Chondrite-normalized Rare Earth Element Research Articles

Geochemistry of hydrothermal illitizations in Eocene Kösedağ magmatic rocks, Zara-Suşehri area, NE Sivas, East-Central Anatolia: Origin and age of alteration

The study area located at the periphery of the collision zone between the Eurasian plate (i.e. Pontides) and Tauride-Anatolide platform, NE of Sivas in the east-central Turkey, which is part of the Tethyan Metallogenic Belt. Mixed-layer illite-smectite (IS) and illite minerals are derived within the hydrothermal alteration zones with a few km2 surface areas (up to 30 km2) in Eocene volcanic and plutonic rocks. The representative IS and illite samples taken from plutonic- and volcanic-hosted alteration zones are investigated by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), major and trace elements and OH isotope geochemistry and KAr dating methods. Different types of hydrothermal alterations, such as propylitic and phyllic alteration in the plutonic rocks and argillic alteration in the volcanic rocks were developed as a result of intrusion of Kösedağ Pluton (syenite) into Karataş Volcanics (basaltic trachy-andesite and trachyte) with relations of hot-hot contact. The main phyllosilicate/clay minerals are characterized by kaolinite and IS in volcanic-hosted argillic alteration zones, whereas IS and illite in plutonic-hosted phyllic zones. The ordering types (Reichweite) of IS and illites are represented by R1 IS (I = 65–80 % in IS) + R3 IS (I = 90 % in IS) in the volcanic-hosted rocks, and R3 IS (I = 90 % in IS) and illite (S = 3–5 %). Dioctahedral (d060 ≤ 1.500 Å) R3 IS and illites have 1 Md + 1 M and 1 Md + 1 M + 2 M1 polytypes, respectively. The major and trace elements such as TiO2, Fe2O3, MgO, Na2O, P2O5, Sc, V, Cu, Ge, Sr, Hf, Zr and Y increase in the volcanic-hosted IS, whereas SiO2, Al2O3, K2O, Pb, W, Mo, As, Sb, Rb and U in the plutonic-hosted IS and illites. The chondrite-normalized distributions of IS and illites present a great similarity to those of host rocks. The chondrite-normalized rare earth element (REE) concentrations are more enriched in the volcanic-hosted IS in comparison with the plutonic-hosted IS and illites having distinctive Eu negative anomaly, which indicate deriving from volcanic matrix and K-feldspar, respectively. Oxygen and hydrogen isotope data of illitic clays indicate that the hydrothermal fluids are originated from magmatic water. According to stable isotopes and fluid inclusion data, IS and illites were formed at the temperature conditions ~150 °C in volcanic-hosted argillic zone, whereas ~250 °C in plutonic-hosted phyllic zones. KAr dating of alunite, IS and illite minerals indicate that the hydrothermal alteration was started at 40.45 ± 1.28 Ma, almost 2 Ma after the Q-syenite intrusion, within the plutonic body as phyllic alteration stage, and continued up to 35.27 ± 2.81 Ma, with a duration of ~5 Ma, and finalized before the exhumation of the Kösedağ Pluton (28–30 Ma). The geochemical characteristics of IS and illites were controlled by host-rock, condition, origin, and ages of alterations and they can be used as an important tool for magmatic-hydrothermal systems.

Metallogenic Difference between the Late Aptian Nansu and Aishan Pluton in Jiaodong: Constraints from in Situ Apatite Elemental and Nd Isotopic Composition

A series of Mo-polymetallic deposits have been developed in the Jiaodong Peninsula. Notably, these Mo-dominant deposits formed essentially during the same period as the well-known world-class Au deposits in this area, hinting at a potentially unique geological correlation between them. Therefore, conducting thorough research on Mo deposits in Jiaodong holds significant importance in exploring the area’s controlling factors of Mesozoic metal endowments. To reveal the petrogenesis and metallogenic potentials of Mo-fertile and ore-barren granitoid, apatite grains from the Late Aptian Nansu granodiorite and Aishan monzogranite are investigated in this study. Detailed petrographical observations, combined with in situ analysis of electron probe micro-analyzer (EPMA) and Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), have been conducted on apatite grains from the Nansu and Aishan plutons. This comprehensive analysis, encompassing both major and trace elements as well as isotopic characteristics of apatite, aims to elucidate the metallogenic differences within the late Early Cretaceous granitoids of Jiaodong. The results reveal that the apatite grains across all samples belong to fluorapatites, suggesting their magmatic origin. Additionally, chondrite-normalized rare earth element (REE) patterns of apatites in ore-fertile and ore-barren granitoids exhibit a “right-leaning” trend, characterized by relative enrichments in light REEs and depletions in heavy REEs. Both the Nansu and Aishan plutons exhibit moderately negative Eu anomalies (with averages δEu values of 0.44 and 0.51, respectively), along with slightly positive Ce anomalies (averaging δCe values of 1.08 and 1.11, respectively). A negative correlation is observed between their δEu and δCe values, indicating that the parental magmas of ore-fertile and ore-barren granitoids were formed in a relatively oxidizing environment. The calculated apatite OH contents for the Nansu pluton range from 0.26 to 1.38, while those for the Aishan pluton vary between 0.24 and 1.51, indicating comparable melt H2O abundances. Consequently, the results suggest that neither the oxygen fugacities nor the water contents of the parental magma can account for the metallogenic differences between Nansu and Aishan plutons. The apatite in the Nansu pluton exhibits a higher Ce/Pb ratio and a relatively lower Th/U ratio, indicating the involvement of a greater volume of fluids in the magmatic evolution process of this ore-bearing granitoid. Apatite grains sourced from the Nansu and Aishan plutons exhibit εNd(t) values ranging from −16.63 to −17.61 (t = 115.7 Ma) and −17.86 to −20.86 (t = 116.8 Ma), respectively. These results suggest that their parental magmas primarily originated from the partial melting of Precambrian metamorphic basement rocks within the North China Craton, with a minor contribution from mantle-derived materials. Additionally, the presence of mafic microgranular enclaves in both the Nansu and Aishan plutons indicates that both have undergone magma mixing processes. The binary diagrams plotting the ratios of Ba/Th, Sr/Th, and U/Th against La/Sm demonstrate that apatite grains of ore-fertile granitoid exhibit a distinct trend towards sediment melting. This suggests the potential incorporation of sedimentary materials, particularly those rich in molybdenum, into the magmatic source of the Nansu pluton, ultimately leading to the occurrence of molybdenum mineralization.

Petrogenesis and Geodynamic Implications of Cretaceous Nb-Enriched Mafic Dykes in the East Kunlun Orogen, Northern Tibet Plateau: Constraints from Geochronology, Geochemistry and Sr-Nd Isotopes

There is a magmatic lull period in the East Kunlun orogen (EKO) during the Jurassic to the Cretaceous. However, due to the lack of records of magmatic activity restricts our understanding of the late Mesozoic magmatic-tectonic evolution of the EKO. Herein, an integrated study of geochronology, whole-rock geochemistry and Sr-Nd isotopes were conducted for the Cretaceous mafic dykes in the EKO, Northern Tibet Plateau, to reveal their petrogenesis and geodynamic implications. LA-ICP-MS Zircon U-Pb dating reveals that the studied mafic dykes comprising diabase and diabase porphyry emplaced at ca. 80.9 ± 0.8 Ma. The Cretaceous mafic dykes have low contents of SiO2 (46.36 wt.%~47.40 wt.%) but high contents of MgO (6.79 wt.%~7.38 wt.%), TiO2 (1.91 wt.%~2.13 wt.%), Nb (12.4~18.3 ppm) and Nb/U ratio (31~39), resembling Nb-enriched mafic dykes. They exhibit chondrite-normalized rare earth element (REE) and primitive mantle-normalized trace element patterns, remarkably similar but not identical to the oceanic island basalts (OIB). The moderate REE fractionation ((La/Yb)N = 3.55~5.37), weak negative Eu anomalies (δEu = 0.87~0.97) and relative enrichment of Rb, Ba, K, as well as high contents of Cr and Ni and slightly depleted Sr-Nd isotopes (εNd(t) = −0.18~1.33), suggest that the studied dykes originate from a partial melting of spinel lherzolite and a little of garnet which was previously modified by subducted sediments. Combined with other evidence, we propose that the studied Cretaceous Nb-enriched mafic dykes in the Northern Tibet Plateau were formed in the intraplate setting, which may be a partial melting of the enriched mantle in the lower lithosphere caused by the activity of the East Kunlun strike-slip fault.

Origin of calcite cements in the Permian Lucaogou Formation tight reservoirs, Jimsar sag, Junggar basin, NW China: Constraints from geochemistry

Understanding the diagenetic evolution of carbonate cementation in hydrocarbon reservoirs is critical to better reconstruct the history of fluid flow during petroleum accumulation. The extensive occurrence of carbonate cements within the lower Permian Lucaogou Formation tight reservoirs is regarded as a major diagenetic factor that causes strong hydrocarbon reservoir heterogeneities. Petrographic and geochemical analyses, including optical microscopy fitted with cathodoluminescence, scanning electron microscopy, carbon and oxygen stable isotopes, in situ rare earth element, as well as fluid inclusion microthermometry, were carried out to decipher the origin of calcite cementation and understand its control on reservoirs quality. Petrography shows that the precipitating cements mostly consist of pore-filling blocky/mosaic calcite, with a dull orange luminescence color. Chondrite-normalized rare earth element (REE) patterns and C–O isotopic compositions of these calcite cements exhibit strongly negative Eu and Tb anomalies, enrichment in light REE, positive carbon (δ13CPDB = 0.58‰–7.45‰) and negative oxygen (δ18OPDB = −11.38‰ to −8.61‰) isotopic values, similar to the dolostone and micritized peloidal grains, suggesting that the calcite-precipitating fluids were derived from dissolution of lacustrine depositional carbonates. The relative timing of calcite precipitation in reservoirs was constrained based on the thermal-burial history of the study region and precipitation temperatures obtained from fluid inclusions. The results show that this cementation episode mainly occurred during the Late Triassic to Early Jurassic, which was synchronous with the tectonic uplift event. Moreover, homogenization temperatures of fluid inclusions and geochemical signatures of the calcite cement are similar to those of the fracture-fillings, suggesting that these two calcite phases may be genetically related and form coevally within one fluid flow system. It can be interpreted as a response to the compressional tectonic deformation given by the collision of the Qiangtang Block with the Eurasia Plate. This tectonic deformation event is regarded as the driver for calcite precipitation during the early burial stage, resulting in a considerable reduction of reservoir quality. Calcite cementation is pervasive and may play a main role in halting hydrocarbon migration through some of the permeable pathways in reservoirs.

Tonian rifting coeval with the last stages of amalgamation of Rodinia: Evidence from southern Borborema province, northeastern Brazil

During the last stages of assembly of the Rodinia supercontinent at 1000-900 Ma, rifting processes were occurring in places that would be part of Gondwana in the late Neoproterozoic. In the Borborema Province, northeastern Brazil, this event is known as Cariris Velhos. It is represented in the Alto-Pajeú Domain from the Central subprovince by a 700 km-long, 70 km-wide NE-SW belt comprising bimodal metavolcanic rocks and granitic orthogneisses. Orthogneisses with similar ages were found in previous works in the western Pernambuco-Alagoas Domain from the Southern subprovince immediately to the south of the ESE-trending dextral West Pernambuco shear zone. The Airi Complex comprises several elongate bodies that extend for at least 80 km. It consists of a bimodal sequence of metafelsic (granitic orthogneisses) associated with layers and enclaves of metamafic (amphibolites) rocks. Seven orthogneiss samples dated by LA-ICPMS yielded zircon U–Pb crystallization ages of 950–1011 Ma. Zircon Hf analyses from two samples yielded εHf(t) values ranging from −1.4 to 2.1 and TDM model ages of 1.7–1.9 Ga. Geochemical analyses allow to distinct different source rocks for the protoliths of the orthogneisses. Orthogneisses derived from metasedimentary sources have modal muscovite ± garnet, are ferroan, alkali-calcic and predominantly peraluminous, exhibiting strong negative Eu anomalies in chondrite-normalized rare earth elements diagrams. Orthogneisses derived from high-K mafic rocks are calc-alkalic, slightly peraluminous, with small or absent negative Eu anomalies. Orthogneisses from tonalitic sources are magnesian, calc-alkalic to alkali-calcic, and slightly peraluminous, without Eu anomalies. There is no correlation between crystallization ages and source rock types. The results indicate that the Airi Complex originated through partial melting of ancient heterogenous crustal sources. Therefore, its geochemistry reflects the nature of these sources, not the tectonic setting of intrusion. Emplacement of the complex was broadly coeval with well-documented extensional processes in the São Francisco/Congo Craton and represents a failed attempt to break-up a larger paleocontinent encompassing this craton and the basement of the Borborema Province.

Geochronology, geochemistry, and tectonic setting of Ordovician metavolcanic rocks in the Liberty–Orrington belt, Maine: implications for the evolution of peri-Gondwanan arcs in the northern Appalachians

The Yarmouth Island Formation of the East Harpswell Group (EHG) is an assemblage of metamorphosed volcanic and sedimentary rocks exposed in Casco Bay, Maine. Although previously interpreted to have been deposited ca. 445 Ma, two new U–Pb zircon ages from metavolcanic rocks in the unit indicate prolonged magmatism between ca. 469–474 Ma and correlation with adjacent rocks of the more regionally extensive Casco Bay Group (CBG) in the Liberty–Orrington belt. New detrital zircon results from metasedimentary rocks in the EHG support this correlation; the age spectra indicate a peri-Gondwanan sedimentary source, consistent with earlier published results from the CBG. Detailed geochemical studies of the metavolcanic rocks in the Yarmouth Island Formation indicate a wide range of sub-alkaline compositions (SiO2 = 47.9–77.5 wt.%), flat chondrite-normalized rare earth element distributions, and a prominent negative Nb anomaly in normalized spider plots. Tectonic discrimination plots suggest eruption in a volcanic arc setting with continental crustal influence. This tectonic setting, when combined with the co-existence of marine sedimentary rocks, suggests a transitional setting between that of subduction and subsidence in a marine setting, perhaps due to the onset of back-arc rifting. Similarities in age, lithologic character, sediment provenance, and volcanic rock geochemistry indicate a strong correlation between these rocks in the Liberty–Orrington belt and those along strike in the southern portion of the Miramichi belt of eastern Maine and southern New Brunswick. These findings confirm the preservation of >500 km long, ca. 470 Ma, arc/back-arc terrane within the Ganderia superterrane in the northern Appalachians.

Unraveling the early Paleozoic tectonic history of the South Qinling Belt: Evidence from geochronology, geochemistry, and Sm-Nd isotopes of meta-sedimentary rocks

The determination of the petrogenesis and age of meta-sedimentary rocks plays a crucial role in enhancing our understanding of regional tectonic evolution. In this study, we conducted comprehensive geochemical, zircon U-Pb, and Sm-Nd isotope dating analyses of the biotite gneiss of the Changjiaoba group to investigate the tectonic evolution of the South Qinling belt. The age range of detrital zircons from the biotite gneiss was estimated to be 446–2798 Ma, with prominent peaks observed at approximately 454, 660, 790, 1998, and 2770 Ma. The earliest data indicate that the final sedimentary age of the Changjiaoba group corresponds to the late Ordovician. The protoliths of the biotite gneiss were argillaceous rocks, classified as parametamorphic rock. The chondrite-normalized rare earth element (REE) diagram exhibited right-inclined patterns with negative Eu anomalies. The upper continental crust (UCC)-normalized trace element patterns exhibited insignificant enrichment of Ba, Sr, and K; negative anomalies of Hf, Th, U, and Ti; and depletion of Cr and Ni. Geochemical indicators suggest that the precursor sediments are felsic rocks that have undergone moderate weathering. The εNd (t) values of the biotite gneiss (−10.2 to −3.4) suggest a mixture of a few juvenile crust components and abundant ancient material, indicating an arc-realted setting. Collectively, our findings suggest that the primary material sources of the Changjiaoba group were predominantly the North Qinling belt during the Paleozoic and the Yangtze block during the Neoproterozoic. The tectonic setting discrimination diagrams imply that the biotite gneiss were formed in an active continental margin environment, supporting the notion of the northward oceanic subduction during the early Paleozoic. In conclusion, our study provides valuable insights into the composition and deposition history of the Changjiaoba group in the South Qinling belt, contributing to our understanding of the regional geology.

Geochemistry and zircon U–Pb dating of amphibolite in the Menderes Massif (western Türkiye): first record of Late Devonian extension

ABSTRACT The timing of extensional events in northern Gondwana remains elusive. In relations to this event, a new zircon U-Pb age and Hf isotopic compositions, and whole-rock geochemistry provided here for the amphibolites in the basement unit of the Menderes Massif (MM) within the Anatolide-Tauride Block (ATB). LA-ICP-MS U-Pb zircon dating of one sample yielded a crystallization age of 367.0 ± 2.5 Ma, providing the first record of Late Devonian (Famennian) mafic magmatism in the Menderes Massif. This sample contains inherited zircon grains with ages spanning from 588 Ma to 541 Ma, likely sourced from late Neoproterozoic country rocks. Chondrite-normalized rare earth element patterns exhibit enrichment in light rare earth elements and flat patterns for heavy rare earth elements, suggesting affinities with tholeiitic EMORB and ocean island basalt. The geochemical data, coupled with the positive εHf(t) values ranging from 0.5 to 7.8, indicate that the amphibolite likely originated from juvenile melts generated by partial melting of the asthenospheric mantle. This melt was subsequently modified by crustal contamination and fractional crystallization. Contemporaneous EMORB- and OIB-like mafic rocks are identified in the eastern Taurides and Iran, respectively. Both regional geological and geochemical evidence proposes that Late Devonian magmatism in the Anatolide-Tauride Block occurred in a within-plate tectonic setting. This magmatic activity might have been triggered by the northward subduction of the Paleotethys beneath the Pontides during the Devonian, a process that would produce a slab-pull force, creating an extensional tectonic regime along the northern margin of Gondwana.

Exploring the CAM18 Crystal as a Potential Reference Material for U–Pb Analysis of Zircon

In the process of in situ zircon U–Pb dating, it is an effective means to overcome the matrix effect by using a matrix-matched external reference material. However, the limited number of available zircon reference materials still makes it difficult to meet the research needs. In this paper, we performed a preliminary analysis of the gemological characteristics, trace elements and U–Pb ages of natural zircon CAM18 to assess its suitability as a reference material for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U–Pb dating. This tawny, gem-quality zircon has no visible inclusions and weighs approximately 0.55 g. Its density, full width at half maximum (FWHM) of the Raman peak and alpha flux (Dα) indicate that the sample has suffered mild-to-moderate radiation damage without any thermal treatment. The LA-ICP-MS U–Pb dating results reveal that the trace elements content and U–Pb ages of the sample are fairly homogeneous at the 50 μm scale, and there is no obvious loss of radiogenic Pb. The 206Pb/238U age (571.0 ± 3.0 Ma, 2s) and 207Pb/235U age (573.4 ± 6.0 Ma, 2s) are consistent within the analytical uncertainty, and the calculated concordia age is 571.4 ± 1.4 Ma (2s, n = 20). The variation in the 206Pb/238U ages is small, with a measurement repeatability of 0.46% (RSD), which is within the uncertainty of the age accuracy obtained by LA-ICP-MS. The oscillatory zoning, Th/U ratio (0.2) and chondrite-normalized rare-earth element (REE) pattern imply a magmatic origin of zircon CAM18. The Ti-in-zircon temperature ranges from 714 to 742 °C, and the oxygen fugacity ranges from ΔFMQ−2.87 to ΔFMQ−3.17, suggesting that it is crystallized in a reducing environment. All the results show that zircon CAM18 may has great potential in LA-ICP-MS U–Pb dating.

Trace element compositions and geochronology of cassiterite from the Bushveld Large Igneous Province, South Africa

This study presents trace element compositions and ages of four representative cassiterite samples from the Zaaiplaats, Union and Rooiberg Sn fields, all spatially associated with the Bushveld Large Igneous Province (LIP), South Africa. The Zaaiplaats Sn field is endogranitic and entirely hosted within the variably-altered Bobbejaankop and Lease granites of the Lebowa Granite Suite. In contrast, the exogranitic Union and Rooiberg Sn fields occur within the Union Tin Member of the Rooiberg Group, and the Pretoria Group of the Transvaal Supergroup, respectively. Collectively, all the cassiterite samples display quasi-parallel chondrite-normalised rare earth element (REE) patterns characterised by relative enrichments in the heavy REE, and yielded ages varying within a relatively restricted interval between 2061 ± 40 Ma and 2054 ± 3 Ma. This age range compares well with those reported from the Bushveld LIP and, when combined with mineral compositions, suggests a common granitic source for cassiterites from all the Sn fields. The exogranitic Rooiberg and Union Sn fields are identified by cassiterites with Zr/Hf of ∼40, whereas the endogranitic Zaaiplaats Sn field is characterised by cassiterites enriched in most incompatible elements (e.g., Nb, Ta, Zr, Hf, In, F and B) and Zr/Hf of ∼10. These Zr/Hf ratios agree with the endogranitic and exogranitic Sn ores from other localities, but are different from the very low Zr/Hf ratios of ∼3 reported for endogranitic cassiterites associated with rare-metal granites. The Zr versus Hf discrimination diagram may therefore be useful for distinguishing the endogranitic and exogranitic origins of cassiterites and for identifying the extent of fractionation of the causative source.

Origin and tectonic setting of Cretaceous ophiolites in the Gaoligong tectonic belt, SW China: Implications for the tectonic evolution of the Bangonghu–Nujiang Meso–Tethys

Whether the ophiolites in the southeast margin of the Gaoligong tectonic belt are related to subduction or rift is hotly debated. The aim of this paper is to present the geological and geochemical data of these ophiolitic blocks in order to understand the significance of these in the tectonic evolution of the Meso–Tethys. The peridotites in the ophiolites are dominantly harzburgites with high Mg# (88.7–92.2) and low Al2O3 (<0.8 wt.%) and CaO (<0.5 wt.%) contents, and display U-shape chondrite-normalized rare-earth element patterns. However, they show two different groups of mineral chemistries and occurrences. Group I are with olivine Fo 90.6–92.3, orthopyroxene Mg# 91.0–92.6, clinopyroxene Mg# 91.1–93.3, and spinel Cr# 42.1–67.4 and Mg# 62.8–71.6. They exhumed adiabatically and were intruded by mafic dikes from the melts through low-degree melting of asthenospheric mantles and by orthopyroxenites in the Early Jurassic. Group II are with olivine Fo 89.8–95.3, orthopyroxene Mg# 91.3–94.6, and spinel Cr# 62.4–94.1 and Mg# 19.5–51.0. They underwent brittle deformation and medium- to low-temperature fluid replacement. The two group’s peridotites have experienced the similar partial melting degrees and are the fragments of subcontinental lithospheric mantles. Extensive continental affinity tholeiites erupted in the Middle Jurassic, coeval with the primary spreading time of the Bangonghu–Nujiang Ocean in the central Tibet. The peridotites, mafic rocks, and marine-facies sediments represent the opening products of the Meso–Tethys in the Jurassic as ophiolites in a continental margin.

Geochemistry and formation of agate-bearing lithophysae in Lower Permian volcanics of the NW-Saxonian Basin (Germany)

Geochemical and mineralogical investigations of the Lower Permian Kemmlitz rhyolite within the NW-Saxonian Basin (Germany) and associated lithophysae (high-temperature crystallization domains) as well as agates were carried out to constrain the genesis and characteristics of these volcanic rocks and the origin of the agate-bearing lithophysae. The volcanic rocks of rhyolitic composition are dominated by quartz, sanidine, and orthoclase and most likely derive from lava flows. Agate-bearing lithophysae were exclusively formed in a glassy facies (pitchstone) of the rhyolites, which was afterwards altered to illite-smectite mixed-layer clays. The results of this study show that agate formation can be related to the alteration of the volcanic rocks accompanied by the infill of mobilized silica into cavities of lithophysae. Fluid inclusion studies point to temperatures of agate formation above 150 °C, indicating that the mobilization and accumulation of silica started already during a late phase of or soon after the volcanic activities. Remarkable high concentrations of B (29 ppm), Ge (> 18 ppm), and U (> 19 ppm) as well as chondrite-normalized rare earth element (REE) distribution patterns of the agates with pronounced negative Eu-anomalies, slightly positive Ce-anomalies and enriched heavy rare earth elements (HREE) indicate interactions of the host rocks and transport of SiO2 with magmatic volatiles (F/Cl, CO2) and heated meteoric water. Characteristic yellow cathodoluminescence (CL), heterogeneous internal textures as well as high defect density of micro- and macrocrystalline quartz detected by electron paramagnetic resonance (EPR) spectroscopy point to crystallization processes via an amorphous silica precursor under non-equilibrium conditions.

Robust dating of Pb–Zn skarn systems by LA–ICP–MS garnet U–Pb geochronology

Lawu and Yaguila are two Pb–Zn skarn deposits in the eastern Nyainqêntanglha metallogenic belt, central Lhasa subterrane, Tibet. The genesis of Pb–Zn deposits in this belt and the crustal processes leading to their formation remain ill-constrained, mostly because of the lack of precise mineralization ages. We integrate textural information, geochemistry, and in-situ garnet U–Pb geochronology to constrain the timing and genesis of Pb–Zn mineralization. Garnets from the two deposits display oscillatory compositional zoning (And14Gr86 to And100) and contain variable U contents (0.07–5.3 ppm). Aluminum-rich garnet displays a chondrite-normalized rare earth element (REE) fractionation pattern in which LREEs are depleted relative to flattish HREE segments. In contrast, Fe-rich garnet shows LREE-enriched, relatively HREE-poor patterns with positive Eu-anomalies. Uranium concentration is correlated with total REE and Fe components in garnets, implying that U incorporation is largely controlled by coupled substitution mechanisms. The same garnets also contain measurable contents of other metals (up to hundreds of ppm), such as Sn, W, and In. The distribution and fractionation of major and trace elements in zoned garnets record periodic fluid pluses with different compositions during hydraulic fracturing. The new garnet U–Pb data show that the Yaguila deposit formed between 68.5 ± 3.4 and 65.0 ± 4.7 Ma, and the Lawu deposit formed at 54.6 ± 2.9 Ma. Within the geochronological framework of igneous rocks and Pb–Zn mineralization in the Nyainqêntanglha metallogenic belt, the new garnet ages suggest a magmatic-hydrothermal origin for related mineralization, with the causative magma likely derived from partial melting of ancient continental material due to rollback and subsequent breakoff of the Neo-Tethys oceanic slab during India–Asia continental collision. This study highlights the opportunities offered by garnet U–Pb dating for elucidating the formation age and ore genesis of base metal skarn systems.

Geochemistry and mineralogy of the Upper Ordovician Wufeng formation, Southwestern China: Implications for Paleoclimate construction

Wufeng Formation shale is an important source rock of unconventional hydrocarbons in the Lower Paleozoic shales of Sichuan Basin. However, the study on its provenance and paleoclimate is still relatively limited. In this study, mineralogical and geochemical data of the shales from the Upper Ordovician Wufeng Formation in southwestern China has been used to interpret the provenance and conditions of weathering and paleoclimate. The Wufeng shales have intermediate to high SiO2 (57.72–82.38 wt. %, av. = 68.84 wt. %) and Al2O3 (5.26–16.17 wt. %, av. = 10.62 wt. %), are rich in transition metal elements (i.e. V, Ni, Cu, Co and Cr) and Y as well as moderate depletion in Na2O and Sr, relative to the concentrations of the upper continental crust (UCC). In the chondrite-normalized (CN) rare earth elements (REE) distributions, these rocks display light REE (LREE) enrichment (La/YbCN = 6.69–12.63, av. = 9.28), flat heavy REE (HREE) (Gd/YbCN = 1.35–2.41, av. = 1.70), and clearly negative Eu anomalies (Euan = 0.50–0.66, av. = 0.58), showing similar characteristics with the CN post-Archean Australian Average Shales (PAAS). Wufeng Formation shales are immature composition without evident recycling sediments, and they are originated from an intermediate-felsic igneous source composed of tonalite–trondhjemite–granodiorite (TTG), granitic and andesitic igneous rocks. The chemical weathering conditions of studied shales decreased from moderate to low in the provenance region, suggesting a gradual cooling trend of the climate at Late Ordovician Thus, this article will be helpful to discern the provenance and variations of chemical weathering conditions and paleoclimate of Wufeng Formation shales.

Possible partial melting and production of felsic melt in a Jurassic oceanic plateau of the Izanagi Plate: Insights from 159 Ma plagiogranites from northern Japan

ABSTRACT A small tonalite – dacite body has been discovered in the Nakanogawa Group, Hidaka Belt, northern Japan, which is a Palaeogene subduction complex formed in the palaeo-Japan trench along the northeastern margin of Eurasia. The tonalites are characterized by extremely low K2O (0.2–0.3 wt.%) and relatively flat chondrite-normalized rare earth element patterns (La/Yb[N] ~2.3), similar to plagiogranites in ophiolites. The major-and trace-element characteristics are consistent with low-pressure partial melting of oceanic crust outside the garnet stability field. Zircon U – Pb dating of the tonalite yielded a weighted-mean 206Pb/238U age of 159.1 ± 1.6 Ma. Late Jurassic oceanic plateau-type basaltic rocks with a small amount of plagiogranitic rocks are distributed sporadically in subduction complexes along the palaeo-Japan arc – trench system. A similar zircon U – Pb age (151.6 ± 1.8 Ma) has been reported for greenstone in the Cretaceous subduction complex along the palaeo-Kuril arc – trench system. The tonalite – dacite block was probably derived from the subduction complex at the junction of the palaeo-Japan and -Kuril arc – trench systems. Thus, the greenstones and the tonalite body were likely part of a large oceanic plateau, which formed at the Izanagi – Pacific–Farallon ridge triple junction during the Late Jurassic – Early Cretaceous.

Geochemistry and provenance of Mesozoic sandstones in Khon Kaen Geopark: Implication for tectonics of the western Khorat Plateau of Thailand.

Khon Kaen Geopark, representing an area of dinosaur fossil diversity, was selected for investigations to reveal the origin and tectonic setting of the Khorat Group. The area occupied by Mesozoic sedimentary rocks of four formal formations of the Khorat Group, namely the Phra Wihan Formation (PWF), Sao Khua Formation (SKF), Phu Phan Formation (PPF), and Khok Kruat Formation (KKF). A field investigation and macroscopic observations suggested that the immature sedimentary rocks of the study area are mainly clast-supported, pebbly sandstone and siltstone with few calcretes. The 50 rock samples that were selected for petrographical and geochemical investigations revealed that the sandstones of the PWF and PPF are quartz arenite and sublitharenite, with some subarkose, whereas those of the SKF are mainly subarkose and sublitharenite. In addition, the KKF dominantly presents sublitharenite with pebbles and calcretes. Mesozoic sandstones contain quartz, feldspars, various types of rock fragments, and accessory minerals (biotite, muscovite, zircon, and tourmaline), with siliceous, ferrous, and calcareous cement. Petrographic (Q-F-L) and geochemical (major and trace element) data suggested that the sources of sediments are mostly quartzose sedimentary rocks and some felsic-intermediate igneous rocks. Chondrite-normalized rare earth element patterns indicated that the origins of the studied sandstones are quartzose sedimentary rocks deposited in a passive continental margin or an upper continental crust. Geochemical traits of the sedimentary successions demonstrated that the provenance of the Khorat Basin prior to reworking by fluvial processes was situated in the passive continental margin or recycled orogen of the paleo-volcanic arc during the Mesozoic period.

Ferroan A-type metagranites from the Pernambuco–Alagoas Domain, northeastern Brazil attest Tonian crustal extension

The southern Pernambuco–Alagoas (PEAL) Domain in the Borborema Province, northeastern Brazil, is a large region characterized by voluminous Cryogenian–Ediacaran (640–580 Ma) calc-alkalic granitic to granodioritic rocks, and minor basement orthogneisses. Field, petrography, geochemistry, isotopic and geochronology studies were conducted on orthogneisses basement within Santana do Ipanema Batholith, southern PEAL Domain to determine their age, petrogenesis, and magmatic setting. The granitic to tonalitic orthogneisses contain abundant mafic microgranular enclaves and exhibit a flat-lying foliation. Biotite, amphibole, titanite, epidote and magnetite are the key mafic minerals. SHRIMP U–Pb zircon age from one sample revealed a Concordia age of 958 ± 10 Ma. Chemically, orthogneisses are metaluminous to slightly peraluminous, calc-alkaline to alkali-calcic, ferroan A-type granite to tonalite. Chondrite-normalized rare-earth and trace element patterns are fractionated, LREE and LILE-enriched, and HREE-depleted. Intensive parameter calculations indicate high-temperature crystallization (∼890 °C) with near-solidus temperature between 700 and 600 °C at a depth of ∼4 kbar. Their Sr–Nd isotopic composition (87Sr/86Sr(t) = 0.7032 to 0.7045; εNd(t) = +2.5 to +3.7 and TDM = 1.1 to 1.3 Ga) suggests derivation from a relatively young lower continental crust. Crustal extension induced sub-continental lithospheric mantle upwelling, which may have driven partial melting of newly created lower continental crust during the Tonian, and fractionation of the melt with little crustal mixing toward ferroan A-type granite geochemistry.

Tectono-Magmatic Significance of the Lower Devonian Mafic Intrusions in the East Kunlun Orogenic Belt: Keys for the Evolution of Proto-Tethys

Studies on post-collisional magmatic rocks can provide key clues to researching the crust–mantle interactions and the tectonic evolution of collisional orogenic belts. This study investigated a suite of newly discovered mafic intrusions in the middle of the East Kunlun orogenic belt through integrated analysis of petrology, petrography, and zircon U–Pb dating. The data could offer new insights into the generation of the Proto-Tethyan tectonic evolution. The result shows that these mafic intrusions are mainly gabbro and diabase, formed in the Early Devonian, with zircon U–Pb ages of 408.9 ± 2.0 Ma for gabbro and 411.1 ± 3.1 Ma for diabase. It consists of plagioclase, pyroxene, and dark minerals, and a small number of calcite and chlorite. Diabase has a small amount of amygdale. Their Na2O + K2O contents range from 3.47 wt.% to 5.45 wt.%, with Na2O/K2O ratios from 1.39 to 3.09, suggesting that they are calc–alkaline rocks. These rocks have an Fe2O3ᵀ content of 7.68 wt.%–11.59 wt.% and Mg# of 50.58–59.48, belonging to the iron-rich and magnesium-poor type. The chondrite-normalized rare earth elements show similar patterns that are characterized by enrichment of light rare earth elements, with (La/Yb)N of 3.27–6.75 and no significant europium anomaly, indicating the rocks are homogenous. The studied rocks are characterized by low contents of compatible elements Cr and Ni, enrichment of large-ion lithophile elements such as Rb, U, Sr, and Nd, and high-field-strength elements such as Nb, Ta, Zr, Hf, and Th. The mafic magma originated from the partial melting of the enriched mantle and was assimilated and mixed with crust materials during the process of migration. Based on the regional tectonic evolution, we interpret that the Proto-Tethys Ocean had closed in the Early Devonian, and that the East Kunlun region was in a post-collisional extensional tectonic setting.

Spatial Relationship between Eclogite and Copper-Nickel Mineralization in East Kunlun, China

In recent years, Cu-Ni deposits have been discovered at different localities in the Eastern part of the Kunlun orogenic belt such as Xiarihamu, Langmuri, Shitoukengde, and Wenquan. Eclogites are usually exposed in the areas associated with these deposits, thereby implying a certain coupling relationship between the Cu-Ni deposits and eclogite distribution. In this study, eclogite samples from the Xiarihamu and Langmuri areas were analyzed using petrogeochemistry, U-Pb zircon geochronology, and electron probe microanalysis (EPMA). Further, eclogite protolith properties, the formation environment, and the metallogenic mechanism were also investigated. Geochemically, eclogite is rich in MgO and FeO and low in alkali and SiO2. Its m/f ratios are 0.72 to 1.53 and Mg# values of 42 to 61. Overall, the chondrite-normalized rare-earth elements (REE) patterns showed characteristics of weak enrichment with LREE, weak negative Eu anomalies, relative enrichment of large-ion lithophile elements such as K and Rb, active incompatible element Th, the depletion of high-field strength elements Nb, Ta, Zr, and Hf, and V-shaped valleys caused by depletion in Sr, P, and Ti. These geochemical characteristics indicated that the protolith is highly differentiated Fe gabbro that formed in a continental margin type of rift environment. The EPMA analyses showed that the composition of garnet consists of almandite and grossularite, and omphacite often contains augite. Geochronological investigations showed that the peak metamorphic age of eclogite in Xiarihamu and Langmuri is 415.6 ± 2.7 Ma (MSWD = 0.43, n = 16) and 449.1 ± 8.5 Ma (MSWD = 0.88, n = 19), which are related to the early Paleozoic orogenic cycle and formed slightly earlier than the formation of the magmatic liquation type of Cu-Ni deposits in this area. On the basis of spatial coupling, formation age approximation, and geochemical correlation between eclogite and mafic rock masses, in combination with the previous research results of earlier work, it has been considered that the Cu-Ni ore deposits in the East Kunlun Range were formed in the post-collisional extension environment after the deep subduction of the continental crust. The ultra-high-pressure metamorphic melange formed by continental deep subduction or the enriched mantle formed by crust-mantle metasomatism was partially melted to form sulfur-rich mafic–ultramafic magmas in the post-collision extension environment. During the deep subduction of the continental crust, a large amount of crust-derived sulfur was brought into the mantle, which is the key factor for the mineralization of Cu-Ni ore in the region.

Petrogenesis and Geochronology of A1-Type Rhyolites in the Late Late Triassic of the East Kunlun Orogenic Belt: Constraints on the End of the Paleo-Tethys Orogenic Event

The rhyolites which are widely exposed to the northern margin of the East Kunlun orogenic belt were chosen as a research object to discern the post-orogenic tectonic evolution of the East Kunlun orogenic belt and reconstruct the post-collision orogenic processes of the Buqingshan- A’nyemaqen Ocean. We researched zircon U-Pb ages and geochemistry characteristics of the Late Triassic rhyolites in the eastern segment of the East Kunlun Orogenic Belt in the northern Tibetan Plateau. Zircon U-Pb dating yields coeval ages of 200.4 ± 1.4 Ma and 202.8 ± 1.2 Ma for the Keri rhyolites of the East Kunlun Orogenic Belt, indicating that the volcanic rocks were formed in the Late Triassic Rhaetian–Early Jurassic Hettangian. The Keri rhyolite is a product of the late magmatism of the Elashan Formation volcanic rocks. The rhyolites include rhyolitic brecciated tuff lavas and rhyolitic tuff lavas. The rhyolites are peraluminous and are high-K calc-alkaline, with high contents of SiO2, K2O, TFe2O3, and low P2O5 contents. The A/CNK ratios range from 0.97 to 1.09, indicating that the rhyolites are metaluminous to weakly peraluminous. The chondrite-normalized rare earth element (REE) distribution shows a significant negative Eu anomaly and low total REE concentrations. All samples are depleted in high field strength elements (HFSEs, e.g., Eu, Sr, Ti, and P), heavy rare earth elements (HREEs), and enriched in large ion lithophile elements (LILEs, e.g., Rb, Zr, Nd, Th, and U) and light rare earth elements (LREEs). The Keri rhyolite has the characteristics of A1-type magmatic rock, formed in an anorogenic environment after the closure of the Paleo-Tethys Ocean, and was the product of late magmatism in the Elashan Formation volcanic rocks.