Trace Element Compositions Research Articles

Actinide isotope analysis and trace element composition of bones of prehistoric animals and humans by inductively coupled plasma mass spectrometry (ICP-MS)

AbstractInductively coupled plasma mass spectrometry (ICP-MS) has been used for analysis of the bones of archanthropus, ancient bear, southern mammoths, dinosaurs, as well as soils collected in various parts of Uzbekistan. The concentrations of 64 elements have been detected including thorium and uranium for which isotope compositions were also analysed. The comparison of the ICP-MS data with the results we obtained earlier for some bones using instrumental neutron activation analysis (INAA) is presented. The concentrations of 234, 235, 238U are up to two orders of magnitude elevated compared to the soils (e.g.238U in south mammoth bone—130.1 mg/kg, and that of soil is only 1.6 mg/kg). The levels of 236U, and 239, 240, 242, 244Pu isotopes (possible neutron capture products of 235U and 238U) correspond to a count rate of blank samples. In addition, the isotope analysis confirms the uranium in the bones and surrounding soils is natural (the average determined for all samples uranium ratios 235U/238U = 0.0071 ± 0.0003 (2-sigma errors). The concentration of 230Th (which is the part of 234U and 238U decay chain) is also elevated in the bones compared to the surrounding soils, however, the concentrations of stable 232Th largely correspond to those of the soil. The excess uranium detected in bones is most probably due to the preferential accumulation from soil, and not to the paleo diet.

A HIMU-like component in Mariana Convergent Margin magma sources during initial arc rifting revealed by melt inclusions

Compositions of island arc and back-arc basin basalts are often used to trace the recycling of subducted materials. However, the contribution of subducted components to the mantle source during initial arc rifting before back-arc basin spreading is not yet well constrained. The northernmost Mariana arc is ideal for studying this because the transition from rifting to back-arc spreading is happening here. Here we report major and trace element and Pb isotopic compositions of olivine-hosted melt inclusions from lavas erupted during initial rifting at 24°N (NSP-24) and compare them with those in active arc front at 21°N and mature back-arc basin at 18°N. NSP-24 high-K melt inclusions have highly radiogenic Pb compositions and are close to those of the HIMU end-member, suggesting the presence of this component in the magma source. The HIMU-like component may be stored in the over-riding plate and released into arc magma with rifting. HIMU-type seamounts may be subducted elsewhere beneath the Mariana arc, but obvious HIMU-type components appear only in the initial stages of arc rifting due to the low melting degree and being consumed during the process of back-arc spreading.

Exploring Quantitative Biological Major, Trace, and Ultratrace Elements Composition and Qualitative Primary-Secondary Metabolites in Lamiaceae Medicinal Plants from Turkey.

Medicinal plants comprise a spectrum of constituents, encompassing both organic and inorganic elements. Elemental composition of 27 species of medicinal plants of Lamiaceae (including 17 endemic) family grown in Turkey was carried out by ICP-MS. The following elements were determined in analysed samples: Na, Mg, Al, K, Ca, Sc, Cr, Mn, Fe, Co, Zn, As, Rb, Sr, Cs, Ba, La, Ce, Sm, U, Se. Quantitative analysis of specific primary and secondary metabolites was carried out. Na and K are major constituents in plants. The concentrations of Na range from 332,495.590g/kg (in sample 10SA) to 279,690.674g/kg (in sample 4SA), while those of K vary from 67,492.456g/kg (in sample 15SA) to 3347.612g/kg (in sample 1A). Some metals such as Al, Cr, Mn, Fe, Co, Zn, As, Se, Rb, Sr, Cs, and Ba were also detected. Flavonoids, carbohydrates and tannins were present in all sample. Saponins were found in all samples except 1C and 2O. Coumarin were detected in samples 2N, 1T, 1O, 1Z, 3SA, 1C, 4SA, 6SA, 8SA, 1M, 11SA, 13SA, 2O, 14SA, 1H, and 16SI. Lipids were present in samples 6S, 9S, 1A, 10S, 1M, 11SA, 12SA, 13SA, 14SA, and 16SI. Plants contain essential, rare earth, and trace elements at mg/kg concentrations, while major elements such as K and Na are present in high levels. Toxic element As (arsenic) was detected in all analyzed plants, but in most samples, its concentration was below the threshold set by World Health Organization.

Deciphering magmatic processes from plagioclase, clinopyroxene and amphibole chemistry and textures: A case study of a basaltic lava flow in the Basque-Cantabrian Basin (Northern Spain)

AbstractThis paper addresses the study of a pillow lava interbedded with Late Albian-Early Cenomanian sediments that crops out in Armintza (Bizkaia, Northern Spain). The lava flow is an alkaline basalt with abundant macrocrysts of clinopyroxene, kaersutite, Ca-rich plagioclase (50-86% An) and ilmenite, which display a variety of textures and complex zoning patterns indicative of open-system magmatic behaviour. Macrocryst cores are likely to be inherited antecrysts that underwent complex processes under deep pre-eruptive conditions (≈ 700-800 MPa). Microcrysts and macrocryst rims formed during magmatic ascent and emplacement at shallower levels (≈ 35 MPa). Hypothetical melts in equilibrium with clinopyroxenes and amphiboles have trace element compositions like metasomatic vein melts containing amphibole, and their patterns overlap with those of the Armintza pillow lava. This suggests a metasomatised lithospheric mantle with amphibole-rich veins as a potential source for the alkaline basaltic melt. It is even conceivable that the Armintza pillow lava and other alkaline volcanic manifestations of the Basque-Cantabrian Basin were part of the same magma plumbing system through which a series of time-limited eruptions of different batches of magma ascended from the lithospheric mantle to the upper crust during the Albian to the Santonian.

Accretion of the lower oceanic crust at fast-spreading ridges: Insights from Hess Deep (East Pacific Rise, IODP Expedition 345)

Abstract At mid-ocean ridges, melts that formed during adiabatic melting of a heterogeneous mantle migrate upwards and ultimately crystallize the oceanic crust. The lower crustal gabbros represent the first crystallization products of these melts and the processes involved in the accretion of the lowermost crust drive the chemical evolution of the magmas forming two thirds of Earth’s surface. At fast-spreading ridges, elevated melt supply leads to the formation of a ⁓6 km-thick layered oceanic crust. Here, we provide a detailed petrochemical characterization of the lower portion of the fast-spread oceanic crust drilled during IODP Expedition 345 at the East Pacific Rise (IODP Holes U1415), together with the processes involved in crustal accretion. The recovered gabbroic rocks are primitive in composition and range from troctolites to olivine gabbros, olivine gabbronorites and gabbros. Although textural evidence of dissolution-precipitation processes is widespread within this gabbroic section, only the most interstitial phases record chemical compositions driven by melt-mush interaction processes during closure of the magmatic system. Comparing mineral compositions from this lower crustal section with its slow-spreading counterparts, we propose that the impact of reactive processes on the chemical evolution of the parental melts is dampened in the lower gabbros from magmatically productive spreading centres. Oceanic accretion thereby seems driven by fractional crystallization in the lower gabbroic layers, followed by upward reactive percolation of melts towards shallower sections. Using the composition of clinopyroxene from these primitive, nearly unmodified gabbros, we estimate the parental melt trace element compositions of Hess Deep, showing that the primary melts of the East Pacific Rise are more depleted in incompatible trace elements compared to those formed at slower spreading rates, as a result of higher melting degrees of the underlying mantle.

Copper for the early oxhide ingots traced to the South Urals

Oxhide ingots are flat, rectangular slabs of metal, most commonly of copper, with protruding corners of varying styles. These Late Bronze Age artifacts were widespread across the Mediterranean for approximately half a millennium between the 16th and 11th centuries BC. Although they are generally known as essentially a Cypriot “commodity brand” by the late 15th century BCE, the origin of this ingot’s distinct shape has remained unknown. With the expansion of the lead-isotope database of Eurasian copper ores, the origin of the oldest chemically characterized oxide ingots may now be defined. The bimodal lead isotope compositions of 15 early, pillow-shaped oxhide ingots excavated in Crete are consistent with those of copper ores from the Southern Urals, which are known to have been actively mined in the Bronze Age. Together, Pb isotope and trace element compositions indicate that the majority of the ingots were cast from copper derived from Ural-type Cu-Zn volcanogenic massive sulfide deposits. However, two ingots enriched in Ni, As, and Co match Main Ural Fault-type ores that are hosted by ultramafic rocks.The characteristic design of the pillow-shaped ingot was likely related to the particulars of overland transport, facilitating their long-distance conveyance on pack animals. There is further support of a non-Cypriot origin of this form in the possible association between the words for “ingot”, “copper” and “hide” across languages of Western Asia and the Mediterranean. Thus, an eastern origin of the oxhide form for ingots is likely.

Petrogenesis of volcanic rocks from the Quaternary Eifel volcanic fields, Germany: detailed insights from combined trace-element and Sr–Nd–Hf–Pb–Os isotope data

Quaternary rocks from the East and West Eifel volcanic fields in western Germany are a key suite of intraplate volcanic rocks that can provide insights into volcanism of the Central European Volcanic Province (CEVP) and into continental intraplate volcanism in general. We present a comprehensive dataset for Eifel lavas including isotope as well as major and trace element data for 59 samples covering representative compositions of the different volcanic fields. In line with previous studies, the lavas are all SiO2-undersaturated, alkaline-rich and mainly comprise primitive basanites, melilitites, and nephelinites (Mg# ≥ 57). Geochemical compositions of samples from both volcanic subfields display distinct differences in their trace-element as well as radiogenic isotope compositions, largely confirming previous subdivisions. Coupled trace-element and radiogenic Sr–Nd–Hf–Pb–Os isotope compositions can now provide firm evidence for spatially heterogeneous mantle sources and compositionally distinct magmatic pulses. Within the West Eifel Field, Sr–Nd–Pb isotope compositions of the younger (≤80 ka), ONB-suite (olivine-nephelinite-basanite) are similar to FOZO (FOcal ZOne) or the EAR (European Asthenospheric Reservoir) and resemble compositions that have been previously reported from plume-sourced ocean island basalts (OIB). In marked difference, older (700 Ma to 80 ka) volcanic rocks from the F-suite (Foidite) in the West Eifel field and from the entire east Eifel Field tap a more enriched mantle component, as illustrated by more radiogenic Sr isotope (86Sr/87Sr up to 0.705408) and variable Pb isotope compositions (206Pb/204Pb = 18.61–19.70, 207Pb/204Pb = 15.62–15.67 and 208Pb/204Pb = 38.89–39.76). Combined trace-element compositions of ONB-suite samples are in good agreement with results from batch melting models suggesting a hybrid composition of Eifel magmas formed through mixing 10% of a FOZO-like melt with 90% of a DMM-like melt, similar to melts from the Tertiary HEVF. However, radiogenic Sr–Nd–Pb isotope compositions of F-suite and EEVF and some ONB lavas require the admixture of melts from lithospheric mantle sources. Elevated Nb/Ta and Lu/Hf ratios in combination with variable 187Os/188Os ratios can now demonstrate the presence of residual carbonated eclogite components, either in the lithosphere or in the asthenospheric mantle. Finally, by combining geochemical and temporal constraints of Tertiary and Quaternary volcanism it becomes evident that CEVP volcanism in central and western Germany has resulted from compositionally distinct magmatic pulses that tap separate mantle sources. Although the presence of a mantle plume can neither be fully confirmed nor excluded, plume-like melt pulses which partially tap carbonated eclogite domains that interact to variable extents with the lithosphere provide a viable explanation for the temporal and compositional cyclicity of CEVP volcanism.

Zircon trace element fingerprint of changing tectonic regimes in Permian rhyolites from the Central European Lowlands

AbstractThe late Carboniferous/early Permian post-collisional rhyolites (305–285 Ma) that formed in Central Europe have generally similar whole rock compositions to that of older Late-Variscan rhyolites (330–310 Ma). However, data compilation combining zircon age with the chemical composition of rhyolites from 20 units shows a trend of increasing zircon saturation temperature with decreasing age. This trend is particularly well identified in rhyolites from the Central European Lowlands (CEL)—consisting of the NE German and NW Polish Basin—and also correlates their location with the zircon saturation temperature increasing from SE to NW from 750°C to 850°C. We infer that these higher temperatures of zircon saturation reflect a contemporaneous change in the tectonic setting from collisional to divergent, reflecting the onset of the Central European continental rifting. This interpretation is further corroborated by the trace element compositions of the CEL zircons, which resembles zircon crystallized in a divergent setting. Interestingly, the zircon formed globally in this type of setting is chemically diverse, especially considering uranium concentration. For example, zircon from locations dominated by mafic magma fractionation, such as rhyolites from Iceland, have low U concentrations and low U/Yb ratios. On the other hand, zircon formed in rhyolites in rifted margins, like western North America, tends to have much higher U and U/Yb ratios. Such high concentrations are not observed in zircon from the CEL, suggesting that the mantle input could be higher and residence times within continental crust shorter than those for rhyolites from the Cenozoic western USA. This may, in turn, suggest that the region might have been affected by a hot spot, similar to that responsible for rhyolite formation of the Snake River Plain. Graphical abstract

Petrologically controlled oxygen isotopic classification of cogenetic magmatic and metamorphic sapphire from Quaternary volcanic fields in the Eifel, Germany

Gem sapphire is commonly retrieved from primary and secondary deposits associated with alkali basaltic fields, but its source rocks are rarely preserved. The Eifel (Rhenish Massif, western Germany), although not producing gem sapphire, shares many petrologic and geochemical similarities with such fields worldwide. Due to the young age of volcanic deposits and active quarrying, sapphire-bearing rocks are readily accessible, along with detrital sapphire from modern sediments. Here, oxygen isotope and trace element compositions are reported for 223 sapphire grains, and rutile and zircon inclusions in sapphire were dated indicating crystallization synchronous with Paleogene–Quaternary volcanism. Endmembers in δ18O range are sapphires from syenites representing mantle-derived differentiated melts with minor crustal contamination (~4–6‰) and contact metamorphic mica schists (>10‰) as purely crustal source rocks. Intermediate values between ~6 and 10‰ require variable degrees of mantle-crust hybridization. Lower crustal granulite sources are dismissed based on their oxygen isotopic compositions being lower than most sapphire crystals. Diffusion modelling of sharp oxygen isotopic zonation in compositionally zoned crystals precludes crystal residence at >900 °C over the lifetime of evolved magma reservoirs in the Eifel (c. 50 ka). This argues against direct mantle or lower crustal sapphire origins. Instead, low temperature residence is consistent with sharp δ18O gradients, coexisting andalusite, and fluid inclusion barometry. Hence, Eifel sapphire crystallization is attributed to contact metamorphic aureoles around upper crustal (5–7 km) magma bodies where phonolite, trachyte, and carbonatite melts differentiated from mafic parental magmas, and reacted with metasedimentary wall rocks.

Optical-spectroscopic and isotope-geochemical characteristics of zircons from diamond-bearing placers in Yakutia as indicators of diamond ore bodies

Research subject. Zircon grains from diamond placers of the Molodo and Ebelyakh rivers of the Yakut Arctic. Aim. To study the indicator characteristics of zircon to determine sources of diamonds and ways of their transfer to placers; to analyze optical-spectroscopic and isotope-geochemical parameters of zircon grains, their microelemental, U-Pb, and Lu-Hf isotope composition. Materials and methods. A LA-ICP-MS analysis of the U-Pb isotopic and trace element composition of zircon was carried out using a NexION 300S mass spectrometer with an NWR 213 attachment. An analysis of the Lu-Hf isotope system was carried out using a Neptune Plus mass spectrometer with an NWR 213 attachment, located in a room of cleanliness class 7 ISO at the Geoanalitik Center for Collective Use (IGG Ural Branch of the Russian Academy of Sciences, Ekaterinburg). Raman spectra were obtained using a LabRAM HR800 Evolution confocal spectrometer. CL spectra were obtained using a Jeol JSM6390LV scanning electron microscope equipped with a Horiba H-CLUE iHR500 attachment. Results. The local optical spectroscopic characteristics (Raman spectra and catholuminescence) of zircon grains were established, which made it possible to substantiate the conclusion about their high crystallinity and homogeneity (monochrony), as well as to select international zircon standards with similar characteristics for use in LA-ICP-MS analysis to ensure similar conditions for evaporation of the substance and fractionation parameters of the U and Pb elements. LA-ICPMS data on the microimpurity, U-Pb and Lu-Hf isotopic composition of zircon grains from diamond placers, as well as the dose values of their self-irradiation, are presented. Conclusions. The obtained U-Pb dating contributes to reconstructing a more precise history, character, and sequence of manifestation of kimberlite magmatism, tectonic processes, and migration routes of kimberlite material and diamonds across the Siberian craton, within the Yakut kimberlite province.

Shallow groundwater quality and health risk assessment of fluoride and arsenic in Northwestern Jiangsu Province, China

Assessing groundwater quality is critical to regional water resource conservation and human health safety, especially in areas with co-existence of toxic constituents fluoride (F−) and arsenic (As). In this study, fourteen groundwater samples were collected in Feng County, Northwestern Jiangsu Province to identify dominant contaminants and their spatial distribution and health risk. The composition and variation characteristics of major ions (K+, Na+, Ca2+, Mg2+, Cl−, SO42−, HCO3−, and NO3−) and trace elements (F−, As, and Mn) were analyzed. The hydrochemical results revealed that high F− groundwater was mainly distributed in the northern areas whereas As-riched groundwater was primarily distributed in southern areas. Notably, over 85.7% and 21.4% of the shallow groundwater samples exceeded the drinking water quality standard of 1.5 mg/L for F− and 10 µg/L for As, respectively. Based on the water quality index (WQI) appraisal result, 71.4% of the groundwater in the study area is classified as “poor”, and thus unsuitable for drinking directly. We assessed the human non-carcinogenic health risk of F− (HQFluoride) and As (HQArsenic) and the carcinogenic health risk of As (CRArsenic). The calculated hazard quotient (HQ) for F− indicated nearly all groundwater samples have an unacceptable risk (HQ > 1) for each age group. However, HQArsenic values revealed that 28.6%, 21.4%, 21.4%, and 21.4% of groundwater samples posed potential non-carcinogenic health risks for infants, children, females, and males, respectively. The calculated results of CRArsenic showed that 0%, 21.4%, 28.6%, and 28.6% of groundwater samples posed unacceptable health risks (CR > 1.0 × 10−4) to infants, children, females, and males, respectively. The groundwater irrigation suitability assessment results showed that 21.4% of samples were doubtful to unsuitable for irrigation, and 85.7% owed magnesium hazards. The findings of this study will assist policymakers in formulating proper remedial policies and mitigation strategies to ensure the safety of drinking and irrigation water.

Genesis of the Devonian Habaqin ultramafic arc complex and associated low-grade Fe–Ti oxide mineralization in the northern North China Craton

In the northern North China Craton (NCC), abundant non-layered ultramafic complexes and associated low-grade Fe–Ti oxide ores (over 1000 million tons) were uncovered. However, their petrogenesis and metallogeny have remained unclear. The Habaqin complex is one of the larger intrusions of the region and hosts the largest low-grade magnetite occurrence. Here we present petrography, zircon U–Pb geochronology, mineral and whole-rock major and trace element compositions, and whole-rock Sr–Nd and zircon Lu–Hf isotopes of the complex to constrain its genesis. The complex includes early pyroxenite (∼75% clinopyroxene, ∼15% amphibole, ∼10% magnetite) and late hornblendite (∼80% amphibole, 15–20% magnetite, 0–5% apatite). Zircon grains from the hornblendite yielded a weighted mean 206Pb/238U age of 395 ± 2 Ma. The increasing whole-rock FeOtot and TiO2 contents from pyroxenite (FeOtot = 18.9 wt%, TiO2 = 1.31 wt%) to hornblendite (FeOtot = 19.1–30.4 wt%, TiO2 = 2.63–3.12 wt%) correlate with higher modal proportions of amphibole and magnetite. The pyroxenite and hornblendite display similar arc-like trace element characteristics of enrichment in LILEs and LREEs, and depletion in HFSEs. The complex formed by fractional crystallization of clinopyroxene, amphibole, magnetite, and apatite from a hydrous parent magma. Early removal of clinopyroxene caused H2O enrichment in evolved residual magmas and crystallization of magnetite and amphibole, forming low-grade mineralization with Ti-V-poor magnetite in hornblendite. The complex displays high initial 87Sr/86Sr ratios of 0.706413–0.707341, negative εNd(t) values of −16.0 to −14.2 and negative εHf(t) value of −30.6 to −12.0, suggesting a parent magma derived from an enriched lithospheric mantle, with possible existence of amphibole-bearing pyroxenite veins within the source. During the Early Devonian, the retreat of the subducted Paleo-Asian oceanic slab as well as arc-continental collision along the northern NCC induced partial melting of the veins and eventually formation of the complex.

A Late Jurassic Epithermal Pb-Zn Deposit: Insights from Rb-Sr Dating of Quartz-Hosted Fluid Inclusions and Sphalerite Chemical Composition

The Kangjiawan Pb-Zn deposit, situated within the Shuikoushan polymetallic ore field in Changning, Hunan Province, China, is a large-scale Pb-Zn deposit unearthed in 1976. Based on detailed geological field investigations, this study presents the results of the Rb-Sr isotopic dating, electron probe microanalyses (EPMAs), and LA-ICP-MS analyses of the Kangjiawan Pb-Zn deposit in order to determine the ore-forming age and the occurrence of trace elements in sphalerite and thereby constrain the genesis of the deposit. The Rb-Sr dating of quartz-hosted fluid inclusions yielded an Rb-Sr isochron age of 150 ± 4 Ma, with an initial 87Sr/86Sr ratio of 0.71101 ± 0.00008 (MSWD = 1.1), suggesting that the Pb-Zn mineralization of the Kangjiawan deposit took place during the Late Jurassic, coeval with the magmatic activities within the ore field. EPMA and LA-ICP-MS analyses showed that Fe, Mn, and Cd were primarily incorporated into the sphalerite lattice through isomorphous substitution. Specifically, Fe and Mn substituted for Zn, whereas Cd replaced both Fe and Zn. Other elements such as Cu, Sb, and Sn occurred within the sphalerite lattice through mineral micro-inclusions or isomorphic substitution. EPMAs and LA-ICP-MS results showed that the FeS contents in sphalerite were less than 14.33%, with corresponding ore-forming temperatures below 259 °C. The LA-ICP-MS results showed that sphalerites from the Kangjiawan Pb-Zn deposit had relatively high Ga/In ratios ranging from 0.01 to 144, providing further support for medium-to-low-temperature mineralization. The trace element compositions of sphalerites from the Kangjiawan Pb-Zn deposit exhibit skarn-type characteristics, suggesting a potential association with contemporary magmatic activities within the Shuikoushan ore field. During the Late Jurassic, extensive granitic magmatic activities occurred in the study area. At the late stage of magma crystallization, hydrothermal fluid containing Pb and Zn precipitated at medium-to-low temperatures and generated the Kangjiawan Pb-Zn deposit.

Regional trends and petrologic factors inhibit global interpretations of zircon trace element compositions

The trace element composition of zircon reveals information about the melt that they are derived from, as such, detrital zircon trace element compositions can be used to interrogate melt compositions, and thus the evolution of the continental crust in time and space. Here, we present a global database of detrital zircon compositions and use it to test whether average global trends for five common petrogenetic proxies truly represent secular changes in continental evolution. We demonstrate that the secular trend is broadly comparable across continental regions for Ti-in-zircon temperatures, but for other trace element ratios interrogated, secular trends are highly variable between continental regions. Because trace element ratios result from multiple petrologic variables, we argue that these petrogenetic proxies can be overinterpreted if projected to global geologic processes. In particular, we caution against the interpretation of crustal thickness from trace elements in zircon, and we argue that our results negate current hypotheses concerning secular changes in crustal thickness.

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-temperature data indicates 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.

First identification of the Early Cretaceous Suolong Cu-rich porphyry in the Geji area, central Tibet: A new clue for regional porphyry Cu exploration

The Tibetan Plateau hosts the majority of porphyry Cu deposits in China. There are two large metallogenic belts, the Gangdese and Bangong-Nujiang belts, in the Lhasa Terrane, Central Tibet. The Lhasa Terrane experienced multistage magmatic activity from the Mesozoic to Cenozoic, and the subaerial volcanic areas of the western part of the terrane are regarded as favorable targets of porphyry Cu deposits. In this paper, we describe the geology of our newly identified Early Cretaceous Suolong Cu-rich porphyry in the western Lhasa Terrane and present new U–Pb ages, trace element and Hf isotopic compositions of zircon and whole-rock elemental and Sr–Nd isotopic compositions. The Suolong porphyry contains zircon grains with ages ranging from 136 to 135 Ma, εHf(t) values ranging from −1.5 ∼ +2.7 and logfO2 values ranging from −16.27 ∼ −9.92. Geochemically, the porphyry rocks are peraluminous in nature, with whole-rock εNd(t) values of −5.7 ∼ −5.4. We infer that the Suolong porphyry originated from a mixture of ∼53 % enriched lithospheric mantle and ∼47 % ancient lower crustal melt, triggered by the roll-back of the northward-subducting Neo-Tethyan Ocean. The conditions of high oxygen fugacity and water content and tectonic transition promoted the formation of the Suolong Cu-rich porphyry, but the condition of a thinned crust may have constrained the mineralization scale of the Cu deposits. This new identification of Early Cretaceous mineralization event provides important clues for identifying new potential exploration targets for porphyry Cu deposits in the western segment of the Lhasa Terrane.

Tectono-metamorphic evolution of the Central Bundelkhand Craton, India from geochemistry and bulk composition modelling of amphibolite enclaves

The Bundelkhand Craton (BuC) represents a significant Archean terrane within the northern Indian Craton and yet its tectono-metamorphic evolutionary history remains relatively understudied. Our investigation involves detailed petrography, geochemistry, and bulk composition modeling of both garnet-bearing and garnet-absent amphibolites with a two-fold objective: (i) to constrain the protolithic nature and tectonic settings involved in the genesis of these rocks, and (ii) to propose a tectono-metamorphic evolutionary history for the BuC. The BuC amphibolites originate from basalt and andesitic-basalt protoliths. Their trace element compositions reveal negative anomalies in Nb, Ta, and Ti, while their rare earth element (REE) normalized patterns indicate enrichment in light REEs over heavy REEs. The basaltic protolith is interpreted to have formed during orogeny in a compressional tectonic regime at the active margins of island arcs in a subduction-related setting. This interpretation is supported by various discrimination plots for amphibolites, such as Nb/Th vs Zr/Nb, Zr vs Zr/Y, and Th/Nb vs Ce/Nb, as well as high Th/Yb and low Nb/Yb contents— all of which suggest an island arc setting influenced by subduction. These amphibolites have undergone three distinct phases of metamorphism, as evidenced by petrography, mineral chemistry, and bulk composition modeling. This interpretation is further supported by geochemical discrimination diagrams which indicate that a subduction tectonic setting was active during peak metamorphism. During the pre-peak phase, the garnet-bearing amphibolites experienced pressure and temperature conditions ranging from 6.25 to 6.5 kbar and 580 to 590ºC, while the garnet-absent amphibolites underwent conditions from 5.0 to 5.8 kbar and 400 to 450ºC. Peak metamorphism was observed at pressures ranging from 6.8 to 7.4 kbar and temperatures from 760 to 805ºC for the garnet-bearing amphibolites, and at pressures from 7.0 to 7.4 kbar and temperatures from 785 to 810ºC for the garnet-absent amphibolites. The metamorphic retrograde conditions for the garnet-bearing amphibolites are defined by P-T conditions ranging from 4.45 to 4.75 kbar and 585 to 615ºC, while for the garnet-absent amphibolites, it ranges from 3.1 to 4.0 kbar and 620 to 710ºC. The mineral assemblages and P-T conditions delineate a clockwise P-T path for both, garnet-bearing and garnet-absent amphibolites from the Babina and Mauranipur regions. This suggests that the rocks underwent a burial process amid subduction tectonic settings in an arc-related environment, followed by a decompression stage that brought them to the surface.

The Origin and Evolution of Rare Earth Element Mineralization in the Muluozhai Deposit (Sichuan, China): Insights from Mineralogical, Trace Element, and Sr-Nd-Pb-C-O-Ca Isotope Data

Abstract Carbonatite complexes are globally significant sources of rare earth elements (REEs); however, mechanisms governing REE deposition in various tectono-lithologic settings, encompassing host rocks, wall rocks, ore-controlling structures, and metasomatism, remain inadequately understood. The Zhengjialiangzi mining camp, situated within the extensive Muluozhai deposit (containing 0.45 million metric tons [Mt] at 4.0 wt % REE2O3) in the northern segment of the Mianning-Dechang belt, Sichuan (southwestern China), is characterized by a complex vein system that evolved within metamorphosed supracrustal rocks of the Yangxin and Mount Emei Formations. The mineralization is coeval with Oligocene intrusions of carbonatite and nordmarkite at ~27 Ma. The major gangue minerals include fluorite, barite (transitional to celestine), and calcite, with bastnäsite serving as the primary host for REEs in all analyzed orebodies. Several other accessory to minor minerals were identified in the ore veins, including some that had not previously been known to occur in the Muluozhai deposits (e.g., thorite and pyrochlore). The stable isotopic (C-O-Ca) and trace element compositions of calcite, along with whole-rock data, suggest that carbonate material was derived from the mantle and subsequently reequilibrated with the Yangxin marbles. The radiogenic isotope (Sr-Nd-Pb) compositions of vein material remained unaffected by wall-rock contamination and suggest a mantle source influenced by crustal recycling, consistent with other REE deposits hosted by carbonatite and nordmarkite in the region. The combined petrographic and geochemical evidence suggests derivation of Muluozhai mineralization from a carbonatitic source and interaction of carbonatite-derived fluids with wall rocks, xenoliths, and early-crystallizing mineral phases, particularly barite.

A multidisciplinary approach to describe population structure of Solea solea in the Mediterranean Sea

Investigating marine species population structure in a multidisciplinary framework can reveal signatures of potential local adaptation and the consequences for management and conservation. In this study we delineate the population structure of common sole (Solea solea) in the Mediterranean Sea using genomic and otolith data, based on single nucleotide polymorphism (SNPs) markers, otolith shape and otolith trace element composition data. We correlated SNPs with environmental and spatial variables to evaluate the impact of the selected features on the actual population structure. Specifically, we used a seascape genetics approach with redundancy (RDA) and genetic-environmental association (GEA) analysis to identify loci potentially involved in local adaptation. Finally, putative functional annotation was investigated to detect genes associated with the detected patterns of neutral and adaptive genetic variation. Results from both genetic and otolith data suggested significant divergence among putative populations of common sole, confirming a clear separation between the Western and Eastern Mediterranean Sea, as well as a distinct genetic cluster corresponding to the Adriatic Sea. Evidence of fine-scale population structure in the Western Mediterranean Sea was observed at outlier loci level and further differentiation in the Adriatic. Longitude and salinity variation accounted for most of the wide and fine spatial structure. The GEA detected significant associated outlier loci potentially involved in local adaptation processes under highly structured differentiation. In the RDA both spatial distribution and environmental features could partially explain the genetic structure. Our study not only indicates that separation among Mediterranean sole population is led primarily by neutral processes because of low connectivity due to spatial segregation and limited dispersal, but it also suggests the presence of local adaptation. These results should be taken into account to support and optimize the assessment of stock units, including a review and possible redefinition of fishery management units.

Trace Element and Isotope Geochemistry of Tschicoma Formation Intermediate Composition Dome Complexes, Jemez Mountains Volcanic Field, New Mexico, USA

Abstract Repeated intrusions of mafic magma have long been known to be a driver of long-lived magmatic systems. Although the importance of mafic recharge of silicic magma systems is well-documented in igneous petrology, the origin of this recharge magma is sometimes obscure. By examining the pre-caldera intermediate dome complexes of the Tschicoma Formation and their relationship to a dacitic recharge event into the Tshirege Member of the Bandelier Tuff, we aim to better understand the origin of mafic recharge events into the Bandelier magma chamber of Valles caldera, and the relationship between different stages of volcanic activity within the broader Jemez Mountains volcanic field (JMVF). Based on major, trace element and radiogenic isotopic data, we divide the Tschicoma Formation into three geochemical groups with similar petrologic evolutionary paths. The Cerro Grande, Cerro Rubio and Pajarito Mountain volcanic dome complexes form group A and have assimilated various amounts of a granitoid crustal component with low εNd, εHf and radiogenic Pb. Group B consists of the Sawyer Dome, Rendija Canyon and Caballo Mountain dome complexes, which have principally evolved through different degrees of fractional crystallization of the same parent magma, itself a result of complex interactions of a mafic mantle-derived magma with the crust. The dacite domes and flows around Tschicoma Peak and the newly described Cañada Bonita dacite form group C and are the result of mixing of Rendija Canyon magma with mafic recharge magma which is preserved as distinct mafic enclaves. At a later stage of the JMVF, during the eruption of the Tshirege Member, distinctive hornblende–dacite pumices formed as a result of the influx of more mafic recharge magma into the system, which mobilized a pre-existing dacite intrusion and injected it into the Tshirege rhyolite ( Stimac, 1996; Boroet al.,2020). Based on trace element and isotopic compositions, we propose that dacite which was injected into the Tshirege magma chamber was related to the earlier-erupted Tschicoma Formation and itself represents a mixing product of Tshirege rhyolite and a precursor to the Tschicoma dacites. This implies that the Tschicoma magmatic system was long-lived yet dormant during the eruption of the Otowi Member of the Bandelier Tuff, then was reactivated shortly before the Tshirege eruption, temporarily co-existing and interacting with the Bandelier system as it erupted.