precipitated as overprinting rims on primary crystal, has the highest REE (145–1071 ppm) and lowest Sr (376–793 ppm) contents. In contrast, Sch-II represents a transitional stage from primary to secondary, with REE and Sr contents at intermediate levels. Sch-I is characterized by LREE enrichment and a positive Eu anomaly in the chondrite-normalized REE patterns, whereas Sch-III shows MREE-rich patterns with a weak positive Eu anomaly. Scheelite U-Pb dating (30.3 ± 1.5 Ma) indicates that the W mineralization is not genetically related to Triassic granitoids in the Yangla district. Instead, it is likely associated with magmatic activities and tectono-thermal events in the Jinshajiang fault zone during the Cenozoic. The high initial 87Sr/86Sr ratios (0.71771–0.72229) in the scheelite, significantly higher than those of Triassic granites and ore-hosting marble, suggest that the geochemical features of Sch-I are inherited from the parental ore-forming fluids. These fluids are likely derived from the mixed hydrothermal fluids involved by the Neoproterozoic strata and/or concealed magmatism.

Fluid source and ore-forming process of the Lishupo Au deposit, NE Hunan: Constraints from fluid inclusions, SIMS oxygen isotope, LA-ICP-MS pyrite trace elements and fsLA-ICP-MS quartz trace elements

The Lishupo Au deposit (4.3 t @ 4.76 g/t) is located in the central Jiangnan Orogen. The processes and origins of regional gold mineralization, as well as the characteristics of the ore-forming fluids, continue to be poorly understood. This study integrates field geology, fluid inclusions, secondary ion mass spectrometry (SIMS) O isotope, femtosecond laser ablation inductively coupled plasma mass spectrometry (fsLA-ICP-MS) trace elements analysis for quartz, and LA-ICP-MS for trace elements study of pyrite to constrain the nature and source of ore-forming fluids, mechanism of gold precipitation, and ore genesis. Field investigations and microscopic observations reveal three mineralization stages at Lishupo: (1) the quartz-pyrite (Qtz1-Py1) stage; (2) the quartz-dolomite-polymetallic sulfides-gold (Qtz2-Py2) stage; and (3) the quartz-carbonate-pyrite (Qtz3-Py3) stage.Cathodoluminescence (CL) observations reveal that Qtz1 and Qtz2 have a homogeneous texture, while Qtz3 exhibits oscillatory zoning. Fluid inclusions in quartz suggest a CO2-H2O-NaCl ± N2 ± CH4 fluid system, which comprise H2O-CO2-NaCl, CO2-rich, and aqueous types. Microthermometry of fluid inclusions indicates low salinity (stage 1: 3.7–7.9 wt% NaCl equiv.; stage 2: 2.2–7.5 wt% NaCl equiv.; stage 3: 1.4–3.9 wt% NaCl equiv.) and medium to low temperature (stage 1: 313–341 °C; stage 2: 209–286 °C; stage 3: 139–198 °C) for ore-forming fluids, consistent with the low Ti content (<10 ppm) found in the quartz. The low Al content (7.99–20.7 ppm) of Qtz1 suggests that the ore-forming fluids were saturated with CO2 and had a near-neutral pH. The Al contents are higher and more variable in Qtz2 (10.7–1959 ppm) and Qtz3 (21.6–713 ppm), which may imply fluctuations in fluid pH. δ18OFluid values for various types of quartz (Qtz1: 9.02–10.95 ‰, Qtz2: 6.30–7.68 ‰, Qtz3: 3.45–3.94 ‰) indicate a metamorphic fluid origin for stages 1 and 2 fluids, which were mixed with the meteoric water during stage 3. The highest concentrations of Au and As in Py2 suggest that the Qtz2-Py2 stage is the primary ore stage. The Co/Ni ratios of all types of pyrite are less than 1, indicating that the ore-forming materials are derived from metamorphic sedimentary rocks. Fluid inclusion microthermometry suggests that fluid immiscibility was responsible for the gold deposition during the Qtz2-Py2 stage. Fluid immiscibility destabilizes Au(HS)2-, leading to the precipitation of native gold. These data strongly suggest that the Lishupo gold deposit is classified as an orogenic-type deposit. Integrating the existing geochronology data and geological context, we emphasize the presence of the Late Triassic orogenic gold deposit in the Jiangnan orogen. This highlights a significant exploration target area within this zone for future gold prospecting.

Quartz fluid inclusions and trace elements in the Lailisigaoer porphyry Mo deposit, Western Tianshan, Xinjiang: Fluid evolution and metallogenic mechanism in magmatic-hydrothermal system

The Lailisigaoer deposit is a typical porphyry Mo deposit located in the late Paleozoic Boluokenu metallogenic belt of Western Tianshan, NW China. This study aims to understand molybdenum mineralization and the dynamics of magmatic-hydrothermal fluid within the porphyry system, focusing on fluid inclusion, cathodoluminescence textures, and trace elemental composition in various generations of quartz. Six vein types in the Lailisigaoer deposit are classified as comb quartz veins with unidirectional solidification texture (UST, QI), actinolite/biotite ± quartz veinlets (M-type, QII), quartz-chalcopyrite vein (A-type, QIII), quartz-molybdenite vein (B-type, QIV), quartz-pyrite vein (D-type, QV) and quartz-carbonate vein (E-type, QVI). Micro thermometry data indicate decreasing homogenization temperatures in primary fluid inclusions from UST to E-type veins. The magmatic-hydrothermal fluids associated with UST and M-, A-, B-, D-, E-type veins underwent a transition from high temperature (342–495℃), high-pressure (∼1.25 kb), and variable salinity (6.7–41.1 wt%NaCl) in the H2O-CO2-NaCl system to low-temperature (142–238℃), low-pressure (∼0.25 kb), and low-salinity (1.6–5.1 wt%NaCl) in the H2O-NaCl system. This evolution is reflected in the proportion of quartz with oscillatory zones decreasing and irregular quartz increasing, indicating a shift from turbulent to stable fluid conditions. Furthermore, a gradual reduction in Ti concentration (from 79 ppm in UST to 1.4 ppm in E-type quartz) suggests a decrease in fluid temperature during the magmatic-hydrothermal evolution. Mineralization primarily occurs in A- and B-type veins, with molybdenum precipitation attributed to fluid immiscibility in a medium–high temperature (240–368 ℃) and high pressure (∼0.95 kb) environment. The A-type veins (mean 31 ppm in Ti concentrations) consist of equigranular (dark-core) (QIII-1) and patchy inhomogeneous CL-gray quartz (QIII-2). The B-type veins (mean 24 ppm in Ti concentrations) are characterized by equigranular (bright-core) inhomogeneous quartz (QIV-1) with growth zones that are cemented by later mosaic homogeneous CL-gray quartz (QIV-2). Based on the quartz-Ti thermometer, the mineralized veins (A- and B-type) were confined to be formed at depths of 2.8–3.6 km, with molybdenum mineralization occurring at 3.4–3.6 km. Molybdenum mineralization initiates during the QIV-1 crystallization period in magmatic-hydrothermal fluids and terminates in the QV-2 generation.

Redefining timing, genesis and geodynamic setting of polymetallic skarn mineralization, Gangdese belt, Tibet, from LA–ICP–MS garnet U–Pb geochronology

Iron, Cu, Pb–Zn, and W–Mo skarn deposits occur in the Gangdese metallogenic belt, Tibet. A lack of precise age constraints for mineralization hinders understanding of the processes contributing to skarn mineralization, particularly identification of the causative intrusions. In this study, new garnet U–Pb geochronological data are provided for the Qiagong (Fe) and Jiaduobule (Fe–Cu) skarns. We place particular emphasis on skarn garnet mineralogy, using scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS), to characterize garnet textures, compositions, and U–Pb isotope systematics. All garnets studied belong to the grossular-andradite series and display oscillatory compositional zoning (And100Gr0 to And20Gr80). Andradite-dominated garnet features a chondrite-normalized REE fractionation pattern exhibiting enrichment in LREE relative to HREE and a positive Eu anomaly, whereas grossular-dominated garnet displays relative LREE depletion and a marked flat HREE fractionation trend. Ore-forming elements, including Sn, W, As, and U, are detected at concentrations up to several hundreds of ppm in the same garnets. Concentrations of W and As are higher in andradite and correlate positively with one another. The correlation between U, Sn and the major oxide composition of garnet is insignificant, potentially resulting from the changing valence states of these elements under different redox conditions. Together with previously published and limited new data for the Gebunongba (Fe), Ri’a (Cu), and Hahaigang (W–Mo) skarns, the new garnet U–Pb age data indicate that the major Fe, Pb–Zn, and W–Mo mineralization event in the Gangdese metallogenic belt took place between 65 Ma and 50 Ma, with marked peaks at ∼ 65 Ma and ∼ 53 Ma. Partial melting of a crustal-dominated source due to the slab rollback (∼65 Ma) and break off (∼53 Ma) of Yarlug–Zangbo Tethyan Ocean and subsequent asthenosphere upwelling induced this regional event during the Paleogene to early Eocene. A less common but regionally widespread Cu (±Au) mineralization event in the same belt formed during the Late Cretaceous (∼85 Ma) and may have resulted from the coupled influence of the northward subduction of the Yarlug–Zangbo Tethyan Ocean and the southward subduction of the Bangong–Nujiang Tethyan Ocean. This contribution highlights the potential significance of the Late Cretaceous Cu(±Au) event and hence the prospectivity of the belt for both skarn and porphyry systems. More broadly, our findings carry implications for Neo-Tethyan metallogeny in the region extending from southwestern China to eastern Europe during the Late Cretaceous.

Geochronology and geochemistry of zircon and columbite–tantalite group minerals from the Weilasituo Sn–polymetallic deposit, northeastern China: Implications for the relationship between mineralization and the magmatic–hydrothermal transition

The Weilasituo Sn–polymetallic deposit, located in the southern portion of the Great Xing'an Range of Inner Mongolia, China, is a super-large Sn deposit associated with abundant Li, Rb, Nb, Ta, Zn, and Cu resources. Despite that previous studies have characterized the age, hydrothermal evolution, and genetic relationship between the alkali feldspar granite porphyry and associated Sn–polymetallic mineralization, the magmatic–hydrothermal evolution and ore–forming processes remain ambiguous. To address these ambiguities and bridge this knowledge gap, this contribution characterizes the texture, geochemistry, and U–Pb isotope composition of zircon and columbite–tantalite group minerals (CGMs) from amazonitized alkali feldspar granite (AMG) and albitized alkali feldspar granite (ABG) in the Weilasituo deposit. Type-I zircon (Zr1) is inclusion-poor, translucent, and is characterized by low light rare earth element (LREE) contents, high (Sm/La)N ratios (mean = 655.7), and low Th/U (mean = 0.21 < 0.3), Zr/Hf (mean = 5.46), and Y/Ho ratios (mean = 4.42), indicating that it formed during the magmatic–hydrothermal transition. Type-II zircon (Zr2) is inclusion-rich, porous, has a low CL response, and is characterized by low Th/U ratios (0.08–0.32, mean = 0.17), high LREE contents, weakly positive Ce anomalies, and low (Sm/La)N ratios (mean = 20.7), indicating that it formed via hydrothermal alteration of Zr1 (i.e., magmatic–hydrothermal zircon). Type-I CGM (CGM1) generally lacks oscillatory zoning, and has similar and positively correlated Ta/(Nb + Ta) and Mn/(Mn + Fe) values (AMG: R2 = 0.93; ABG: R2 = 0.75), indicative of a magmatic origin. Type-II CGMs (CGM2) occur as rims on CGM1 and are characterized by higher Ta/(Nb + Ta) and lower Nb/Ta ratios than CGM1, indicative of precipitation from a hydrosilicate liquid during the magmatic–hydrothermal transition. Based on the characteristics of CGMs, two stages are evident in the evolution of the Weilasituo granite porphyry: an earlier magmatic differentiation stage and a later magmatic–hydrothermal transition stage. Furthermore, the magmatic–hydrothermal transition stage can be subdivided into the AMG and ABG substages within the porphyry system based on petrological and mineralogical characteristics. The U–Pb ages for zircons and CGMs from the alkali feldspar granite porphyry range from 137.2 ± 2.0 Ma to 129.8 ± 1.4 Ma, without a notable age gap. The similarity in U–Pb ages between CGM1–CGM2 and Zr1–Zr2 indicates that the magmatic stage and the magmatic–hydrothermal transition at Weilasituo were continuous processes that occurred during the Early Cretaceous.

Magmatic–hydrothermal evolutionary processes in highly evolved granitic systems: Insights from zircons of the Baishitouquan pluton, NW China

Abstract As a robust accessory mineral in igneous rocks, the mineralogical and geochemical characteristics of zircon can record the lithological differentiation and magmatic–hydrothermal evolution of highly evolved granitic systems. The F-Rb–rich, highly evolved Baishitouquan pluton of NW China exhibits gradual lithological changes from leucogranite, amazonite-bearing granite, and amazonite granite in the lower levels of the pluton to topaz-bearing amazonite granite, topaz albite granite, and pegmatite in the upper levels. In this study, three types of zircon grains were identified in five lithological zones based on textural and chemical characteristics. Type I zircon, which mostly occurs in leucogranite and amazonite-bearing granite, exhibits oscillatory zoning in cathodoluminescence images and experienced low degrees of radiation damage (0.21–0.68 × 1015 α-decay events/mg), which is indicative of its magmatic origin. Type II zircon, which mostly occurs in amazonite granite and amazonite pegmatite, exhibits textures that are indicative of hydrothermal alteration (e.g., spongy texture, porosity, and microcracks), and has elevated concentrations of some cations, such as Ca and Al. Type II zircon contains a higher concentration of non-formula elements, including rare earth elements (REEs), and Hf, Th, and U, than Type I and III zircons. Additionally, Type II zircon exhibits a significant M-type lanthanide tetrad effect and experienced varying levels of radiation damage (3.75–11.72 × 1015 α-decay events/mg). These characteristics suggest that Type II zircon has a hydrothermally altered origin. Type III zircon, which is restricted to the topaz-albite granite, has the smallest crystal size among all types of zircon grains, shows a euhedral to anhedral mottled appearance, and is characterized by patchy, cloudy, or irregular zoning, with numerous fluid inclusions. This type of zircon contains higher concentrations of Ti (110–1030 μg/g) than other types of zircon grains. Additionally, this type of zircon experienced limited radiation damage (2.18–3.69 × 1015 α-decay events/mg), and has a smooth surface and homogeneous internal textures. These characteristics suggest that Type III zircon is the product of fluid interaction with hydrothermally altered Type II zircon. Accordingly, this type of zircon crystallized directly from a Zr-saturated hydrothermal fluid during the later stages of magmatic–hydrothermal evolution. These contrasting textural and compositional features of the three types of zircon grains are indicative of three stages of magmatic–hydrothermal evolution of the Baishitouquan pluton: magmatic, magmatic–hydrothermal transition, and hydrothermal. These magmatic and hydrothermal processes were involved in the enrichment, transport, and precipitation of rare metals, such as Rb. Accordingly, this contribution demonstrates that the textures and chemistry of zircon grains can serve as petrogenetic indicators for assessing magmatic–hydrothermal evolution and rare-metal mineralization in highly evolved granitic systems. Furthermore, this study presents a model of the magmatic–hydrothermal evolution of F-rich, highly evolved granitic systems through the lens of zircon.

Zircon in tin granite as tracer for fluid metasomatism and Sn mineralization

Most tin deposits in the world are genetically related to tin granite and form during complex magmatic-hydrothermal processes. Zircon is a common accessory mineral in granite and related ore systems and can host a number of ore metals, such as Sn, W, Nb, Ta, U and Th, in its crystal lattice. However, whether metal enrichment/depletion can trace ore-forming processes is still unclear. Here, we report that the metal concentrations in various types of zircons from the Mopanshan tin granites in the southern Great Xing'an Range (Northern China) can be used as good indicators of fluid metasomatism and Sn mineralization. Two lithological zones are developed in the Mopanshan pluton, including porphyritic syenogranite (PG) in the center and fine-grained syenogranite (FG) at the margin. Zircons in the PG (PGZ-1, PGZ-2, and PGZ-3) are all magmatic in origin, while zircons in the FG can be categorized into magmatic zircons (FGZ-1 and FGZ-2) and metasomatic zircons (FGZ-3). The PGZ-1 and FGZ-1 grains are transparent prismatic crystals with bright oscillatory zonation, whereas the PGZ-2 grains are murky crystals with dark oscillatory zonation. PGZ-3 and FGZ-2 grains occur as overgrowths of previously formed zircon (PGZ-1, PGZ-2, and FGZ-1) or as brown individual crystals, showing dark and homogeneous cathodoluminescence (CL) textures. The metasomatic FGZ-3 grains are translucent-opaque porous crystals with vermicular CL zonation and commonly replace FGZ-2. The trace element compositions of magmatic zircons are completely melt controlled, providing a record of magmatic evolution as a constant decrease in Zr/Hf ratios and a gradual increase in Th, U, Nb, and Ta contents. Moreover, the structure of magmatic zircons transforms from a crystalline state to an amorphous state as a consequence of radioactive decay of U and Th. A coupled dissolution-reprecipitation process is proposed for the formation of metasomatic FGZ-3. The reactive fluid is the magmatic fluid that exsolved from the melt in the late magmatic stage. The magmatic fluid replaced biotite and rare earth phosphates (mainly monazite and apatite) enclosed within biotite, resulting in significant amounts of Nb, Ta, Sn, P, Al, Ca, Fe, and REEs, which subsequently reacted with the FGZ-2 zircons to leach Th, U, Y, and HREEs. Eventually, REEs, Y, Th, and U in the fluid combined with P to form monazite and xenotime, while the other elements partially precipitated with the crystallization of the FGZ-3 zircons. Although the alteration of biotite only released approximately 190 ppm of Sn into the fluid, this is still a significant Sn source for the Sn deposits surrounding the Mopanshan pluton, taking the granite size (∼50 km2) and the volume proportion of biotite (∼5%) into account. Furthermore, based on previous studies on tourmaline from the Mopanshan granite and regional geochemistry, it may be inferred that the addition of wall rock components may also play an important role in Sn mineralization.

Mineralogical and geochemical constraints on the origin of alunite and APS minerals from advanced argillic alteration systems: A case study from Kuh-e-Lakht Au-Ag-Cu mineralization, NE Isfahan, Iran

A significant association of alunite supergroup minerals commonly associated with quartz and pyrite is found in the Kuh-e-Lakht district of NE Isfahan, Iran. These minerals occur as pervasive alterations and within hydrothermal quartz veins. Based on field observations, microscopic studies, and geochemical analyses, the alunite subgroup exhibits noticeable variations in morphology, composition, and geochemical signatures between areas with moderate to high mineralization and those with poor mineralization. Poorly mineralized regions contain aluminum-phosphate-sulfate (APS)-free minerals of the alunite subgroup formed from steam-heated acid or supergene processes at an estimated temperature of about 200 °C, with a higher K2O than Na2O content. These crystals exhibit pseudocubic or acicular habits and zoned formations with rhythmic bands and lack APS minerals. Moderately to highly mineralized areas in Kuh-e-Lakht host tabular to platy and bladed alunite subgroup crystals with a hypogene origin, formed at around 250 °C, characterized by a higher or equal Na2O content compared to K2O. These areas also feature APS minerals with different modes of occurrence. In the southwestern, north-central, and northwestern parts, a strong genetic link with high-sulfidation minerals like pyrite, enargite, and chalcopyrite is observed. Alunite subgroup crystals with the highest Na2O/K2O ratio or equal values, as well as APS minerals with svanbergite-woodhouseite composition, occur within alunite crystals or as individual euhedral crystals exhibiting complex oscillatory zoning. These characteristics confirm a close association with the ore formation period and also the influence of higher-temperature fluids with magmatic-hydrothermal components, likely originating in closer proximity to intrusive sources. The estimated temperature for the alunite subgroup and associated ore minerals in these areas falls in the range of approximately 250 °C to 300 °C.

Microstructural and microchemical analysis of zircon in a syenite lithic fragment from Ulleung Island volcano, South Korea

Abstract Background The intricate textural patterns commonly observed in metamorphosed and recrystallized zircon (ZrSiO4) underscore the crucial necessity of understanding the underlying mechanisms governing their formation to ensure accurate interpretation of the chemical and isotope data they contain. This study employed a combination of microanalytical techniques, including electron backscattered diffraction (EBSD) analysis, electron microprobe (EMP) mapping, and scanning electron microscope (SEM) imaging, to investigate the processes of formation and modification of zircon in a late Pleistocene (~ 35 ka) syenite enclosed within the Nari Tephra Formation on Ulleung Island in South Korea. Findings Under cathodoluminescence (CL), zircons within the syenite reveal dark, featureless, or oscillatory-zoned cores containing numerous inclusions of britholite. These cores are partially or entirely replaced by inward-penetrating bright-CL domains that exhibit minimal inclusion presence. Despite these changes, the external morphologies of the zircons remain largely unchanged, and the faded oscillatory zoning is preserved in the replaced regions. EMP mapping discloses amoebiform micro-domains with high Y, U, and Th concentrations within the dark-CL cores, while the bright-CL domains are relatively deficient in these trace elements. Microstructural analysis of the zircons using EBSD mapping indicates no significant misorientation between the dark-CL cores and the bright-CL rims. Deformation-related low-angle boundaries by lattice distortion are clearly observed in certain grains, cutting across the discrete SEM and EMP domains, and often aligned along submicron pore trails. Conclusions Microstructural and microchemical analyses carried out in this study establish that the zircons within the Ulleung syenite have undergone subsolidus recrystallization, a process likely influenced by the presence of fresh melts or fluids. This recrystallization process could be attributed to either coupled dissolution and reprecipitation or thermoactivated particle and defect volume diffusion due to inherent lattice strain. The subsequent deformation observed in the zircons might be a result of increased stress within the magma system after the recrystallization.

Mineralogy and geochemistry of multi-coloured sapphires at the Portezuelo de Pajas Blancas' deposits, northern Chile: revealing crystal growth processes

Portezuelo de Pajas Blancas' primary metasomatic deposits host sapphires that differ in size, colour, and colour distribution through different lithological units. The discovery of sapphire-bearing secondary aeolian placer deposits enabled a detailed analysis of sapphire types to determine the causes of this heterogeneity. Representative single sapphires from the primary and secondary deposits were analysed using various techniques, including SEM-CL, OM-CL, Micro-XRF, Raman spectroscopy, and polarised transmitted light multi-focus optical microscopy. Based on the results, seven sapphire types were identified according to their colours and colour distribution. Fe and Ti concentrations mainly contribute to the colour and micro-textures occurrence. The primary growth textures include cores, progressive, oscillatory, and diffusion zoning, whereas the secondary alteration features correspond to micro-brecciation, re-arrangement, and overgrowth. Inclusions such as euhedral andalusite, anhedral anhydrite, and anhedral rutile were identified in the sapphires. The formation of Portezuelo de Pajas Blancas sapphires can be divided into five genetic stages: (i) core growth development; (ii) chemical imbalance due to open system behaviour that produces progressive and oscillatory zoning; (iii) low-temperature deformations that produce micro-brecciation; (iv) re-arrangement of pre-formed sapphire fragments and subsequent sapphire overgrowth; (v) diffusion zoning that produce Fe- and Ti-enriched outer rims. In conclusion, the Portezuelo de Pajas Blancas' sapphires were formed through at least five stages of oxidised contact metasomatism at varying temperatures and low pressures, where a heterogeneous forming condition predominates during sapphire formation.Graphical

Plagioclase as archive of the incremental assembly of the Quxu batholith, South Tibet: Implication for the nature of magma reservoir

The formation of magma reservoir and resultant construction of large batholith are increasingly recognized as long-term incremental processes. Here we employed back-scattered electron and cathodoluminescence images, in-situ major and trace elements, and Sr isotopes of plagioclase for five lithological groups from the Quxu complex batholith (south Tibet), which shed new light on the nature and incremental construction processes of batholith. Our results show that plagioclases display diverse textures and show systematic differences in geochemistry and Sr isotopes for different lithologies, indicating that their host rocks originated from multiple magma sources and/or underwent distinct magmatic processes. Plagioclases in Group I granodiorites and Group III mafic dykes and mafic magmatic enclaves exhibit comparable textural features (e.g., resorption and sieved textures) and share similar Sr (< 1500 ppm) and Ba (< 200 ppm) contents, and 87Sr/86Sr ratios (ISr) (0.7035–0.7050) at given lower An (20–50) values, suggesting that they were evolved from similar mafic magma sources. The significant variations in An (20–90), Sr and Ba contents of plagioclase in Group III indicate both fractional crystallization and magma mixing. Plagioclases in Group II monzogranites have a similar An ranges to Group I but higher Sr (900–2200 ppm) contents and ISr (mostly 0.7045 to 0.7066) values, suggesting that they formed from partial melting of juvenile mafic crust without significant mantle contribution. Plagioclases in Group IV granodiorites and Group V monzogranites exhibit higher Sr (500–3000 ppm) contents than other groups at given An values. Their ISr values fall within the range of Group II, indicating a similar magma source. Abundant plagioclases displaying normal and oscillatory zonings in them implies that fractional crystallization occurred, while the presence of typical glomerocrysts in Group V indicates mush disaggregation. The simulation results of the trace elements indicate that the different lithologies of the Quxu batholith represent different states of magma reservoirs, corresponding to crystal mushes with varying degrees of extracted melts. The incremental growth processes of lager batholith operate as an open system, in which magma convection, mixing and recharge, crystal accumulation, recycling and reaction with melts, and mush disaggregation commonly occur.

Garnet zoning patterns record multiple processes of chemical transfer during subduction

Subduction is the principal mechanism by which volatiles are transferred from the Earth's surface to its interior. In garnets from eclogites and blueschists formed within the subduction setting, fine-scale, oscillatory elemental zoning is a common feature, sometimes considered to record open-system fluid exchange during prograde metamorphism. We present oxygen isotope data for garnets with such zoning from five exhumed subduction zone complexes. Short length scale fluctuations in elemental and oxygen isotope zoning (which are themselves spatially decoupled) cannot be linked to open-system fluid exchange during garnet crystallization in all samples; these data do not provide evidence for a genetic relationship between elemental oscillations and fluid fluxing. However, garnets from one setting do provide clear evidence for syn-growth ingress of elementally and isotopically buffering fluids, a process that operated simultaneously with the formation of elemental oscillations. Our findings indicate multiple mechanisms of chemical transfer operate at the grain–rock scale during subduction, and that some subduction zone rocks may experience only limited interaction with external prograde fluids. These results are consistent with a picture of highly heterogenous volatile transfer during subduction, and suggest that some proportion of the fluid inventory inherited at shallow depths may be transferred to sub-arc depths.

Modelling ancient magma plumbing systems through clinopyroxene populations: a case study from Middle Triassic volcanics (Dolomites, Italy)

Modelling plumbing systems dynamics of active volcanoes through textural and chemical studies of mineral phases is crucial to unravel their eruptive behaviour, but it is rarely applied in ancient volcanic and volcano-plutonic systems. Here, we present an investigation of the architecture, magma dynamics and pre-eruptive timing of Middle Triassic plumbing systems in the Dolomites area (Southern Alps) through a detailed investigation of textures and compositional zoning of clinopyroxenes in lavas and dykes from Predazzo, Mt. Monzoni, Cima Pape and Sciliar volcano-plutonic complexes. The clinopyroxene composition varies between low-Mg# (67–78), low-Cr augite and high-Mg# (77–91), Cr-rich diopside. Diopside is less frequent and appears as variably thick single or multiple bands between augitic cores and rims or as resorbed homogeneous, or patchy-zoned and mottled cores. Rims are homogeneous or oscillatory zoned, with augitic composition. The mid- to low-crustal plumbing systems of all volcanic centres were characterised by the presence of a mildly evolved trachyandesitic magma (Mg# 45; T = 1044–1118 °C), where augitic clinopyroxene formed. Periodic mafic injections of more primitive and hotter trachybasaltic magma (Mg# 56; T = 1056–1170 °C) caused frequent crystallisation of diopsidic bands around augitic cores. The presence of resorbed or patchy-zoned mottled diopsidic cores in clinopyroxene phenocrysts, as well as of rare clinopyroxenitic xenoliths with analogous diopsidic composition, indicates the recycling and remobilisation of antecrysts from the deeper part of the plumbing system, which was probably located at a depth of 10–17 km. Diffusion chronometry models based on Fe–Mg interdiffusion in clinopyroxene revealed that the time elapsed from the mafic injection into the shallow portion of the plumbing systems to the eruption ranges from decades to < 1 year. Our findings enabled us to resolve the different plumbing system dynamics acting at the local scale beneath each volcanic centre. Our data indicate a striking similarity with magma dynamics and timing of pre-eruptive processes at active volcanoes: therefore, we posit that this work sets a starting point to deepen our knowledge of the volcano-plutonic links and, in turn improves our ability to interpret the main processes acting in active plumbing systems.

Numerical Simulation of the Self‐Organizational Origin of Concentrically Zoned Aggregates of Siderite and Pyrite in Sediment‐Hosted Massive Sulfide Deposits

AbstractConcentrically zoned pyrite aggregates (CZPA) are common in sediment‐hosted massive sulfide (SHMS) deposits and have been widely used to interpret the ore‐forming processes. There is considerable uncertainty, however, over the formation of aggregates that are oscillatorily zoned and contain randomly‐orientated pyrite microcrystals. Guided by the results of examination of the micro‐textures of CZPA and in‐situ chemical analyses, we conducted a quantitative diffusion‐reaction simulation to assess the mechanism of CZPA formation. Our study shows that oscillatory zoning results from the feedback between the diffusion of reactants and the nucleation‐growth of Fe‐sulfides. Externally derived Fe2+ diffuses into the early diagenetic sediments containing decomposing organic matter (2CH2O + SO42− = 2HCO3− + H2S) and reacts with H2S to form a pyrite layer via an intermediate pathway (Fe2+ + H2S → FeS + 2H+, FeS + H2S → FeS2 + H2). This growth of pyrite layers depletes the local concentration of reactants and suppresses nucleation until the diffusive reaction front advances and another layer is formed. Intermediate phases, for example, mackinawite, nucleate instead of pyrite, because of their greater ease of nucleation due to the low surface tension, and lead to the domination of nucleation over growth. The nucleation of mackinawite and occurrence of siderite in the CZPA are consistent with a low temperature, high pH, anoxic early diagenetic environment. Our study demonstrates that CZPA in SHMS deposits are formed by intrinsic self‐organizational processes rather than by extrinsic changes of ore‐forming fluids. The CZPA in SHMS deposits are thus indicative of their diagenetic origin with Fe2+ infiltrated and diffused from hydrothermal fluids into the sediments.

Tungsten mineralization in the Huangjindong gold deposit, southern China: Insights from scheelite texture, in-situ trace elements and Sr isotope compositions

Scheelite and wolframite are two primary tungsten minerals in nature. The occurrence of tungsten minerals varies in different types of deposits, with scheelite rather than wolframite typically forming in orogenic gold deposits. However, the explanation for this phenomenon remains unclear. Huangjindong deposit, located in the center of the Jiangnan Orogenic Belt in southern China, is a typical orogenic gold deposit with scheelite mineralization. Texture, in-situ trace elements and Sr isotope compositions of scheelite from this deposit were investigated to explore the formation process of scheelite and the source of tungsten of similar orogenic gold deposits.Three hydrothermal stages have been identified at this deposit: milky scheelite + quartz (pre-gold Stage I); gold + sericite + sulfide + quartz (syn-gold Stage II); and dolomite + quartz (post-gold Stage III). Scheelite primarily occurs during the initial pre-gold stage. Local color differences in CL image have developed along rims and in domains adjacent to fractures of scheelite due to slight late-stage hydrothermal alteration of scheelite along their fractures. The intense development of sericite and chlorite alteration in the host rocks indicates that the water–rock reaction consumed a large amount of H+. Within the scheelite-quartz veins, the presence of brecciated slate enclaves and localized quartz geodes, indicating that the fluid experienced significant pressure drop. This indicates that the water–rock reaction and the decrease in pressure resulted in the precipitation of scheelite. The dominance of tungsten mineral precipitation due to pressure reduction serves as the main factor driving the development of scheelite over wolframite within the deposit, which also elucidates the reason that tungsten mineralization associated with orogenic gold deposits predominantly features scheelite. The characteristics of scheelite without oscillatory zoning, high Sr (1180–8600 ppm) and low Mo (bdl-0.18 ppm) concentrations, and flat REE pattern are similar to those of scheelite in orogenic gold deposits worldwide. The high 87Sr/86Sr ratio (0.7539–0.7663) indicates that the tungsten-bearing ore-forming fluids derived from deep-seated metamorphic fluids.

Bridging the Gap in Garnet Diffusion Models at Low Temperatures: Recalibration Using Western Tianshan Eclogitic Breccia

Abstract Models concerning the diffusion of divalent cations (Ca2+, Mg2+, Fe2+, and Mn2+) in garnet have been subject to extensive research and application over several decades, yet discrepancies among available models persist. Particularly the diffusion rate of Mn2+, which is the fastest in garnet, varies by more than two orders of magnitude for garnets in eclogite. In this study, we use an eclogitic breccia sample from the Western Tianshan (ultra-) high-pressure metamorphic belt for calibration. The thermobarometry indicates that the sample experienced exhumation from ~2.45 GPa, ~480°C to 1.85 GPa, ~515°C. Previous geochronological constraints estimate the exhumation duration to be a couple of million years to up to 15–20 Myr, with an average slab exhumation rate of ~3.5 mm/year. Although the estimates entail significant uncertainties, this range is still smaller than the discrepancy of Mn diffusion rate predicted among diffusion models. Thus, this natural sample provides valuable insights for calibrating the available diffusion models. Our analysis of garnet compositional profiles demonstrates that the diffusion rates (Di) at the pressure and temperature of interest are DCa:DFe:DMg:DMn = 0.2:0.4:1:2.4. By integrating garnet profiles, pressure–temperature–time information, and existing experimental data, we refine each diffusion model for Mn2+, thereby reducing the uncertainties associated with down-temperature extrapolation. Application of the newly calibrated models indicates that the oscillatory zoning of Mn2+ at the garnet rim is best described by a brief thermal excursion (~0.4 Myr, &amp;gt;20°C) at ~1.9 GPa. This minor thermal pulse punctuating the general exhumation path could be indicative of shear heating between nappes or momentary involvement in the mantle wedge, suggesting stacking or partial reactivation of the thrusts during exhumation.

A possibility of Klein paradox in quaternionic (3 + 1) frame

In light of the significance of non-commutative quaternionic algebra in modern physics, this study proposes the existence of the Klein paradox in the quaternionic (3+1)-dimensional space-time structure. By introducing quaternionic wave function, we rewrite the Klein–Gordon equation in extended quaternionic form that includes scalar and the vector fields. Because quaternionic fields are non-commutative, the quaternionic Klein–Gordon equation provides three separate sets of the probability density and probability current density of relativistic particles. We explore the significance of these probability densities by determining the reflection and transmission coefficients for the quaternionic relativistic step potential. Furthermore, we also discuss the quaternionic version of the oscillatory, tunnelling, and Klein zones for the quaternionic step potential. The Klein paradox occurs only in the Klein zone when the impacted particle’s kinetic energy is less than [Formula: see text]. Therefore, it is emphasized that for the quaternionic Klein paradox, the quaternionic reflection coefficient becomes exclusively higher than value one while the quaternionic transmission coefficient becomes lower than zero.

Polymetallic tungsten skarn mineralisation related to the Periadriatic intrusion at Lienzer Schlossberg, East Tyrol, Austria

Abstract A regional tungsten anomaly was discovered and explored in the Lienzer Schlossberg area that is part of the crystalline Austroalpine nappe complex of the Eastern Alps in the 1970/80-ties. Tungsten is present as scheelite, which occurs in steeply SSW dipping WNW-ENE oriented quartz veinlets and joints within the porphyritic dioritic to tonalitic/granodioritic host rocks of the Oligocene Lienz/Edenwald intrusion and in the exoskarn, which developed at the contact of the intrusion with Ca-rich lithologies. The skarn system is characterised by two stages: (1) a primary high-temperature calc-silicate stage characterised by grossular, diopside-hedenbergite, vesuvianite, wollastonite and Ca-plagioclase and (2) a retrograde skarn stage including scheelite-bearing massive sulphide ores (pyrrhotite, chalcopyrite, tremolite-actinolite, diopside-hedenbergite) and scheelite-rich fault rocks with calcite, sericite and chlorite. The two ore stages, the mineral paragenesis and composition is like that of a reduced tungsten skarn; i.e., garnet is grossular-rich, clinopyroxene is diopside-hedenbergite. Vesuvianite contains up to 1.8 mass % fluorine. Scheelite has been studied by cathodoluminescence (CL), electron probe microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. Three types of scheelite (Scheelite 1–3) are distinguished. In short-wave UV light, all types show blue fluorescence but CL revealed internal micro-textures in scheelite grains which are dominated by oscillatory zoning. Prolonged hydrothermal activity is indicated by dissolution-replacement and overgrowth textures affecting the primary zonation and trace element composition of scheelite. The distribution of rare earth elements (REE) in Scheelite 1 in tonalite-hosted quartz veinlets shows a convex (i.e., middle REE-enriched), heavy REE-depleted pattern with negative Eu anomalies (EuA ). The evolution of REE patterns from skarn-hosted Scheelite 2 and 3 illustrates a gradation of convex REE patterns with high ΣREE and distinct negative Eu anomalies to relatively flat REE patterns with small to no EuA . Scheelite at Lienzer Schlossberg has one of the highest ΣREE+Y contents of all scheelite-bearing ore settings in the Eastern Alps but incorporates minor Mo and the least Sr. High Na and Nb contents together with the positive correlation of REE+Y vs. Na+Nb+Ta suggests that the main exchange vectors for REE incorporation in scheelite is via a combined coupled substitution mechanism. Results of this study confirm the genetic similarity with reduced tungsten skarns and highlight the tungsten potential of this area.