REE Patterns Research Articles

Hydrothermal rutile chemistry and U-Pb age fingerprinting of the formation of the giant Nurkazgan porphyry Cu-Au deposit, Central Kazakhstan

The porphyry Cu-related intrusions commonly comprise multiple phases such as the large Nurkazgan porphyry Cu-Au deposit in Central Kazakhstan, hosted in the Karagandinsky dioritic to granitic intrusive complex. Here, SHRIMP and LA-ICP-MS zircon U-Pb dating on the multiple ore-bearing intrusions from this complex confirms a punctuated magmatic history distributed over 35 m.y., and marked by three episodic porphyry events rather than a single event, with the oldest event being the early granodiorite and quartz diorite porphyries at ca. 437–440 Ma, the second being the quartz diorite porphyry at 429.7 ± 2.1 Ma, and the last being the late granodiorite and quartz diorite porphyries at 402.8 ± 3.7 Ma and 402.0 ± 3.9 Ma, respectively. The mineralization is related to the two younger episodic intrusions of quartz diorite porphyry at ∼ 430 Ma and ∼ 402 Ma, respectively. SIMS U-Pb dating of hydrothermal, Cu-rich (up to 20.9 ppm) rutile from the breccia-type ores directly constrains the timing of porphyry mineralization at 428.9 ± 6.9 Ma, which is coincident with the emplacement age of the ∼ 430 Ma quartz diorite porphyry, and thus demonstrates this porphyry as a causative intrusion generating main-stage mineralization. This close genetic link is also supported by the chondrite-normalized REE patterns of rutile, which show remarkably similar light REE-enrichments and moderate negative Eu anomalies to those of the ∼ 430 Ma quartz diorite porphyry. A molybdenite sample obtained from the main-ore stage vein, however, has a Re-Os age of 418.6 ± 1.8 Ma, which is slightly younger than the U-Pb age determinations of rutile. This indicates that the Re-Os isotope system was disturbed by the second (post-ore) thermal event related to ∼ 402 Ma quartz diorite porphyry. In line with published data, this study suggests that the rutile U-Pb age in combination with its REE patterns can be a powerful tool to trace the causative porphyry. Moreover, the typical LREE-enriched REE patterns coupled with the high Cu anomalies, inherited from the causative porphyry and related exsolving fluids, can be as diagnostic proxies for distinguishing the porphyry Cu-related hydrothermal rutile from those formed in orogenic gold deposits. Based on these two geochemical discriminators and U-Pb ages, rutile can serve as unique fingerprints to help improve porphyry copper exploration in green field or covered terranes to complement detrital zircon fertility indicators.

MINERALOGICAL, PETROGRAPHIC AND GEOCHEMICAL EVIDENCE FOR ZIRCON FORMATION CONDITIONS WITHIN THE BURPALA MASSIF, NORTHERN BAIKAL REGION

This paper reports investigation on zircons from quartz syenite, alkaline and foid syenite, as well as metasomatic rock from the fenitization zone hosted by the Burpala massif. It is performed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), cathodoluminescence (CL), laser ablation inductively coupled plasma mass spectrometry (LA ICP MS), and Raman spectroscopy. Generally, all zircons from igneous rocks show rhythmic, crystal growth zoning or sector zoning (type I) except for some zircons from alkaline syenites (type II) showing patchy zoning. They systematically contain pores or cavities. The REE patterns of magmatic zircons share similar features: e.g. depletion of LREE ((Yb/La)N up to 35000), large positive Ce (Ce/Ce* 6–427) and small negative Eu (Eu/Eu* 0.37–0.93) anomalies. Zircons crystallized from quartz syenites at 830±30 °C at the early stage of rock formation, while zircons from alkaline and foid syenites crystallized at the later stage of rock formation (680–750 °C). Meanwhile, crystallization of zircons with rhythmic zoning (type I) occurs at later magmatic stage, while the formation zircons of type II is probably related to the separation of the highly fluorinated aqueous fluid from the residual melt.Zircons from fenites have a bipyramidal habit holding a heterogeneous mosaic core and a homogeneous (or rhythmic zoning) rim. The cores of zircon show flat REE patterns without significant anomalies, while the rims are characterized by noticeable fractionation of REE ((Yb/La)N 85–615) and show a positive Ce anomaly (Ce/Ce* 4–18). The Raman spectra of the cores show a higher degree of crystallinity than the rims, and their flat REE spectra are probably related to the contamination by micro inclusions. The discordant U-Pb age of 295±3 Ma was obtained for zircon rims, which is consistent with the age of formation of igneous rocks of the Burpala massif (298–291 Ma). The latter supports the syngenetic origin of metasomatic ore mineralization with the main stage of massif formation.

Petrogenesis and tectonic setting of the proto-tethyan dachaidan ophiolite, North China: insights from clinopyroxene chemistry and whole-rock Sr–Nd–Pb and zircon Hf isotopes

IntroductionThe Dachaidan ophiolites outcrop within an ultrahigh-pressure metamorphic belt along the northern margin of the Qaidam Basin. However, their age, source, and tectonic setting remain still in debate.MethodIn this study, we investigated the geochemistry and geochronology of the Dachaidan ophiolitic gabbros.Results and DiscussionZircon U–Pb dating yielded a crystallization age of 510.0 ± 2.8 Ma and 510.0 ± 2.9 Ma for the gabbro. The gabbros have low SiO2 contents (47.15–50.10 wt.%) and high MgO contents (6.35–9.04 wt.%) and Mg# values (55–74). The total rare earth element (∑REE) contents are 8.35–28.07 ppm, lower than those of normal-type mid-ocean ridge basalts (MORBs), and the gabbros exhibit light REE depletion or flat REE patterns, with small positive Eu anomalies (Eu/Eu* = 1.06–1.40). Trace element patterns are depleted to enriched in Nb and Ta, similar to island arc rocks and MORB. Clinopyroxene thermobarometry indicates the parental magma of the gabbros formed by high-temperature (1,318°C–1,363°C) and medium-pressure (1.27–1.64 GPa) partial melting in a mantle wedge. The gabbros have depleted Sr–Nd–Pb-Hf isotopic compositions, with (87Sr/86Sr)i = 0.704586–0.707441, εNd(t) = 4.7–6.6, and zircon εHf(t) = 7.6–11.4. The age-corrected Pb isotope ratios of these volcanic rocks are variable, with 206Pb/204Pb(t) = 18.085–18.253, 207Pb/204Pb(t) = 15.595–15.614, and 208Pb/204Pb(t) = 37.880–38.148, which are similar to the isotopic compositions of typical Indian MORBs. The source of the Dachaidan ophiolite is inferred to have been depleted mantle. The Dachaidan ophiolite likely formed in a forearc oceanic setting along the northern margin of the Qaidam Basin, during the initial subduction of an oceanic plate.

Insights into the North Patagonian Massif Lower Crust: Petrology and Microstructure of Granulite Xenoliths

Abstract The continental lower crust constitutes a key zone for understanding the mantle–crust magmatic and mechanical transfers, but its study is hampered by the paucity of lower crust samples. Here, we characterise the petrological, geochemical and petrophysical processes structuring the lower crust of the North Patagonian Massif (NPM; Argentina) using a suite of representative mafic granulite and websterite xenoliths. These xenoliths were entrained by alkaline lavas from five volcanic centres that erupted between the Oligocene and Pleistocene. Electron microprobe and Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-ICPMS) were used to obtain in situ geochemical data on the minerals, while microstructural data were obtained by Electron BackScatter Diffraction (EBSD). Both granulites and websterites display a granoblastic texture and sometimes a weak inherited magmatic layering. Mafic granulite xenoliths show a plagioclase + clinopyroxene ± orthopyroxene assemblage commonly associated with spinel or titanomagnetite. Websterite xenoliths show an association of clinopyroxene + orthopyroxene + spinel, along with accessory plagioclase. Mafic granulites and websterites have SiO2 contents ranging from 44 to 53 wt %, while their Mg# varies from 53 to 79. Clinopyroxenes are characterised by weak convex upward chondrite-normalised Rare Earth Elements - REE patterns (Light-REE </<< Mid-REE > Heavy-REE) which are similar to clinopyroxene phenocrysts and megacrysts from intra-plate basalts. Calculated liquid in equilibrium with clinopyroxene have similar REE patterns to those found in Cenozoic basalts from the NPM, suggesting that the xenolith suite represents evidence for underplating processes, possibly related to one of the magmatic events that have occurred in the NPM since the Permo-Trias. Mafic granulites and websterites show a weak mineral shape preferred orientation and an associated weak Crystal Preferred Orientation (CPO) related to the magmatic layering. Recorded plastic deformation is associated with the activation of both (100)[001] and (001)[100] slip systems in clinopyroxene, (100)[001] in orthopyroxene and (010)[001] in plagioclase. However, the activation of slip systems is generally not correlated with CPO in granulites, suggesting that the lower crust underwent subsolidus equilibration and weak plastic deformation in an inactive tectonic context, thereby preserving an inherited magmatic layering. Two-pyroxene (Fe–Mg) thermometer and pseudosection calculations define P–T conditions of the main paragenesis at 760°C to 1120°C and 7.2 to 10.3 kbar, which allows to define the Cenozoic geotherm of the NPM crust at 30°C/km and to reconsider the petrologic Moho depth at ca. 40 km.

Influence of Triassic and Jurassic arc magmatism in Lower Jurassic Sierra de Santa Rosa Formation, Northwestern México: Constraints from geochemistry and U-Pb geochronology

The Permo-Triassic and Lower Jurassic sedimentary succession of the El Antimonio Group in northern Sonora, Mexico is inferred to be deposited in a forearc basin and its age has been constrained by fossil assemblages and detrital zircon geochronology. In this work, petrography, geochemistry and detrital zircon U-Pb geochronology were undertaken on the Sierra de Santa Rosa Formation, the younger unit of the El Antimonio Group in the locality of the Sierra del Álamo, to constrain its tectonic setting, age, source area paleoweathering, and provenance. Sandstone of Sierra de Santa Rosa Formation is petrographically classified as arkose. The elemental ratios, REE patterns and Eu anomaly, as well as bivariate and ternary plots suggest igneous felsic sources subjected to weak to moderated chemical weathering under arid climatic conditions for detritus of the Sierra de Santa Rosa Formation. Detrital zircon U-Pb geochronology of seven sandstone samples of this unit record main populations of Proterozoic age (58% of the total grains) with age peaks at 1.68. 1.39 and 1.14 Ga and Triassic age (31% of total grains) with age peak at 219 Ma, and subordinate groups of Paleozoic, Jurassic and Archean ages. Main sources for the zircon grains are the regional nearby igneous-metamorphic Proterozoic basement rocks, recycled detritus from the Proterozoic and Paleozoic sedimentary cover, and the Permo-Triassic and Jurassic continental magmatic arcs of southwestern North America. The detrital zircon U-Pb geochronology of the dated samples allows to establish Sinemurian to early Toarcian maximum depositional ages for the Sierra de Santa Rosa Formation in the locality of the Sierra del Álamo.

Geochemical (δ13C, δ18O, 87Sr/86Sr, REEs) characterization of travertine in Tengchong, China: Insights into travertine origin and reservoir conditions

Geochemical characterization is extensively employed in travertine research, yet few studies have explored the potential of travertine geochemistry for elucidating the subterranean details of spring systems. In this study, we systematically characterized the geochemical signatures (δ13C, δ18O, 87Sr/86Sr, REEs, Zr, Th, Sr, Mn) of travertine from six spring systems in Tengchong (SW China) and compared them with those of potential reservoir rocks, aiming to understand travertine origin and assess reservoir conditions. Our results revealed substantial variations in the δ13C and δ18O of travertine among the examined systems, but the water temperature and parent CO2 assessments suggest a hot spring thermogene origin of the travertine. The 87Sr/86Sr of the studied travertine also varies significantly among the systems and overlaps with that of potential reservoir rocks. However, only the springs systems with reservoir temperatures exceeding 150 °C are likely to have precipitated travertine with 87Sr/86Sr resembling the whole-rock 87Sr/86Sr of the reservoir rocks. REE contamination by exogenous detritus and FeMn (oxyhydr)oxides was noted, emphasizing the need for careful REE contamination evaluation in travertine research. The REE comparison reveals that the studied travertine does not fully replicate the REE signature of its potential reservoir rocks, but the REE pattern, (Eu/Eu*)SN, and (Ce/Ce*)SN characteristics of the travertine reveal informative reservoir conditions. In summary, this study shows that the geochemistry of the travertine offers valuable insights into its origin and reservoir conditions. These findings could assist in the geochemical interpretation of travertine and the exaction of hypogean reservoir conditions from travertine.

Unraveling the metallogenic mechanisms of uranium-rich ore bodies: Insights from Xinqiaoxi’s pitchblende geochronology and pyrite geochemistry

Granite-related uranium deposits are essential for the global uranium supply, with the uranium-rich ore bodies within these deposits being crucial to their value. However, the sources of uranium, fluid characteristics, and metallogenic mechanisms within these uranium-rich ore bodies remain unclear. In this study, we analyzed pitchblende and pyrite from the Xinqiaoxi uranium deposit to determine uranium age and clarify the mineralization of uranium-rich ore bodies. The pitchblende samples provided a U-Pb age of 58.5 ± 3 Ma (MSWD = 3.4), closely aligns with the mineralization ages in other uranium deposits within the Xiazhuang uranium ore-field. This consistency suggests a significant uranium mineralization event in South China during this period. The vein-like and concentric structure of the pitchblende, coupled with its enrichment in U, Sr, As, W, and Mo but depletion in Th, Pb, and REEs, indicates a strong association with hydrothermal activity. Moreover, its REE pattern closely resembles that of the host rock (Xiazhuang and Maofeng granites), suggesting the latter as a crucial uranium source. Pyrite and pitchblende are coeval, yet pyrite was formed slightly earlier than pitchblende. Pyrite exhibits depletion in Co and Ni but enrichment in As, along with high Co/Ni ratios ranging from 1.68 to 12.2, indicative of a medium- to low temperature hydrothermal genesis. Furthermore, the positive cerium (Ce) anomaly observed in pyrite may indicate elevated oxygen fugacity in the fluids during precipitation. The δ34S values of pyrite (−10.42 ‰ to −15.26 ‰, averaging −13.44 ‰) are consistent with those of the host rock (Xiazhuang and Maofeng granites), indicating a primary sulfur source from the host rock. Additionally, pyrite may serve as a reductant, facilitating the formation of uranium ore. Our proposed genetic model suggests that CO2-rich oxidizing fluids facilitate uranium leaching from host rocks, resulting in the formation of a uranium-enriched fluid that migrates along faults, where U6+ undergoes reduction to U4+ within secondary fracture zones, facilitated by reductants such as pyrite.

Timing and origin of the Lomagundi-Jatuli Event: Insights from U[sbnd]Pb geochronology, C-O-Fe isotopes and REE compositions from the Jingshan Group, North China Craton

The Lomagundi-Jatuli Event (LJE) represents perhaps the largest and longest positive carbon isotope excursion of Earth history. However, the synchroneity, scale, and linkage of the LJE to Earth's early history of atmospheric oxygenation remain controversial. Strata of the Paleoproterozoic Jingshan Group of the North China Craton that preserve the isotopic record of the LJE excursion in marble layers and abundant graphite deposits provide an opportunity to elucidate the significance of the LJE. Carbon isotopic values (δ13CV-PDB) of the LJE based on analysis of 20 samples of the Lugezhuang Formation, lower Jingshan Group, range from −0.8 to +9.6 ‰ and display positive co-variance with stable oxygen isotope values (δ18OV-PDB). The positive carbon isotope excursion is constrained to 2140.6 ± 8.5 Ma (MSWD = 0.82, n = 25) based on magmatic zircon UPb geochronology of biotite granulite. Variation of facies-dependent carbon isotope values, the presence of graphite deposits of the Douya Formation, upper Jingshan Group, and the absence of a Ce anomaly in PAAS normalized REE patterns of marble samples suggest that the positive carbon isotope excursion is not linked to a marked increase of organic carbon burial and associated significant atmosphere oxygenation. Elevated concentrations of iron and PAAS-normalized middle REE enrichment of analyzed Jingshan Group marble samples point to anoxic and ferruginous oceanic conditions during accumulation of Jingshan Group carbonate. A positive Eu anomaly (average = 1.58), low La (average = 0.23), (Nd/Yb)N (average = 1.27), and Y/Ho (average = 36.6) anomalies, and negative iron isotope values (average δ56Fe = −0.12 ‰) are consistent with accumulation of Paleoproterozoic Jingshan Group carbonate in a restricted marine setting that was affected by high temperature hydrothermal fluids. Enrichment of the studied samples in heavy carbon isotope suggests elevated bio-productivity in the restricted, redox stratified marine setting in which Jingshan Group carbonate accumulated. Thus, it is likely that the positive stable carbon isotope excursion associated with Jingshan Group strata as well as other contemporaneous isotope excursions are local signals that are linked to a global perturbation of the carbon cycle.

Geochemical Constraints on Arsenic and Rare Earth Elements in Groundwater of Ganges Delta, Nadia District, West Bengal

ABSTRACT Geochemical studies of groundwater from 302 tubewells and aquifer sediments of the Ganges delta plain of Quaternary age are conducted. The geochemical behaviour of Fe, Mn, SO42-, arsenic (As), REEs, and Eu parameters in groundwater indicates two contrasting environments: (i) a more oxic condition in the fluvial environment of the Jalangi River in the northern part, and (ii) a less oxidizing/reducing environment in the palaeo-lacustrine environment towards south of the study area. Arsenic concentration in groundwater is more in palaeo-lacustrine environment due to (i) reductive desorption from Fe-oxyhydroxide in the high pH reducing environment and (ii) mobilization by ion exchange with the help of fertilizer used in agricultural activities. Both these phenomena are attributed to the strong spatial correlation of arsenic (As) with pH, PO4, and SO4. However, the dissimilar nature of REE pattern in groundwater and aquifer sediment indicates that REE geochemistry of groundwater is being modified by the “reductive dissolution of Fe-oxyhydroxides” in sediment which releases REE into the groundwater. We conclude that desorption and “reductive dissolution of Fe-oxyhydroxide” controls release of As and REE into the groundwater in both oxic and reducing aquifer conditions in the Ganges delta.

Mesoproterozoic depleted spinel peridotites metasomatized by high-K hydrous melt in the Patagonian back-arc

Here we report the first investigation of spinel-bearing mantle xenoliths from Los Gemelos volcano, Canquel Plateau, Patagonia. They are highly-depleted Mesoproterozoic (ReOs model ages of 1.3–0.9 Ga) harzburgites and clinopyroxene-poor lherzolites characterized by typical indicators of partial melt extraction, such as low whole-rock Al2O3 and CaO contents (<1.5 wt%), high Mg# of silicate phases (90–95), and Cr-rich spinel (Cr# 0.20–0.42). Depletion of incompatible highly siderophile elements (Re, Ru, Pd) relative to the primitive upper mantle supports high degrees of melt extraction. The occurrence of phlogopite and K-rich alkaline glass veins with high- and low-SiO2 compositions is clear evidence of modal metasomatism. The light rare earth element (LREE) enrichment in clinopyroxene, as well as the whole-rock U-shaped REE pattern, confirms cryptic metasomatism. This melt-rock interaction is corroborated by major (i.e., Mg# vs. basaltic elements) and trace (i.e., La/YbN vs. Sr/Y and Ti/Eu; and Sr vs. Ti/Eu) element contents of pyroxenes. The calculated compositions of melts in equilibrium with clinopyroxene coexisting with phlogopite suggest interaction with slab-derived materials. This metasomatism has been generated by a chromatographic fractionation-reaction process, from deep to shallow mantle domains. The percolation of a high-K hydrous magma probably is associated with the upwelling of asthenospheric material through a slab-window, which caused partial melting of oceanic crust and overlying sediments during the Paleocene. The varying intensities of metasomatic imprints recorded by mantle xenoliths from Los Gemelos provide valuable insights into the interaction of slab-derived materials near the lithosphere-asthenosphere boundary, at a distance of ∼600 km from the Andean volcanic arc.

Prolonged arc accretion during growth of juvenile crust in the Arabian Nubian Shield: Insights from the granitoids of northern Ethiopia

The Arabian Nubian Shield (ANS) is one of the largest juvenile continental crust formed after the Archean. To determine the timing and understand the mechanism of its early crustal growth, we conducted geochronological and geochemical studies on granitoids from northern Ethiopia. A plagiogranite, dated at 929.7 ± 2.2 Ma, represents one of the early granitoids from the ANS. It shows low K2O, TiO2, and REE contents, flat REE pattern and absence of Eu anomaly. Moreover, it exhibits (87Sr/86Sr)i, ƐNd(t) and ƐHf(t) values of 0.70341, +5.0 and +8.4, respectively. Its zircon δ18O value is 4.8‰, lower than the mantle value. These characteristics suggest that it was derived from partial melting of altered oceanic crust. The oxygen fugacity obtained from zircon trace elements is ΔFMQ+1.3, consistent with a subduction setting.Other plutons have much younger ages ranging from 860 to 840 Ma and are mainly medium K, I-type granitoids. These granitoids show low MgO, Ni and Cr contents, low Sr/Y, (La/Yb)N, Nb/Ta and Zr/Sm ratios. They exhibit whole-rock (87Sr/86Sr)i values of 0.70236–0.70304, ƐNd(t) values of 4.2–5.2, ƐHf(t) values of 5.8–7.6 and zircon ƐHf(t) values of 5.5–10.4, slightly lower than coeval depleted mantle. Furthermore, they exhibit fractionated REE patterns, enrichments in LILE and depletion in HFSE. These geochemical features suggest that these granitoids were generated by remelting of arc crust. Compiled data show that the associated basaltic rocks are of arc affinity, which confirms the coeval development of arc magmatism in the southern ANS. Our results suggest that the growth of juvenile crust in the southern ANS started from the early Neoproterozoic and peaked at ca. 880 to 800 Ma, much earlier than those in the northern ANS. The prolonged history accounts for the growth of the vast juvenile crust in the ANS.

Provenance, Intensity of Weathering, and Economic Potential of Placer-bearing Sediments on the Shelf off Quilon, Southwestern Coast, India

ABSTRACT In this study, the mineralogy and geochemistry of sediments of the continental shelf off Quilon, southwest coast, India is used as proxies to constrain their provenance, the intensity of weathering at source, and economic potential. The weathering index calculations were carried out on the sediments and the results showed that Chemical Alteration Index (CIA) (Average = 72.88), Chemical Index of Weathering (CIW) (Average = 92.72), and Plagioclase Alteration Index (PIA) (Average = 89.74) are high, indicating moderate to intense source area weathering. High source area weathering is also supported by high Th/U ratio (Average = 5.68) which is above the average crustal Th/U ratio of 3.8. The sediments are first-cycle sediments derived from the nearby source area, as evidenced by the identification of unaltered heavy minerals and rock-forming minerals, along with a high Average Composition Variability Index (ICV) (Average = 1.20). The high K2O/Na2O ratios (Average = 3.88), and LREE/HREE ratios (Average = 20), plotting of samples in the felsic field of various binary plots (SiO2 vs. Al2O3/TiO2, Zr vs. TiO2, Ce vs. La/Yb and La/Th vs. Hf binary plots) and normalized REE patterns with LREE enrichment and negative Eu anomaly indicate the sediments were primarily derived from Khondalites of the Trivandrum block and were transported by the Kallada and Ithikkara rivers. Average Σ REE, Th, and U concentrations are 222 ppm, 15.2 ppm, and 2.58 ppm respectively in the bulk sediments. The heavy mineral separates showed significantly increased concentrations of Σ REE (Average = 3009 ppm), Th (Average = 478 ppm), and U (Average = 30 ppm) due to the presence of monazite. Due to high Σ REE, Th, and U concentrations in the sediments due to monazite, present study recommend for further exploration of these sediments, which could contribute significantly to the resource base of the nation.

Provenance and tectonic setting of sandstones of the Lomas Coloradas Formation, Cabullona Group, Sonora, México: Constraints on petrography and geochemistry

The sedimentary rocks of the Cabullona Group are well exposed in the Cabullona Basin of northeastern Sonora, México, which represent syntectonic sedimentation associated with Laramide-style deformation during the Campanian−early Maastrichtian. The sandstones of the Lomas Coloradas Formation deposited at the upper part of the Cabullona Group. Petrography and geochemical (major, trace, and rare earth elements) studies were carried out on the sandstones to interpret the palaeoweathering, provenance, and tectonic setting of the Lomas Coloradas Formation sandstones. Most of the sandstone modal analysis data plotted in the QFL and QmFLt ternary diagrams fall into the fields of dissected arcs and recycled orogens, respectively. Geochemically the sandstones are classified as litharenites while few samples plot into the arkosic field. The chondrite-normalized REE diagrams for sandstones have LREE-enriched, relatively flat HREE patterns with negative Eu anomalies. CIA values and the A‒CN‒K diagram indicate a low intensity of chemical weathering in the source area. The tectonic setting diagram suggests both arc and rift settings for the studied sandstones. The bivariate and ternary diagrams and elemental ratios suggest a felsic source for the Lomas Coloradas Formation. The average REE patterns of the studied sandstones are comparable with REE patterns of the granite from the Caborca block, the rhyolite and granite of the Tarahumara Formation, and the Mesozoic felsic volcanic rocks. The modeled mixture of 40% Proterozoic granite, 30% Triassic arc, 10% Jurassic arc, and 20% Laramide arc represents the probable source rocks for the Lomas Coloradas Formation.

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

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

Extra-terrestrial mantle samples: Rare Earth Element variations and evidence for melt metasomatism in ureilite meteorites

Ureilites are meteorites derived from the mantle of a reduced differentiated asteroid, the “Ureilite Parent Body” (UPB), which was later disrupted by impact with another Solar System body. They have ultramafic compositions dominated mostly by olivine and pigeonite with rare orthopyroxene and augite; aluminous phases are generally absent. Ureilites vary from abundant peridotites to much rarer pyroxenites, and their core olivine compositions range from Fo74 to Fo97 across different samples. The UPB experienced sufficiently high temperatures to undergo silicate partial melting, as shown by depletion in the Light Rare Earth Elements (LREE) in bulk restitic ureilites. Plagioclase and merrillite were probably present in the UPB mantle but have been completely removed during silicate partial melting. Partial melts of the UPB mantle are represented by glassy melt inclusions, igneous clasts in ureilite breccias, cumulus augite in some ureilites, and rare trachyandesitic fragments. These melts are generally intermediate and sub-alkaline in composition, although a few are alkaline. They have more enriched and flatter bulk REE patterns than the restitic ureilites and often show positive Eu anomalies. Glasses (representing melts) in ureilites from this study range from 57 to 79 wt% SiO2. One sample (AhS 22) shows petrographic and geochemical evidence for interaction between magma and the solid UPB mantle by forming metasomatic augite.Silicate minerals in ureilites analysed by LA-ICP-MS are generally LREE-depleted, with negative Eu anomalies. Ureilitic olivines have the lowest REE contents and the smallest negative Eu anomalies. Low-Ca pyroxenes have similar patterns with slightly stronger Eu anomalies. Augites have the highest REE contents and the most negative Eu anomalies. Augites show REE disequilibrium with olivine and low-Ca pyroxene, suggesting that they were not part of the restitic assemblage but were added by silicate melts passing through the UPB mantle, i.e. they are metasomatic in origin. We also discuss the size of the original UPB, using silicate minerals as evidence for it being a typical asteroid rather than a planet-sized object.

Mineral chemistry of the Geyer SW tin skarn deposit: understanding variable fluid/rock ratios and metal fluxes

AbstractThe Geyer tin skarn in the Erzgebirge, Germany, comprises an early skarnoid stage (stage I, ~ 320 Ma) and a younger metasomatic stage (stage II, ~ 305 Ma), but yet, the source and distribution of Sn and the physicochemical conditions of skarn alteration were not constrained. Our results illustrate that contact metamorphic skarnoids of stage I contain only little Sn. REE patterns and elevated concentrations of HFSE indicate that garnet, titanite and vesuvianite of stage I formed under rock-buffered conditions (low fluid/rock ratios). Prograde assemblages of stage II, in contrast, contain two generations of stanniferous garnet, titanite-malayaite and vesuvianite. Oscillation between rock-buffered and fluid-buffered conditions are marked by variable concentrations of HFSE, W, In, and Sn in metasomatic garnet. Trace and REE element signatures of minerals formed under high fluid/rock ratios appear to mimic the signature of the magmatic-hydrothermal fluid which gave rise to metasomatic skarn alteration. Concomitantly with lower fluid-rock ratio, tin was remobilized from Sn-rich silicates and re-precipitated as malayaite. Ingress of meteoric water and decreasing temperatures towards the end of stage II led to the formation of cassiterite, low-Sn amphibole, chlorite, and sulfide minerals. Minor and trace element compositions of cassiterite do not show much variation, even if host rock and gangue minerals vary significantly, suggesting a predominance of a magmatic-hydrothermal fluid and high fluid/rock ratios. The mineral chemistry of major skarn-forming minerals, hence, records the change in the fluid/rock ratio, and the arrival, distribution, and remobilization of tin by magmatic fluids in polyphase tin skarn systems.

Sediment composition and U–Pb ages of detrital zircons in the Salina Cruz and Puerto Ángel beaches along the Gulf of Tehuantepec, Mexican Pacific

The Salina Cruz and Puerto Ángel beach areas in the Gulf of Tehuantepec, Mexican Pacific coast represent an important economic sector of the region. In this study, the mineralogy and geochemistry of bulk sediments, and geochronology of 400 detrital zircons recovered from the beach sediments were analysed to investigate their origin. The sediments are abundant in quartz, feldspar, ilmenite, cordierite, aragonite and anorthite. The chemical index of weathering revealed a moderate to intense weathering in the source area. The chondrite normalized REE patterns of bulk sediments are similar to the found in the Upper Continental Crust, suggesting the derivation of sediments from felsic igneous rocks. The REE patterns of zircons and the trace elemental ratios reveal a continental crust origin. Zircon U–Pb ages in the Salina Cruz beach were represented by Proterozoic (~545.1–1314.1 Ma; n = 170) and Cenozoic (~0.01–66 Ma; n = 20). The Puerto Ángel beach was abundant in Proterozoic zircon grains (~600.9–1171.4 Ma; n = 109) and followed by Mesozoic grains (~73.78–246.9 Ma; n = 40). The comparison of zircon U–Pb ages of this study with probable source rocks reveals that the Oaxaquia Terrane and Chiapas Massif Complex were the major contributors of Proterozoic zircons to the coastal areas. Similarly, the results indicate that the Cenozoic zircons were contributed by the Chiapas Massif Complex, coastal batholith and Cuicateco Terrane. The Mesozoic zircons are very few, derived from the nearby Xolapa Complex and the Chuacús Terrane.

Forearc magmatism in the Pannonian basin recorded by metasomatised skarnoid xenoliths in Pliocene basalt (Novohrad-Gemer Volcanic Field, Slovakia)

Anorthite-diopside-spinel-forsterite xenoliths occur in basaltic lava flow in northern part of the Pannonian basin in the Novohrad-Gemer Volcanic Field (NGVF). Several lines of geochemical evidence suggest that the typical skarn assemblage originated by multiple carbonatitic and alkaline silicate metasomatism of pristine basalt to picrobasalt protolith rather than by the modification of crustal carbonates around shallow magma chambers. Interaction with mantle-derived magnesite or dolomite carbonatite melt triggered the crystallization of neoformed forsterite at the expense of primary clinopyroxene. The alkaline silicate metasomatism resulted in the replacement of primary diopside and augite by neoformed aegirine and aegirine-augite accompanied by amphiboles (richterite, katophorite, arfvedsonite). Weakly metasomatised Group 1 xenoliths retained their fore-arc magmatic geochemical signatures: flat REE patterns, low concentrations of high-field strength elements (Ti, P, Zr) and Ni compared to MORB, low ratios of highly-to-less incompatible elements (Ti/V, Zr/Y) relative to MORB, low Na2O, low total REE, and supra-subduction affinity of primary clinopyroxenes, being thus analogues to fore-arc basalts (FAB). In contrast, strongly metasomatised Group 2 xenoliths exhibit LREE-enriched patterns sub-parallel with those of host trachybasalts. Some Group 1 xenoliths also exhibit large positive Eu anomalies and strongly depleted signatures diagnostic of low-pressure plagioclase-pyroxene cumulates. One xenolith with complementary negative Eu, Sr and positive Rb anomalies has been identified as high-Mg basaltic andesite melt residuum. Sr and Nd isotopes plot along the OIB-MORB array. The Group 1 converges at initial 87Sr/86Sr and 143Nd/144Nd ratios of 0.7038–0.7041 and 0.5127–0.5128, respectively, thus recording a 140–190 Ma old mantle source. Thermobarometry data on metasomatically unmodified pyroxenes have been arranged along decompression cooling trend, propagating from ∼1230 °C and ∼ 1 GPa and ending at ∼1160 °C around atmospheric pressure. The maximum pressure indicates the melt generation zone ∼35 km deep, reflecting thin lithospheric mantle. The FABs identified for the first time in the AlCaPa megaunit corroborate the affinity of the NGVF lithospheric segment to Dinarides.

Geochronology and Petrogenesis of Late Carboniferous to Early Permian Basalts in the Central Lhasa Subterrane, Southern Tibet: Implications for the Evolution of the Sumdo Paleo‐Tethys Ocean

AbstractBasalts from the Late Carboniferous to Early Permian are extensively developed in the central Lhasa subterrane, southern Tibet. Studying the petrogenesis of these rocks may have implications for the late Paleozoic arc magmatism along the central Lhasa subterrane uncovering more of the evolution of the Sumdo Paleo‐Tethys Ocean and its dynamic mechanism. Basalt samples from the Luobadui Formation in the Leqingla area, NW of Linzhou City in the central Lhasa subterrane, southern Tibet exhibit arc‐like geochemical signatures in a subduction‐zone tectonic setting characterized by high Al2O3 and low TiO2 contents, fractionated REE patterns with low Nb/La ratios and high LREE concentrations, and negative HFSE anomalies. Based on their higher Th/Ce, Nb/Zr, and lower Ba/Th, Pb/Nd ratios, slightly negative to positive εNd(t) values, and the relatively high Sr‐Pb isotopic compositions, these samples were probably derived from partial melting of a depleted mantle source of garnet + spinel lherzolite, metasomatized by subducted sediments around 297 Ma. Modeling of the trace elements indicates that these basalts experienced fractional crystallization of olivine, clinopyroxene and minor plagioclase during magma ascent and eruption. It is proposed that these Late Carboniferous–Early Permian basalts are associated with the northward subduction of the Sumdo Paleo‐Tethys Ocean seafloor along the southern margin of the central Lhasa subterrane.

Post-orogenic magmatic-hydrothermal system in the southern Songpan-Ganze Orogen, eastern Tibetan Plateau

ABSTRACT Post-orogenic magmatism is uncommon in the Songpan-Ganze Orogen (SGO), and could provide deep insights into geodynamic evolution and related metallogenesis. Here we present zircon U-Pb-Hf isotopes and whole-rock geochemical data, for post-orogenic granitoids newly identified in the southern SGO. The Longxigou and Yangfanggou granites yield crystallization age of ca. 165 Ma and εHf(t) values of +3.8 to −9.1. This age post-dates regional ca. 220–200 Ma orogenic magmatism and ca. 205–190 Ma peak metamorphism, and corresponds to ca. 200–150 Ma post-orogenic magmatism which is exemplified by neighbouring and coeval Wenjiaping and Wulaxi felsic plutons. They are crosscut by ca. 133 Ma granitic pegmatites, with εHf(t) values of −4.3 to −14.2. These post-orogenic granites show high SiO2 contents, as well as low Mg# values, (Zr + Nb + Ce + Y) concentrations and zircon saturation temperatures. They have continental crust-like REE patterns and trace element profiles, and exhibit negative Eu anomalies, enrichment in large ion lithophile elements and depletion in high field strength elements. Their mineral assemblages lack typical high-temperature (e.g. pyroxene and fayalite) and peraluminous (e.g. garnet and cordierite) varieties. All these features indicate an I-type granite affinity, and a dominant derivation from thickened lower crust. In comparison, these post-orogenic granites are compositionally distinct from regional late-orogenic (>200 Ma) categories, which have more positive εHf(t) values and higher Mg# values, with subduction-related signatures involving significant mantle components. Further, several high-grade stratiform Cu deposits and a tungsten deposit occur to the south of these granitic plutons, and have mineralization ages of 164–151 Ma together with biotite alteration age of ca. 134 Ma. Hence, ca. 165–133 Ma magmatic-hydrothermal system was most likely responsible for Cu-W mineralization and effective upgrading of metal deposits in the southern SGO.