Anomalous Enrichment Research Articles

Anomalous tellurium enrichment associated with gold mineralization: A mineralogical and isotopic study of the Yongxin Te-Au deposit, northeast China

The Yongxin tellurium-gold (Te-Au) deposit, a large epithermal deposit in the Duobaoshan polymetallic metallogenic belt (DPMB) within eastern section of the Central Asian Orogenic Belt (CAOB), is mainly hosted by syenogranite and mylonite. However, the Te-Au occurrence, precipitation mechanism and genesis in this deposit remain elusive. In this study, pyrite, the primary host of Te-Au mineralization, was studied utilizing multiparametric techniques such as scanning electron microscope (SEM), electron probe microanalysis (EPMA), in-situ laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) and femtosecond laser ablation coupled multi-collector inductively coupled plasma mass spectrometry (fs LA-MC-ICP-MS). The results show that there are three generations of pyrite termed here as Py1, Py2 and Py3. The coarse euhedral Py1 and fine vein Py2 contain negligible to low contents of Te and Au, whereas the anhedral aggregated Py3 with porosity and grain boundary (GB) shows the highest concentrations of Te and Au. Representative LA-ICP-MS profiles show that Te-Au occurs either as solid solution in the Py1 and Py2 or submicroscopic Au-Ag-Te-Bi inclusions, electrum and native gold in Py3. Thermodynamic data of telluride and sulfide show that the Te-Au was deposited under relatively oxidizing conditions with values of log f Te2 ranging from −15.2 to −11.2 and log f S2 from −16.7 to −12.1. at 200 °C. We infer that fluid mixing and fluid-rock interaction were the dominant mechanisms that triggered the precipitation of Te-Au in the Yongxin Te-Au deposit. Geochemical and geochronological data indicate that the likely source of Te is Te-rich oceanic sediments originating from the Western Pacific Plate. Pyrite and telluride from the gold deposits can be potential targets for Te exploration in the DPMB.

Abnormal densification of dislocation networks during creep deformation in a single crystal superalloy with a small γ/γ′ lattice misfit

Generally, with a large lattice misfit, dislocations tend to move smoothly via cross-slip in γ channels, and rapidly reorient themselves from the 〈110〉 to 〈100〉 direction on the surface of γ′ cuboids to form complete networks in single-crystal superalloys. However, in this study, dense and complete dislocation networks also formed in a single-crystal superalloy with a small γ/γ′ lattice misfit during high-temperature creep deformation. The abnormal densification of dislocation networks was proven to be related to the anomalous enrichment of W and Ta in γ′ phases during the secondary creep stage. Microstructural analysis suggested that anomalous enrichment contributed to an elevated antiphase boundary energy (APBE) of γ′ phases and led to more vacancies within the γ phase, promoting dislocation climb. The higher APBE of γ′ phases impeded dislocations from cutting into γ′ phases, providing enough time for interfacial dislocations to climb through vacancies and rotate to form dense dislocation networks.

Anomalous cobalt enrichment in pyrite from an altered mafic dike in the Linglong gold deposit, Jiaodong Peninsula, China: Mechanisms and implications

Traditionally, gold deposits in the Jiaodong gold province of China have been regarded as gold-only deposits lacking economic base metals. However, recent studies found some cobalt (Co) enrichment in those deposits. The mechanisms of this Co enrichment remain poorly understood. In this study, we identified a type of pyrite highly enriched in Co (concentrations up to 32800 ppm) at the Linglong gold deposit, Jiaodong gold province. The pyrite was collected from a hydrothermally altered mafic dike contacting with gold ore veins. To decipher the enrichment mechanisms of Co, in-situ textural, elemental and sulfur isotopic analyses were conducted on the pyrite. The pyrite typically exhibits core-mantle-rim textures. The cores (Py-m1) have high Co concentrations (up to 5950 ppm) with homogeneous texture and elemental distribution, which could be the primary pyrite formed by pyritization of the mafic dike. The mantles (Py-m2) have the highest Co concentrations (up to 32800 ppm) and contain abundant mineral inclusions (chalcopyrite, galena, and sphalerite) and pores, showing the formation through coupled dissolution-reprecipitation (CDR) reactions. The rims (Py-m3) have low concentrations of Co (0.14–559 ppm) and show cubic shapes, forming directly from hydrothermal fluids. The δ34S values increase from the cores (4.2 ‰ to 9.1 ‰, mean of 8.0 ‰) to the mantles (8.9 ‰ to 11.9 ‰), but vary between the above two in the rims (4.2 ‰ to 12.2 ‰, mean of 9.0 ‰). The sulfur isotopic compositions of the Py-m are similar to those of pyrite (4.8 ‰ to 9.5 ‰) from the neighboring auriferous quartz-sulfide veins at Linglong in previous study. Combined with the geological and textural features, it is inferred that hydrothermal fluids during gold mineralization extracted abundant Co from the mafic dikes, leading to the primary enrichment of Co in the Py-m1. The Py-m1 was dissolved and re-precipitated during subsequent hydrothermal activities, forming Py-m2 with enhanced re-enrichment of Co. Basically, the Co-rich mafic dike provided the initial enrichment of Co while the gold-bearing hydrothermal fluids contributed to concentrate Co further. Considering the widespread mafic rocks and extensive hydrothermal activities during gold mineralization throughout the Jiaodong gold province, there might be a considerable Co resource formed through the above processes.

Links between hydrographic restriction, redox conditions, and organic matter accumulation in the Early Cambrian intrashelf basin, South China

There was a strong relationship between paleo-oceanic conditions and organic matter accumulation during the critical period of the Early Cambrian. The Yangtze Platform in South China provides an opportunity to study this relationship, but the basin architecture and paleo-hydrographic dynamics remain poorly understood, which hinders one’s understanding of the evolution in oceanic redox state and its relationship to organic matter accumulation. To fill the knowledge gap, a newly obtained data set from the Lower Cambrian Niutitang Formation shales (Late Cambrian Stage 2-Stage 3) of the intrashelf basin is used. Results show that the molybdenum–uranium covariation, along with the abnormally low Mo contents and Mo/TOC ratios in the anoxic (ferruginous and euxinic) Niutitang shales of the intrashelf basin, indicate a hydrographic circulation that is moderately to strongly restricted. The hydrographic evolution at different stages, influencing redox conditions to a certain extent, in conjunction with variations in primary productivity, controls the enrichment of organic matter. In particular, the relatively low sea level during Interval I (Late Stage 2) resulted in weak connectivity between the intrashelf basin and open ocean; this, coupled with high primary productivity and enhanced chemical weathering, formed stable stratified water (euxinic bottom-water) conditions that were favorable for organic matter enrichment. In contrast, Interval II (Early–Middle Stage 3) and Interval III (Late Stage 3) involved less organic matter enrichment due to weakened restricted hydrographic circulation (Interval II) and oxic bottom-water conditions (Interval III). This study highlights how hydrodynamic processes affected the marine environment during the Early Cambrian and reveals that sluggish oceanic circulation combined with high primary productivity led to anomalous enrichment of organic matter. This may be a common feature of basins with restricted hydrographic circulation in deep time.

Not so fast: Million-years of metal precipitation in Mississippi Valley type deposits inferred from in-situ petrochronology of hydrothermal carbonates

Mississippi Valley-type (MVT) deposits contain about 20% of global zinc resources and host critical raw materials crucial to the development of green technologies. Despite their economic and strategic importance, there is a lack of consensus on the duration of mineralizing fluid flow events in MVT systems. This study couples in-situ U-Pb dating with Sr-isotope and trace element analysis of syn- and post-ore gangue carbonates to establish: (1) timing and duration, (2) redox evolution, and (3) flow rates of mineralizing fluids in the world-class San Vicente Zn-(Pb) deposit (Peru). New radiometric ages bracket the crystallization of syn-mineralization dolomite, characterized by high Fe and Mn contents and Sr isotopic values overlapping with that of host carbonates, between 103.2 ± 4.1 Ma and 70.6 ± 5.6 Ma. This age interval reveals a direct genetic relationship between flow of mineralizing fluids and late Cretaceous Andean compressional tectonics. Basinal fluid expulsion coeval with known tectonic events continues in the district until Pliocene times, driving episodic crystallization of post-ore hydrothermal carbonates between 61.6 ± 9.3 and 2.7 ± 0.2 Ma. The low Mn and Fe content and high 87Sr/86Sr values characteristic of these post-ore, bedding-parallel and cross-cutting carbonate veins indicate a colder, oxidized environment. Our findings highlight the contribution of paired carbonate geochemistry and U-Pb geochronology in drawing links between tectonic events, fluid expulsion and the waxing and waning of mineralization potential in foreland basins. The results of this study challenge our understanding of timescales in MVT systems and imply that anomalous metal enrichment in basinal fluids over a short temporal interval is not a necessary precondition to form economic-sized, sediment-hosted Zn-Pb deposits. Rather, it is the coexistence of a focused fluid flow in an interconnected aquifer with suitable metal depositional mechanisms over a prolonged period of time (106–107 yr) that allows precipitation of economic amount of base metals at a specific site in the upper crust.

Giant Rare Earth Element Accumulation Related to Voluminous, Highly Evolved Carbonatite: A Microanalytical Study of Carbonate Minerals From the Bayan Obo Deposit, China

Abstract The giant Bayan Obo deposit in China represents the largest rare earth element (REE) resource in the world, but the mechanisms for its highly anomalous REE enrichment have long been controversial. The central debate concerns the nature and origin of the ore-hosting dolomite. In this study, a texturally constrained microanalytical study of carbonate minerals from the Bayan Obo ore-hosting dolomite is presented to resolve this controversy. The dolomite rocks contain two major components: the early-stage coarse-grained dolomite (CD) and the late-stage fine-grained dolomite (FD). The CD dolomite grains have C-O isotope ratios (δ13CVienna-PeeDee Belemnite (V-PDB): –4.8 to –3.3‰; δ18OVienna-standard mean ocean water (V-SMOW): 7.1 to 11.9‰) plotting in or adjacent to the primary igneous carbonatite field, with a narrow range of low 87Sr/86Sr ratios (0.70262–0.70327). The mantle-like C-O and Sr isotopes indicate that the coarse-grained dolomite rocks are magmatic in origin. Dolomite grains from the FD have experienced extensive hydrothermal alteration related to both REE mineralization and post-ore metamorphism of the Bayan Obo deposit. The domains of primary unaltered dolomite have high SrO and MnO contents that clearly distinguish them from sedimentary carbonates. The 87Sr/86Sr ratios of unaltered dolomite domains range from 0.70271 to 0.70473, with the majority lower than 0.7035, contrasting with higher 87Sr/86Sr ratios of Mesoproterozoic sedimentary carbonates globally. Thus, the primary unaltered fine-grained dolomite, the precursor to the FD, is also proposed to be a carbonatite. Compared with dolomite grains from the CD, most of the unaltered dolomite domains within the FD are more enriched in FeO and MnO and have higher δ13CV-PDB (-4.9 to 0.3 ‰) and δ18OV-SMOW (9.4 to 17.1 ‰) values. In addition, the FD contains abundant REE- and volatile-rich hydrothermal minerals and Fe-Mg carbonates, which are rare in the CD. The geochemical and mineralogical data in conjunction indicate that the melts forming the late-stage FD were much more evolved than those forming the early-stage CD. It is noteworthy that the unaltered dolomite domains within the FD have a wider range of 87Sr/86Sr ratios than those within the CD, which implies that the CD and FD, at least a proportion of them, are unlikely to have crystallized from the same progenitor magmas. Some FD was possibly the product of fractionation of less-evolved carbonatitic magma that generated the CD, whereas other FD crystallized from new pulses of magmas that were highly fractionated at depth. When compared with other carbonatite complexes, the Bayan Obo carbonatite suite is notable for having a large surface area (~48 km2 in outcrop) and containing an anomalously large proportion of highly evolved components. The voluminous evolved carbonatite clearly provided a basis for the accumulation of significant ore metals. Therefore, the giant-sized REE deposit is proposed to be associated with large-volume, highly evolved carbonatite at Bayan Obo.

An original set of nanometer-scale mineralogical analyses of cookeite and the implications for Li enrichment: No. 21 coal, Mengjin Mine, western Henan

Critical elements in coal deposits, such as lithium (Li), have attracted attention recently due to their economic value. Many studies have suggested that the high enrichment of Li in coals is predominantly associated with cookeite, a Li–bearing chlorite mineral of hydrothermal origin. However, the identification of cookeite in coal has primarily relied on indirect methods, owing to the low atomic number of Li, which presents significant challenges for precise observation. The Shanxi Formation No. 21 coal in North China is enriched in Li. This study established a nanometer–scale mineralogical analytical technique (including high–resolution transmission electron microscopy (HR–TEM), fast Fourier transformation (FFT), and standard mineral simulation single-crystal diffraction (SSCD)) for the identification of the cookeite and evaluated the Li enrichment mechanism and recovery in this coal (low–volatile bituminous to semi–anthracite) based on a model for the Li mineralization. The Li content of the No. 21 coal ranges from 25.2 to 203 ppm. The Li content shows a strong correlation with the ash yield, Al2O3, SiO2, and detrital elements, indicating a dominant aluminosilicate affinity and detrital origin. The major aluminosilicate minerals in coal are kaolinite, chlorite, and illite. The geochemical indicators (the Al2O3/TiO2 ratio and its relationships with the Zr/TiO2, Nb/Y, and Nb/Yb ratios) indicate that the sediment sources are determined to be intermediate–felsic igneous rocks, probably the Mesoproterozoic moyite (a type of K– feldspar granite) in the Yinshan Oldland. Additionally, the coal can be divided vertically into three sections (Sections I, II, and III), corresponding to three stages of peat formation. Overall, from Section I to Section III, the degree of detrital input increased, and the groundwater and marine influences strengthened and weakened, respectively. Section II exhibits anomalous Li enrichment mainly associated with reducing environments and the geochemical barrier caused by the interaction between infiltrating seawater and groundwater. The detrital kaolinite assemblage with authigenic minerals such as secondary REE–rich minerals (bastnasite), chamosite, and quartz, as well as the REY enrichment patterns, suggests that the No. 21 coals, mainly Section II, may have existed the hydrothermal alteration. Cookeite is identified primarily in Section II and coexists with kaolinite based on TEM observations, suggesting that the cookeite is of hydrothermal origin and formed from pre–existing Li–rich kaolinite. Most samples from Section II meet the mining grade of Be–Li–Nb–Ta ore deposits (Li2O > 0.2%). Thus, this study offers valuable insights into the extraction and recovery of Li from coal combustion residues, particularly when cookeite is the primary Li–bearing mineral.

Anomalous patterns of clay minerals in fault zones

The anomalous enrichment of clay minerals in fault zones is considered a key factor affecting the seismic behavior of faults, fault permeability, and mineralization. This process also weakens the rock strength and triggers deformation, instability, and geological disasters. Nevertheless, the geological factors affecting the growth and anomalous enrichment patterns of clay minerals in fault zones are not systematically understood. In this study, the anomalous enrichment patterns of clay minerals within 220 natural faults are investigated (detailed information can be found in Appendix A). The main geological factors and processes affecting the anomalous enrichment of clay minerals in fault zones are revealed. The main formation modes and occurrence forms of the clay minerals in fault zones are investigated. The anomalous patterns of clay minerals in fault zones are classified into four categories and eight types, i.e., the felsic anomaly category (illite type and kaolinite type), mafic anomaly category (chlorite type), ultramafic anomaly category (smectite type, serpentine + talc type, vermiculite type, and palygorskite + sepiolite type), and argillaceous anomaly category (mixed-layer type). The 220 case studies include different types of faults and fault rocks. Thus, the results are promising for a wide range of engineering geological applications, e.g., analysis of fault activity and permeability changes and studying the genetic mechanisms of geological disasters near faults.

Natural enrichment of Cd and Tl in the bark of trees from a rural watershed devoid of point sources of metal contamination

To help understand the bioaccumulation of Cd and Tl in beaver tissue, we examined the enrichment of these metals in vegetation available to the animals. Bark was collected from 40 species of trees and shrubs, along with a complete soil weathering profile, within a small watershed devoid of trace metal contamination. Weathering resulted in a 5x enrichment of Cd in the soils relative to the underlying sediments, and a 6x Tl depletion: while Cd was lost from calcite and accumulates in the organic matter and oxyhydroxide fractions, Tl occurred only in the residual fraction. Soil processes alone, however, cannot explain the anomalous concentrations and enrichments of Cd in willow and poplar which contain up to 8.5 mg/kg Cd. The concentrations of Cd and Tl in the dissolved fraction (<0.45 μm) of the Wye River are similar (1.2 ± 0.4 and 1.6 ± 0.1 ng/L, respectively), and are taken to estimate their bioavailability in soil solutions. Normalizing the Cd/metal ratios in bark to the corresponding ratios in water yields the Stream Enrichment Factor: this novel approach shows that all plant species are enriched in Cd relative to Ni; 33 relative to Cu, 13 relative to Zn, and 7 relative to Mn. Thus, many plants preferentially accumulate Cd, especially willow and poplar, over these essential micronutrients. Clearly, the enrichment of Cd over Tl in bark is not a reflection of differences in bioavailability, but rather on the preferential uptake of Cd by the plants. The profound natural bioaccumulation of Cd in the bark of willow and poplar, the two favourite foods of the beaver, has ramifications for the use of these aquatic mammals as biomonitors of environmental contamination, as well as for the direct and indirect consumption of bark for traditional food and medicine.

Mineralogical study on the distribution regularity of niobium in various types of ores in the giant Bayan Obo Fe-REE-Nb deposit

The Bayan Obo Fe-REE-Nb deposit is the largest rare earth deposit in the world, which also contains huge amounts of niobium resources, hosting 83% of industrial reserves in China. The previous researches focused on the REE mineralogy, mineralization age and REE source, whereas only a few studies paid attention to the genesis of Nb mineralization. The REE and Nb might present systematic mineralization difference as the degree of REE and Nb mineralization is distinct in different types of ores in host dolomite. Many complicated factors such as low grade, fine-grained dissemination and complex mineral composition are the main obstacles to hinder the effective utilization of Nb. In this study, a variety of niobium-bearing minerals have been identified, including aeschynite, fergusonite, columbite, pyrochlore, fersmite, baotite, and ilmenorutile. The distribution regularity of niobium in various types of ores in the giant Bayan Obo Fe-REE-Nb deposit is asserted. In massive Nb-REE-Fe ore and dolomite-type Nb-REE-(Fe) ore, niobium-bearing minerals are represented by columbite, while niobium mineralization in aegirine-type Nb-REE-Fe ore is characterized by pyrochlore and aeschynite. The major niobium-bearing mineral in the riebeckite -type Nb-REE-(Fe) ore and fluorite-type (banded) Nb-REE-Fe ore is aeschynite, and major niobium-bearing mineral in biotite-type Nb-REE-Fe ore and diopside-type niobium ore is fergusonite. The μ-XRF results and SEM observations display that columbite contains dolomite, magnetite and monazite inclusions and show obvious genetic links with apatite. Columbite, apatite and magnetite in massive Fe-REE-Nb ore and dolomite-type Nb-REE-(Fe) ore occur at same mineral generation, both having magmatic origins. Pyrochlore from aegirine-type Fe-REE-Nb ore also showsclose genetic relationship with apatite, which is formed by fractional crystallization during the magmatic stage of carbonatite. Aeschynite in fluorite-type (banded) Fe-REE-Nb ore, riebeckite-type Nb-REE-(Fe) ore, and fergusonite in biotite-type Fe-REE-Nb ore and diopside-type niobium ore are large in grain size and have hydrothermal origins. Moreover, intensive Nb mineralization in a series of ores related to fluoritization and alkali-metasomatism demonstrates the critical role of hydrothermal process in niobium enrichment in the Bayan Obo deposit. Fluid-rock interaction leads to the generation of alteration minerals, such as fluorite, biotite and aegirine, and contributes to a slash of K, Na and/or F in hydrothermal fluids, facilitating precipitation of niobium-bearing minerals. By using scanning electron microscope (SEM), X-ray energy dispersive analysis (EDS), Micro-XRF spectral analysis (μ-XRF) and TESCAN Intergrated Mineral Analysis (TIMA), detailed mineralogical study on niobium occurrence and typical niobium mineral compositions in various types of Fe-REE-Nb ores was conducted to provide an important reference for mineral processing and niobium prospecting and give a deeper understanding of the niobium anomalous enrichment mechanism of the Bayan Obo Fe-REE-Nb deposit.

New Data on the Rock and Mineral Composition of Kharchinsky and Zarechny Volcanoes (Central Kamchatka depression): Heterogeneity of the Mantle Source and Peculiarities of Magma Evolution in Crust

The Kharchinsky and Zarechny volcanoes and the Kharchinsky Lake zone of monogenetic cones are unique eruptive centers of magnesian lavas located above the northern margin of the Pacific Plate subducting beneath Kamchatka. This work presents new geochemical data on the composition of rocks (55 samples) and minerals (over 900 analyses of olivine, pyroxenes, amphibole, and plagioclase) of these centers analyzed by XRF and LA-ICP-MS (rocks) and electron microprobe (minerals). Most of the studied rocks are represented by magnesian (Mg# = 60–75 mol. %), medium-K basalts and basaltic andesites. Moderate-magnesian (Mg# = = 52–59 mol. %) basaltic andesites are present among the monogenic cones of the Kharchinsky Lake. The rare rock varieties include high-K basalts-basaltic andesites of dikes in the center of the Kharchinsky volcano and magnesian andesites (Mg# = 58–61 mol. %) of the extrusions of Zarechnу volcano. The distribution of trace element contents in these samples demonstrates the enrichment of large-ion lithophile elements, light REEs and depletion of high field strength elements and heavy REEs typical of arc rocks. High-K basalts and basaltic andesites show anomalous enrichment in Ba (1000 ppm), Th (3.8 ppm), U (1.8 ppm), Sr (800 ppm, Sr/Y 50) and light REE (La 20 ppm); their compositions are close to those of low-Si adakites. Basalts and basaltic andesites contain high-Mg olivine phenocrysts (up to Fo92.6) and clinopyroxene (Mg# up to 91 mol. %). The rocks show petrographic and geochemical signs of fractional crystallization along with the processes of mineral accumulation and magma mixing. Some of the olivine phenocrysts show high NiO contents (up to 5000 ppm) and elevated Fe/Mn ratio (up to 80), interpreted as evidence of participation of the pyroxenite source in the magma generation processes. The use of Ca/Fe and Ni/Mg ratios allowed us to distinguish the composition fields and evolution trends of olivines associated with different sources – peridotite and pyroxenite, formed by the reaction of mantle wedge peridotites and high-Si melts of the subducted oceanic crust. The new data are consistent with other evidence of melting of the subducted Pacific plate edge beneath the northern part of the Central Kamchatka depression at the Kurile-Kamchatka and Aleutian subduction zone junction and testify to significant heterogeneity of the mantle in this area.

Anomalous Enrichment of As and Hg in Underground Coal Dust: A Case from Xishan Coalfield, Shanxi Province, North China.

Coal dust is an important source of coal workers' pneumoconiosis, which is harmful to the health of underground workers. The coal dust samples were directly collected using a coal dust sampler from four major production positions in the underground coal mine. The particle size distribution, mineralogy, and occurrence of As and Hg in the coal dust samples were investigated. The results indicated that the contents of As and Hg were depleted or normal in the parent coal samples compared with the average values of C-P coal in North China and Chinese coal, but they were anomalously enriched in coal dusts. The concentrations of As and Hg in the coal dust samples studied are greater than the values of the elements in the parent coal. The As content in the coal dust samples studied is about one to three orders of magnitude above the parent coal value and the Hg content in the studied coal is 1.28 to 20.28 times higher than the parent coal value. The modes of occurrences of As and Hg were studied by sequential chemical extraction in combination with field emission scanning electron microscopy-energy dispersive spectroscopy (FESEM-EDS) and high-resolution transmission electron microscopy-EDS (HRTEM-EDS). The occurrence of As is dominated mainly by pyrite and secondarily by carbonate and silicate in the coal dust samples. Pyritic Hg and organic Hg may be the dominant forms in mining face and heading face samples, and carbonate and pyritic Hg are the main forms in rocks roadway and return airway samples. It is considered that the mechanochemical effect resulted in the formation of surface active sites and modification of the morphology. Harmful trace elements, such as As, Cd, Hg, Se, Pb, Co, Sb, and Tl, and minor grains associated with nanominerals that bear much hazardous elements, could easily be originally fractionated or adsorbed by airborne particulates. This research aims to provide a theoretical basis for the prevention of occupational disease and underground environmental evaluation.

Origin and evolution of vanadium‐rich oxide and titanite phases in lamprophyre and mafic dykes from the Nuapada diamondiferous Lamproite field, BastarCraton‐EasternGhats Mobile belt contact, India: Metallogenic and geodynamic implications

Transitional boundaries of the craton and mobile belt mark diverse and long‐term tectono‐thermal events like hot and cold lithospheric contact, back‐arc‐type subduction, and also constitute a favourable locale for metallogeny. The exact nature and origin of such metallogenic enrichment in the lithospheric mantle source beneath contact zones are still uncertain. The contact of Bastar Craton and the Eastern Ghat Mobile Belt (EGMB), India, provides an ideal geological setup to study the metallogenic enrichment processes. In this study, we present a detailed petrographic and mineralogical investigation of various iron oxide phases and titanites in spatially and temporally distinct lamprophyre and mafic dykes from the diamondiferous Nuapada Lamproite Field (NLF) at the contact between Bastar Craton and EGMB. Diverse textural assemblages of oxides, namely, trellis, sandwich‐type exsolutions and reaction–replacement, are widespread. Ilmenites, magnetites and titanites from the mafic dykes as well as lamprophyre exhibit an anomalous enrichment of vanadium (V2O3up to 3.7 wt%), whereas ilmenites are also characterized by their elevated manganese content (MnO up to 3.8 wt%). Mineral chemistry‐based plots and thermo‐oximetric studies suggest the magmatic origin of iron oxides belonging to the Fe–Ti–V‐type ore in which partitioning and sequestration of the elements were controlled by differential crystallization, exsolution and fractionation rather than any imprints of contamination. Multiphase sequestration of vanadium as well as manganese in lamprophyre and mafic dykes, separated in space as well in relative depths of origin, signifies the presence of a fertile mantle. The role of subduction‐derived metasomatized fluids as a causative factor of vanadium metallogeny in this domain is evaluated. Low‐Mg and high‐Mn ilmenites of this study are consistent with the reported occurrences of diamonds from the NLF and adjoining areas of the Bastar Craton.

Discovery of anomalous molybdenum enrichment in Ordovician and Silurian stone coal: Relevance, origin and recommendations

Molybdenum (Mo) is a strategic element but has a notably low concentration at the Earth's surface. Consequently, competition for molybdenum resources at the national strategic level has begun to emerge, and in recent years, large-scale mining has led to the gradual depletion of molybdenum deposit resources. Here, thirty-four element enrichment patterns of Ordovician and Silurian stone coals in central China are reported. Molybdenum is the most enriched element, with an average of 208 mg/kg (58.2–440 mg/kg), which is 99 times the global hard coal average, and this molybdenum enrichment is associated with Ba–Ga–U–Cr–Na–K–-Cu–Se–Zn enrichment and elevated SiO2, CaO, K2O, MgO, Na2O, MnO and P2O5 concentrations. These analyses reveal four stone coal samples with molybdenum concentrations of 260, 312, 403 and 440 mg/kg, which meet the grade for the molybdenum mineral exploitation formulated standard, indicating that the Ordovician and Silurian stone coal deposits should be considered promising alternative sources of molybdenum. The crude reserve estimate of molybdenum is approximately 29.2 × 104 tons. The anomalous molybdenum in the studied stone coal was sourced from a complex combination of hydrothermal fluids, original biomass and terrigenous materials. The unique paleogeographic location and geological structure in central China resulted in the anomalous molybdenum concentrations in the stone coal forming at that time, producing a unique type of coal-hosted molybdenum deposit. Future studies will consider the ecological effects of the molybdenum extraction mode and the cost savings effects of extracting molybdenum from stone coal. A comprehensive utilization plan is also needed. Next, a thorough study of molybdenum exploration related to black rock series must be performed to increase the total molybdenum resources and support Chinese international competitiveness.

Microstructural evolution of Ti2ZrHfV0.5Mo0.2 refractory multi-principal alloy under low-energy, high-flux He ion irradiation

The irradiation response of refractory multi-principal element alloys (RMPEAs) has gained increasing attention for the potential applications in future fusion devices. In controlled fusion reactors, plasma-facing materials have to suffer continuous low-energy high flux helium (He) ion irradiations. During high flux He irradiation, vacancy-interstitial pairs can be generated through trap mutation mechanism even without cascade collision. To simplify the model, Ti2ZrHfV0.5Mo0.2 RMPEA was irradiated with 50 eV He+ (less than the minimum He displacement energy of the alloy EdTi = 67 eV) under 1200 K to various fluences of 5 × 1024 - 1 × 1026 ions/m2, and the microstructural evolution was investigated. In the irradiated RMPEA, the intense sputtering of Ti, the growth and degradation of fuzz mainly composed of Zr, Hf elements on the surface, as well as the formation of V, Mo enriched band and high density large He cavities in the subsurface layer were observed. Although the sputtering threshold energy for He of V is similar to that of Ti (ETi = 24 eV, EV = 29 eV), V showed anomalous enrichment in the subsurface layer. Moreover, unlike the W fuzz growth process, the adatoms used to form fuzz in Ti2ZrHfV0.5Mo0.2 were derived from the Zr, Hf atoms diffusing through the vacancy-solute exchange mechanism, rather than from the atoms formed by the loop-punching mechanism. The anomalous enrichment of V atoms and the different fuzz growth mechanism were attributed to (i) different migration rates for different species of atoms in the alloy under vacancy diffusion mechanism and (ii) the formation of AB2 (A = Ti, Zr, Hf; B = V, Mo) phase blocking the continued formation of prismatic dislocation loops mainly composed of V and Mo.

Biogeochemical cycling of dissolved manganese in the Arabian Sea

The study of marine biogeochemical cycling of Mn, a bio-essential trace metal, is crucial to decipher its relative role in controlling the production and diversity of marine phytoplankton. Furthermore, Mn oxides and oxyhydroxides act as sinks for other trace elements in the water column, and Mn redox cycling may exert a major control on the vertical distribution of these elements. Dissolved Mn (dMn) concentrations are measured along two GEOTRACES-India (GI) transects, GI05 and GI10, for a basin-wide investigation of biogeochemical controls on the dMn distribution in the Arabian Sea (AS). Surface dMn distribution shows a strong spatial gradient, with relatively dMn-rich levels in the eastern AS (3.4–5.7 nmol kg−1) compared to the central and western AS (1.2–2.3 nmol kg−1). This correlates with the higher model estimates of soluble Mn input from the atmospheric dust deposition in the eastern AS (∼1.5–2.0 times of input in the western and central AS), and probable additional Mn input from riverine discharge and shallow shelf region of the eastern AS. In the south-eastern AS, a correlated increase in surface dMn with a decrease in salinity indicates the Mn input by the advection of dMn-rich, low-salinity Bay of Bengal (BoB) surface waters to the AS under the influence of the Northeast Monsoon Current. Our mass balance estimates for dMn in the euphotic waters (upper 100 m) suggest important contributions from atmospheric Mn deposition (14–99% of the total estimated input flux), and dMn input/dilution (13–74% of the total estimated input or removal flux) due to lateral/vertical advective-eddy diffusive mixing. Mn-oxidation and passive scavenging are determined to be the dominant processes for the dMn removal (61–99%) from the euphotic zone (upper 100 m), while export via Mn bio-assimilation is comparatively negligible.In the AS denitrification zone, the observed dMn maxima in the upper thermocline depths (∼200–400 m) result from the in situ reductive dissolution of Mn oxides and oxyhydroxides, and lateral advective-eddy diffusive Mn flux from the reducing sediments of the western Indian margin. Outside the denitrification zone, in the northern and western AS, a shift of dMn maxima to the lower thermocline waters (∼500 m) indicates the change in the source region and dMn input from the reducing margins of the north (Pakistan Margin) and north-western AS (Oman Margin), intersecting the core of the oxygen minima at the depth range of 400–600 m.Deep water (>1500 m) dMn concentrations are low (<0.3 nmol kg−1) in most of the AS regions. Anomalous dMn enrichment in the deep waters is observed in the southern and western AS, presumably indicating the influence of hydrothermal plumes emanating from the active hydrothermal vents over the Carlsberg Ridge and spreading ridges in the Gulf of Aden. A correlated and localized increase in dMn and dAl levels close to the Murray Ridge hints at dMn input from the sediment resuspension over the ridge and subsequent Mn dissolution in low-oxygen waters (DO < 20 µM) and/or diffusive flux from the Mn-rich pore waters.

Proteomics-Compatible Fourier Transform Isotopic Ratio Mass Spectrometry of Polypeptides.

Measuring the relative abundances of heavy stable isotopes of the elements C, H, N, and O in proteins is of interest in environmental science, archeology, zoology, medicine, and other fields. The isotopic abundance measurements of the fine structure of immonium ions with ultrahigh resolution mass spectrometry obtained in gas-phase fragmentation of polypeptides have previously uncovered anomalous deuterium enrichment in (hydroxy)proline of bone collagen in marine mammals. Here, we provide a detailed description and validation of this approach and demonstrate per mil-range precision of isotopic ratio measurements in aliphatic residues from proteins and cell lysates. The analysis consists of proteomics-type experiment demanding sub-microgram amounts of a protein sample and providing concomitantly protein sequence data allowing one to verify sample purity and establish its identity. A novel software tool protein amino acid-resolved isotopic ratio mass spectrometry (PAIR-MS) is presented for extracting isotopic ratio data from the raw data files acquired on an Orbitrap mass spectrometer.

Trace Element Geochemistry of Alluvial TiO2 Polymorphs as a Proxy for Sn and W Deposits

The Segura mining field, the easternmost segment of the Góis–Panasqueira–Segura tin–tungsten metallogenic belt (north–central Portugal), includes Sn-W quartz veins and Li-Sn aplite-pegmatites, which are believed to be genetically related to Variscan Granites. Sediment geochemistry indicates granite-related Ti-enrichments, locally disturbed by mineralization, suggesting magmatic and metamorphic/metasomatic titaniferous phases. Therefore, Segura alluvial samples and the geochemistry of their TiO2 polymorphs (rutile, anatase, and brookite) were investigated, and their potential as exploration tools for Sn and W deposits was evaluated. The heavy-mineral assemblages proved to be good proxies for bedrock geology, and TiO2 polymorph abundances were found to be suitable indicators of magmatic and/or metasomatic hydrothermal processes. The trace element geochemistry of Segura’s alluvial rutile, anatase, and brookite is highly variable, implying multiple sources and a diversity of mineral-forming processes. The main compositional differences between TiO2 polymorphs are related to intrinsic (structural) factors, and to the P-T-X extrinsic parameters of their forming environments. Anomalous enrichments, up to 9% Nb, 6% Sn and W, 3% Fe, 2% Ta, and 1% V in rutile, and up to 1.8% Fe, 1.7% Ta, 1.2% Nb, 1.1% W 0.5% Sn and V in anatase, were registered. Brookite usually has low trace element content (&lt;0.5%), except for Fe (~1%). HFSE-rich and granitophile-rich rutile is most likely magmatic, forming in extremely differentiated melts, with Sn and W contents enabling the discrimination between Sn-dominant and W-dominant systems. Trace element geochemical distribution maps show pronounced negative Sn (rutile+anatase) and W (rutile) anomalies linked to hydrothermal cassiterite precipitation, as opposed to their hydrothermal alteration halos and to W-dominant cassiterite-free mineralized areas, where primary hydrothermal rutile shows enrichments similar to magmatic rutile. This contribution recognizes that trace element geochemistry of alluvial TiO2 polymorphs can be a robust, cost- and time-effective, exploration tool for Sn(W) and W(Sn) ore deposit systems.

Iron deposition during recovery from Late Devonian oceanic anoxia: Implications of the geochemistry of the Kawame ferromanganese deposit, Nedamo Belt, Northeast Japan

The Late Devonian, during which one of the “Big Five” Phanerozoic mass extinction events occurred, was one of the most important time intervals in Earth history. Nevertheless, the paucity of deep-sea records due to subduction has hampered elucidation of the pelagic environment during the Late Devonian in Panthalassa. However, ancient hydrothermal ferromanganese sediments, which were deposited on the abyssal seafloor and then accreted onto continental margins, are preserved as umber deposits and exposed in accretionary prisms. These sediments can provide key information to characterize the paleo-ocean. An Upper Devonian (Famennian) umber deposit is exposed in Kawame Quarry, Nedamo Belt, northeastern Japan. We investigated the bulk chemical composition and osmium isotopic ratio ( 187 Os/ 188 Os) of the Kawame umber to discuss the pelagic environment of the Panthalassa Ocean during the Late Devonian. The Kawame umber shows positive correlations between Fe content and the levels of P, V, Os, and rare earth elements, suggesting that hydrothermal Fe-oxyhydroxide particles adsorbed these elements from ambient seawater in the same way as hydrothermal ferromanganese sediments in the present-day ocean. Newly obtained initial 187 Os/ 188 Os values of Late Devonian seawater are 0.49–0.57, lower than that of present-day seawater (~1.06) and comparable to Paleogene and Late Cretaceous values. One of the most remarkable characteristics of the Kawame umber is its markedly high Fe levels (up to 90 wt%) compared to present-day seafloor hydrothermal ferromanganese sediments and younger umber deposits in Japanese accretionary complexes. Because seawater 187 Os/ 188 Os values were not notably different from those during the Paleogene and Late Cretaceous, anomalously vigorous hydrothermal activity in the Late Devonian is unlikely to have caused the increased Fe deposition. The rare earth element patterns of the Kawame umber (normalized to post-Archean average Australian shale) show weaker negative Ce anomalies than those of younger umbers and present-day hydrothermal ferromanganese sediments, suggesting that the Kawame umbers were deposited under less oxidizing conditions. Considering that many red beds were deposited at ~370 Ma, during recovery from the oceanic anoxic events (OAEs) of the Late Devonian (early Famennian), the anomalous Fe enrichment in the Kawame umber likely reflects enhanced oxidization and precipitation of abundant dissolved Fe during the post-OAE transition from anoxic to oxic conditions. • Geochemistry of Late Devonian Panthalassa was reconstructed from NE Japan. • Weakly negative Ce anomaly may reflect recovery from oceanic anoxia. • Reoxygenation of seawater caused Fe-enrichment in the Kawame umber. • Late Devonian seawater 187 Os/ 188 Os ratio was 0.47–0.57.

Geological Controls on Geochemical Anomaly of the Carbonaceous Mudstones in Xian’an Coalfield, Guangxi Province, China

The anomalous enrichment of the rare earth elements and yttrium (REY), U, Mo, As, Se, and V in the coal-bearing intervals intercalated within the carbonate successions in South China has attracted much attention due to the highly promising recovery potential for these elements. This study investigates the mineralogical and geochemical characteristics of the late Permian coal-bearing intervals (layers A–F) intercalated in marine carbonate strata in the Xian’an Coalfield in Guangxi Province to elucidate the mode of occurrence and enrichment process of highly elevated elements. There are two mineralogical assemblages, including quartz-albite-kaolinite-carbonates assemblage in layers D–F and quartz-illite-kaolinite-carbonates assemblage in layers A–C. Compared to the upper continental crust composition (UCC), the REY, U, Mo, As, Se, and V are predominantly enriched in layers A and B, of which layer A displays the REY–V–Se–As assemblage while layer B shows the Mo–U–V assemblage. The elevated REY contents in layer B are primarily hosted by clay minerals, zircon, and monazite; Mo, U, and V show organic association; and As and Se primarily display Fe-sulfide association. Three geological factors are most likely responsible for geochemical anomaly: (1) the more intensive seawater invasion gives rise to higher sulfur, Co, Ni, As, and Se contents, as well as higher Sr/Ba ratio in layers A–C than in layers D–F; (2) both the input of alkaline pyroclastic materials and the solution/rock interaction jointly govern the anomalous enrichment of REY; and (3) the influx of syngenetic or early diagenetic hydrothermal fluids is the predominant source of U, Mo, V, Se, and As.