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Discovered within the North Himalayan Metallogenic Belt (NHMB), the Zhaxikang Pb–Zn–Ag–Sb deposit stands as the sole super-large scale ore deposit in the region. This deposit holds significant quantities of Pb and Zn (2.066 million tons at 6.38% average grade), Ag (2661 tons at an average of 101.64 g/t), and Sb (0.235 million tons at 1.14% average grade), making it one of China's foremost Sb–polymetallic deposits. Stibnite represents the main carrier of Sb in this deposit and has been of great attention since its initial discovery. However, the trace element composition of stibnite in the Zhaxikang deposit has not yet been determined. This study carried out an analysis of the distribution patterns and substitution processes of trace elements within stibnite gathered from the Zhaxikang deposit, aiming to provide crucial information on ore-forming processes. Utilizing high-precision laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), we discovered that the studied stibnite is notably enriched in arsenic (~100 ppm) and lead (~10 ppm). Furthermore, the notably consistent time-resolved profiles suggest that elements such as Fe, Cu, As, In, Sn, Hg, and Pb predominantly exist as solid solutions within stibnite. Consequently, it is probable that the enrichment of Cu, Pb, and Sn in stibnite is due to isomorphic substitution reactions, including 3Pb2+↔2Sb3+, Cu+ + Pb2+↔Sb3+, and In3+ + Sn3+↔2Sb3+. Apart from that, Mn, Pb, and Hg with the spiky signals indicate their existence within stibnite as micro-inclusions. Overall, we found that the trace element substitutions in stibnite from the Zhaxikang Pb–Zn–Ag–Sb deposit are complicated. Incorporations of trace elements such as Pb, Cu, and In into stibnite are largely influenced by a variety of factors. The simple lattice structure and constant trace elements in studied stibnite indicate a low-temperature hydrothermal system and a relatively stable process for stibnite formation. [ABSTRACT FROM AUTHOR]

The conducted study shows that apatite is one of the key accessory minerals in the ultramafic-mafic rocks of the Khudolaz differentiated complex in the Southern Urals, including late pegmatoid gabbro. Petrographic and mineralogical investigations determine apatite crystallizing simultaneously with hornblende in pegmatoid gabbro from the residual water-saturated melt after plagioclase crystallization at a temperature of 990–800 °C, a pressure of 1–3 kbar, oxygen fugacity from −13.9 to −10.7, and water content of 3.9–5.5 wt. %. Pegmatoid gabbro apatite (Appg) from the Severnyi Buskun composite massif differs from early ultramafic-mafic apatite having a fairly high potential for sulfide-platinum metal mineralization in low chlorine and high fluorine content. Low sulfur concentrations in Appg testify to the lack of sulfide-platinum metal mineralization potential of pegmatoid gabbro, but a scanty potential for rare-metal mineralization (e.g., REE) is possible. Appg is quite poor in REE despite the enrichment of pegmatoid gabbros in REE relative to early ultramafic-mafics, which indicates REE accumulation in the fluid. The ratios of cerium and europium anomalies characterize the Appg crystallization under conditions transitional from the magmatic to the hydrothermal stage. Generally, apatite is a good indicator of the difference in the conditions of formation of late pegmatoid gabbro and early ultramafic-mafic rocks, which determines the importance of this mineral in mineralogical and petrological studies. [ABSTRACT FROM AUTHOR]

Gem-quality green vanadium grossular (var. tsavorite) is exclusively hosted in the Neoproterozoic Metamorphic Mozambique Belt (NMMB). The geochronology of tsavorite is limited until now, and the accurate crystallization age of the tsavorite in Kenya has remained unknown. Based on conventional gemological analyzing, by means of modern testing methods such as gemological analysis, UV-visible spectroscopy, Infrared spectroscopy, Raman spectroscopy, Electron probe, the spectral characteristics and chemical composition of tsavorite were determined, aiming to investigate the coloring elements of green garnets and trace the origin of tsavorite samples. The UV-Vis-NIR spectra and chemical composition analysis results show that vanadium and chromium are the main coloring elements in green tsavorite from Kenya. Combining the values of the δ18O (14.11‰) with the V/Cr ratio (around 4.4) of the tsavorite samples, the accuracy of the sample source has been identified. U–Pb dating of tsavorite from Kenya provides a concordant U-Pb age of 626.3 ± 4.6 Ma, in agreement with the weighted mean 206Pb /238U age of 625.9 ± 4.7 Ma (MSWD = 0.36), which indicated that Kenyan tsavorites were generated during the East African orogeny. Application of in situ laser U-Pb geochronology on gem-quality tsavorite to determine the mineralization time of Neoproterozoic Metamorphic Mozambique Belt of Kenya, which is the first step in characterizing the in situ dating analysis of gemstone tsavorite in Kenya mineral deposits [ABSTRACT FROM AUTHOR]

Simultaneous U–Pb and U–Th dating using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on the ca. 0.1 Ma Toya tephra and the ca. 0.08 Ma SS14-28 U–Th zircon reference material. In U–Pb dating, both Th/U and Pa/U partitioning between magma and minerals were considered. In U–Th dating, both abundance sensitivity and molecular interferences on 230Th were reevaluated. As a result, the Toya tephra yielded an accurate weighted mean U–Pb age of 0.103 ± 0.029 Ma (2σ) using zircon and monazite. Conversely, the SS14-28 zircon yielded an inaccurate U–Pb age (0.25 ± 0.10 Ma), which was attributed to low 206Pb signal intensity. Both the Toya tephra zircon and the SS14-28 zircon yielded accurate U–Th model ages of 0.108 ± 0.014 Ma and 0.078 ± 0.007 Ma, respectively. The agreement of U–Pb and U–Th ages for Toya indicates that simultaneous U–Pb and U–Th dating is possible and viable. The inappropriate age of SS14-28 U–Pb age and appropriate U–Th model age also indicates it is preferable to apply both U–Pb and U–Th dating simultaneously for young (<0.4 Ma) zircons to check internal consistency. The proposed double dating approach may be especially useful for small grains when it otherwise would be impossible to obtain multiple ages from a single grain. By adopting simultaneous U–Pb and U–Th dating using LA-ICP-MS, zircon crystallization ages as old as 4.5 Ga to as young as 0.1 Ma (or even younger) can be obtained in a quick and cost-effective manner with a reasonable (~5% at 1σ) uncertainty. [ABSTRACT FROM AUTHOR]

The Perron deposit, located in the northern part of the Archean Abitibi belt, bears some of the highest gold-grade mineralization for orogenic-vein-type deposits worldwide (High-Grade Zone: HGZ). More than 13 gold-bearing zones with different sulfide assemblages, hydrothermal alterations, and gold grades have been recently outlined, and they range from volcanogenic to orogenic in origin. In addition, seven zones are hosted in a restricted volume of ~1 km3, which is called the Eastern Gold Zone. Pyrite, sphalerite, pyrrhotite, and chalcopyrite—each from a different gold-bearing zone—were analyzed with LA-ICP-MS to decipher their genetic links, mineralizing processes, and temperature of formation. The temperatures calculated with the sphalerite GGIMFis thermometer range from 348 to 398 °C. All gold-bearing zones recorded volcanogenic hydrothermal inputs at different intensities, manifested by pyrrhotite. Pyrite was late-metamorphic and related to the orogenic gold system induced by the contact metamorphism of amphibolite facies. The pyrrhotite grains had very homogeneous trace element signatures in all zones, which is a characteristic of metamorphic recrystallization, exhibiting a loss of mobile elements (Au, Te, Bi, Tl, Sn, W, In) but high concentrations of Ni, Co, and As. Conversely, the pyrite was systematically enriched with all elements depleted from pyrrhotite, bearing five specific signatures of element enrichments: W, Tl, Sn, In-Cd-Zn, and Bi-Te-Au. For gold-rich zones (e.g., the HGZ), gold was linked to the Bi-Te-Au signature of pyrite, with Bi enrichment occurring at up to 72,000 times the background level in Archean shale pyrite. It was concluded that gold was transported, at least in part, as Bi-Te melts in the previously documented non-aqueous orogenic fluids, hence accounting for the very-high-grade gold content of the HGZ. Genetically, the metamorphism of primary gold-bearing volcanogenic mineralizations was the main source of gold during the overprinting of amphibolite (600 °C) in a metamorphically induced orogenic mineralizing event. A strong volcanogenic pre-enrichment is considered the main factor accounting for the gold endowment of the Eastern Gold Zone. [ABSTRACT FROM AUTHOR]

The Bou Dahar Pb-Zn district, located in the Moroccan High Atlas, is a typical carbonate-hosted Pb-Zn ore district (>30 Mt at 4 wt.% Pb, 4 wt.% Zn). In situ trace element analysis was performed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on galena and cerussite from different ore types. The galena is generally enriched in Ag and Sb, secondarily enriched in Cu, with a trace amount of Cd and As, but extremely depleted in Bi and Tl. The main substitution mechanism in galena is (Ag, Cu)+ + Sb3+ ↔ 2Pb2+, and at high Sb concentrations, the further substitution of 2Sb3+ + □ ↔ 3Pb2+ (where □ represents a vacancy) took place. Micro-inclusions of Cu-Sb-bearing minerals (such as tetrahedrite) and Ag-bearing minerals (such as acanthite) may exist in some situations. The features of trace elements in galena show the existence of different coupled substitutions in vein-related ore, breccia-related ore, and strata-bound ore. This suggests that the Bou Dahar district experienced multistage mineralization. The MVT model alone cannot fully explain the ore-forming process. The cerussite replacing strata-bound galena is enriched in Sr, Ba, Ag, and Cu, with minor Sb, As, and Tl. Strontium and Ba are directly substituted with Pb in the cerussite lattice. Copper and Ag are likely present in cerussite as nano-inclusions, which differs from the coupled substitution mechanism of the original galena. High concentrations of Ag may occur due to minor electrum inclusions. The enrichment of Ag, Cu, and Au in cerussite during the oxidation process may guide the optimization of ore processing, especially in extracting valuable trace/minor elements. [ABSTRACT FROM AUTHOR]

In this work, a reliable and robust in situ non-matrix-matched calibration method is proposed for element composition determination in scheelite samples. With external calibration against the silicate glass standard reference material NIST SRM 610, the concentrations of both major elements (Ca and W) and trace elements (Si, Fe, Mo, Y, rare earth elements, etc.) in scheelite are determined using an ArF 193 nm excimer nanosecond laser ablation-inductively coupled plasma mass spectrometer (LA-ICP-MS). Here, the ablation was performed by hole drilling under a helium (He) environment using a laser spot size of 35 μm and a laser repetition of 5 Hz, and the aerosols were then transported to a quadrupole ICP-MS by a mixture of He and make-up gas argon (Ar) with a total gas flow rate of 1.6 L/min. Results showed that there was no apparent matrix effect between the NIST SRM 610 and scheelite by this proposed method. With internal standardization against W, the obtained concentrations of CaO and WO3 were found to yield an average matrix CaO/WO3 mass fraction ratio of 0.245 (2σ = 0.003, n = 19), which agreed well with the value of 0.243 (2σ = 0.002, n = 15) from electron probe microanalysis (EPMA). Furthermore, the accuracy of trace element analyses with this proposed non-matrix-matched calibration in situ method was evaluated by comparing the concentration results with those from bulk analysis by solution nebulizer ICP-MS (SN-ICP-MS). It was found that the quantification results from LA-ICP-MS and SN-ICP-MS were comparable, in particular showing a relative concentration bias of the total ∑REE+Y contents of less than 2%. This confirmed that scheelites can be accurately analyzed in situ by LA-ICP-MS without matrix-matched calibration standards. By using this developed in situ method, the element compositions in a series of scheelite samples from different W-associated deposits in China were successfully quantified, promising further genetic process investigation and associated geologic activities of the polymetallic resources. [ABSTRACT FROM AUTHOR]

The giant Changba-Lijiagou (Ch-L) Pb-Zn deposit is in the northeast part of the Xicheng ore cluster, Western Qinling Orogen. The ore genesis remains controversial; it could be either a sedimentary exhalative genetic type or an epigenetic hydrothermal genetic type. Here, in situ titanite U-Pb dating for the two kinds of titanite is presented, yielding ages of 212.8 ± 3.0 Ma in the mineralized skarn ore and 214.6 ± 5.1 Ma in the host rock. These ages conform to the previously reported magmatic zircon age (229–211 Ma) based on the in situ zircon U-Pb dating of plutons in this district and the time of large-scale magmatic–hydrothermal activities in Western Qinling Orogen (229–209 Ma). Titanites occurring in mineralized skarn and those that are calcite-hosted are similar to hydrothermal-origin titanites in major element characteristics. The Eu anomalies in the two types of titanite record oxidizing conditions during the mineralization process. A mineral assemblage of garnet, pyroxene, riebeckite, biotite, and potash feldspar, replacing the albite, is well-developed in the deposit. The mineralogical and geochronological characteristics indicate that the Ch-L Pb-Zn deposit is a distal skarn deposit and the result of intensive tectonomagmatic processes in the Xicheng ore cluster during the process of the Late Triassic orogeny. [ABSTRACT FROM AUTHOR]

Coal fly ash represents a potential resource of some critical elements, including rare earth elements (REEs), which are retained and concentrated during coal combustion. Understanding the distribution and modes of occurrence of REEs within fly ash is vital to developing effective recovery methods and enhancing their economic value. Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) was applied to investigate the in situ elemental constituents of coal fly ash phases, including aluminosilicates, Ca-(Fe)-enriched aluminosilicates, Fe-oxides, and SiO2/Quartz, in order to explore the distribution of REEs in combustion products. LA-ICP-MS results show that V, Cr, and Nb are mainly enriched in Ca-Ti-enriched aluminosilicates with trace element concentrations referenced to the original fly ash composition. Lithium is primarily enriched in SiO2 glassy grains, followed by Ca, (Fe)-enriched aluminosilicates. Co, Ni, and Cu present a concomitant distribution in the Fe-enriched phases, such as Fe-oxides and Fe-enriched aluminosilicates. The chondrite normalized REE distribution patterns show characteristics of LREE enrichment and Eu-negative anomalies in most phases, while the REE patterns of SiO2 glassy grains have a distinct positive anomaly in Sm, Gd, and Dy, coupled with a deficiency in LREEs. Compared to feed coal, elements such as Li, V, Cr, Co, Ni, and Nb and REEs are enriched 2~10 times in various phases of fly ash, with REEs notably concentrated six times higher in aluminosilicates and Ca-Ti-enriched aluminosilicates than the original coal. This study further discusses the feasibility, calibration principles, and advantages of using LA-ICP-MS to determine REE distribution, as well as the economic implications of REE extraction from coal fly ash. [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) is a prevalent neurodegenerative disorder characterized by cognitive decline and neuropathological hallmarks, including β-amyloid (Aβ) plaques, Tau tangles, synaptic dysfunction and neurodegeneration. Emerging evidence suggests that abnormal iron (Fe) metabolism plays a role in AD pathogenesis, but the precise spatial distribution of the Fe and its transporters, such as ferroportin (FPN), within affected brain regions remains poorly understood. This study investigates the distribution of Fe and FPN in the CA1 region of the human hippocampus in AD patients with a micrometer lateral resolution using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). For this purpose, we visualized and quantified Fe and FPN in three separated CA1 layers: stratum molecular-radial (SMR), stratum pyramidal (SP) and stratum oriens (SO). Additionally, chromogenic immunohistochemistry was used to examine the distribution and colocalization with Tau and Aβ proteins. The results show that Fe accumulation was significantly higher in AD brains, particularly in SMR and SO. However, FPN did not present significantly changes in AD, although it showed a non-uniform distribution across CA1 layers, with elevated levels in SP and SO. Interestingly, minimal overlap was observed between Fe and FPN signals, and none between Fe and areas rich in neurofibrillary tangles (NFTs) or neuritic plaques (NP). In conclusion, the lack of correlation between Fe and FPN signals suggests complex regulatory mechanisms in AD Fe metabolism and deposition. These findings highlight the complexity of Fe dysregulation in AD and its potential role in disease progression.

New U-Pb zircon ages are reported for granulite facies crustal xenoliths brought to the surface by mafic lavas in the Snake River Plain. All samples yield Meso-to-Neoarchean ages (2.4–3.6 Ga) that significantly expand the known extent of the Archean Wyoming Craton at least as far west as the west-central Snake River Plain. Most zircon populations indicate multiple growth episodes with complexity increasing eastward, but they bear no record of major Phanerozoic magmatic episodes in the region. To extrapolate this work further west to the inferred craton boundary, zircons from southwestern Idaho batholith granodiorites were also analyzed. Although most batholith zircons record Cretaceous formation ages, all samples have zircons with inherited cores—with some recording Proterozoic ages (approaching 2 Ga). These data enhance our perspectives regarding lithosphere architecture beneath southern Idaho and adjacent areas and its possible influence on Cenozoic magmatism associated with the Snake River Plain–Yellowstone "melting anomaly". [ABSTRACT FROM AUTHOR]

Electron backscatter diffraction (EBSD) methods are used to investigate the presence of microstructures in pyrite from the giant breccia-hosted Olympic Dam iron–oxide copper gold (IOCG) deposit, South Australia. Results include the first evidence for ductile deformation in pyrite from a brecciated deposit. Two stages of ductile behavior are observed, although extensive replacement and recrystallization driven by coupled dissolution–reprecipitation reaction have prevented widespread preservation of the earlier event. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) element maps of pyrite confirm that many pyrite grains display compositional zoning with respect to As, Co, and Ni, but that the zoning is often irregular, patchy, or otherwise disrupted and are readily correlated with observed microstructures. The formation of ductile microstructures in pyrite requires temperatures above ~260 °C, which could potentially be related to heat from radioactive decay and fault displacements during tectonothermal events. Coupling EBSD methods with LA-ICP-MS element mapping allows a comprehensive characterization of pyrite textures and microstructures that are otherwise invisible to conventional reflected light or BSE imaging. Beyond providing new insights into ore genesis and superimposed events, the two techniques enable a detailed understanding of the grain-scale distribution of minor elements. Such information is pivotal for efforts intended to develop new ways to recover value components (precious and critical metals), as well as remove deleterious components of the ore using low-energy, low-waste ore processing methods. [ABSTRACT FROM AUTHOR]

The preparation of matrix-matched material for elemental quantitative analysis in rice flour matrix is proposed here for the first time as part of a feasibility study using the SN-ICP-MS and LA-ICP-MS methods. It was prepared via the spiking process in colloidal solution of rice flour with different levels of arsenic (As), cadmium (Cd) and lead (Pb), followed by drying in a climatic chamber. Comparative studies of the results on external calibration and gravimetric standard addition ICP-MS approaches through the use of calibration standard solutions were discussed. Method bias from the external calibration method was investigated, demonstrating the systematic effect arising from the sample matrix. Characterizing the concentration of measurands was then reasonably proposed using the gravimetric standard addition ICP-MS. Using powdered rice matrix reference material for ICP-MS calibration following acid digestion, the study showed a good agreement of recovery studies. A feasibility study of the LA-ICP-MS method as a direct solid analysis performed on the matrix-matched standard was then discussed. In the study, large fluctuation of signals was found for constructing calibration curve, generating poor linearity, especially for As and Pb, although yttrium (Y) as internal standard was applied. This might be ascribed to a limited microscale of homogeneity, and particularly laser-induced preferential evaporation of volatile elements. Using a number of measured data points, the mean and median were statistically recommended to improve precision. An attempt to use of similar matrix in both standard and sample is a critical point to consider to minimize the elemental fractionation effect. The proposed approach to prepare matrix-matched material could be a potential means for achieving elemental quantitation. [ABSTRACT FROM AUTHOR]

The Shuangwang Au deposit (with a gold resource of approximately 70 t Au), is located in the Fenxian-Taibai fore-arc basin in the West Qinling Orogen of central China. Igneous intrusions in the region include the Xiba granitic pluton and granite porphyry and lamprophyre dykes. The Xiba pluton is composed of granodiorite and monzonite granite. The granodiorite is typical I-type granite, and it yields a crystallization age of 221.1 ± 1.2 Ma and a two-stage Hf model age of 1432–1634 Ma. The monzonite granite shows a transitional characteristic between I-type and A-type granite, and it yields a crystallization age of 214.8 ± 1.2 Ma and a two-stage Hf model age of 1443–1549 Ma. The granitoid was derived mainly from a crust–mantle mixed source. The ages indicate that the granodiorite and monzonite granite formed during two different stages. The REE distribution patterns of the Xiba granitoid exhibit significant fractionation between LREE and HREE, showing right-dipping curves, with an enrichment of LREE and a deficit of HREE. The granodiorite displays a light negative Eu anomaly, while the monzonite granite displays an obvious negative Eu anomaly. The granite porphyry dikes are distributed in the No. I breccia and Jiupinggou granite porphyry, and they yield crystallization ages of 219.9 ± 1.5 Ma and 213.1 ± 0.89 Ma, respectively, and two-stage Hf model ages of 1382–1501 Ma and 1373–1522 Ma, respectively. The lamprophyre dikes in the deposit yield a crystallization age of 214.4 ± 2.7 Ma. After the collision event between the Yangtze and the North China Plates along the Qinling orogenic belt, at approximately 220 Ma in the Late Triassic, the detachment of the slab produced the upwelling of the asthenosphere material. Under conditions of mantle heat and tectonic stress, widespread partial melting of the subducted continental crust and the upper lithosphere mantle occurred, forming granitoids with various degrees of adakite characteristics. [ABSTRACT FROM AUTHOR]

The Clarion–Clipperton Fracture Zone of the east Pacific contains numerous shallow buried nodules that are in direct contact with pore water in sediment, providing a direct reflection of the interaction between nodules and sediment. However, research on the geochemical behavior of these shallow-buried nodules is limited. This study used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), high-resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD) to compare mineral and element distribution in shallow buried nodules with surface nodules. The shallow buried nodules are products of nodules entering the burial stage. In comparison to surface nodules, shallowly buried nodules develop a fourth oxidized-suboxic diagenetic growth layer after entering the burial stage, in addition to the three main growth inner layers (L1, L2, L3). We suggest that L4 is not influenced by the bottom water source and that the presence of todorokite and the high flux of Mn2+ in the sediment pore water compete with other metal elements to enter the lattice of manganate, resulting in significantly higher Mn, W, and Li contents in L4 compared to L2. However, the content of Ni, Mg, and other hydrogenetic elements is much lower in L4 compared to L2. We suggest that the instantaneous change in surface primary productivity results in a sudden shift in the redox environment of the upper sediment layer. This reaction leads to the reduction of solid-phase Mn, providing growth opportunities for the buried nodules. Simultaneously, this may also be the reason why the growth layer of the nodules is jointly controlled by the sedimentary processes of hydrogenetic, oxic diagenetic, and suboxic diagenetic processes. [ABSTRACT FROM AUTHOR]

The Huanggang deposit is the most important and largest skarn Fe–Sn polymetallic deposit in the Southern Great Xing'an Range of Northeast China. Cassiterite, magnetite, and other metal minerals are related to the garnets within skarn systems. The zoned garnets from various skarn stages are able to record numerous geological and mineralizing processes including variations in physicochemical conditions and hydrothermal fluid evolution. In this contribution, we present the mineralogy, systematic major, trace, and rare earth element (REE) concentrations of zoned garnets from the Huanggang Fe–Sn polymetallic skarn deposit. The in situ analytical results of garnets in the prograde skarn stage from andradite core (Grt I) to grossular rim (Grt II) reveal that core sections were formed from a fluid that was generally LREE-rich, with relatively high ∑REE, high LREE/HREE ratios, and weak negative Eu anomalies, whereas rim sections were crystallized from a fluid that was typically HREE-rich, with relatively low ∑REE, low LREE/HREE ratios, and obviously negative Eu anomalies. The garnets of the retrograde skarn stage from Fe3+-rich andradite core (Grt III) to andradite rim (Grt IV) demonstrate that the core sections have a flat trend with high ∑REE and obvious negative Eu anomalies, whereas rim sections were formed from a fluid with relatively low ∑REE, HREE-rich and obviously negative Eu anomalies. The garnets from the prograde skarn stage principally display relatively lower U and higher Y and F concentrations than those from the retrograde skarn stage. Based on optical and textural characteristics, REE patterns, Eu anomalies, and trace element variations in zoned garnets, it can be shown that, during skarn formation, Huanggang hydrothermal fluids shifted from near-neutral pH, oxidizing conditions, and high W/R ratios with relatively low LREE/HREE ratios characteristics to acidic, reducing conditions, and low W/R ratios with relatively high LREE/HREE ratios characteristics. We infer that variations in fluid compositions and physicochemical conditions may exert major control on formation and evolution of garnets and skarn hydrothermal fluids. [ABSTRACT FROM AUTHOR]

Cenozoic dolomitization of reefal carbonates has been widely found on many tropical islands worldwide. However, most ages and geochemical data obtained from bulk samples prevent a clear understanding of the previous complex diagenetic processes of these island dolostones due to a lack of in situ age and fluid composition. In this study, one deep borehole penetrated Cenozoic carbonates on Meiji Island in the southern South China Sea and massive dolostones with thicknesses over 400 m were uncovered. The in situ U–Pb geochronology and elemental analysis were conducted on the lower Nanwan Formation (upper Miocene) comprising undolomitized calcite (bioclast), replacive dolomite, and dolomite cement. Strontium isotope ages and U–Pb dates show that the penecontemporaneous replacive dolomitization occurred at 11.0–8.5 Ma, close to the deposition of precursor limestone. The dolomite cement precipitated at 8.5–6.0 Ma. In situ elemental analyses indicate that the formation of replacive dolomite and dolomite cement in the Nanwan Formation was probably controlled by seawater. The higher Mg/Ca ratio and lower Mn and Sr contents in dolomite cements show that their fluid underwent more evaporation. The dolomite content is positively related to the porosity of reefal limestones in the Nanwan Formation, suggesting that primary voids play an important role in fluid transportation during following dolomitization. Coralline algae and lime mud with algal fragments are beneficial for the rapid nucleation of dolomite. This study demonstrates that in situ elemental analysis using laser ablation has great potential for identifying the source of multistage dolomitizing fluids and can help refine the existing dolomitization model of isolated atolls. [ABSTRACT FROM AUTHOR]

The Nanmushu Zn–Pb deposit is a large-scale and representative deposit in the Mayuan ore field on the northern margin of the Yangtze Block. This study investigates the trace element geochemistry of sphalerite from this deposit using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The results show that the main trace elements in sphalerite include various trace elements, such as Mn, Fe, Cu, Ga, Ge, Ag, Cd, Pb, Co, Hg, Tl, In, Sn, and Sb. Among them, Ag, Ge, Cd, and Cu are valuable components that may be recovered during mineral processing or smelting techniques. The histograms, LA-ICP-MS time-resolved depth profiles, and linear scan profiles indicated that most trace elements occur in sphalerite as isomorphs, while partial Pb, Fe, and Ag occur as tiny mineral inclusions. The correlation diagrams of trace elements revealed that Fe2+, Mn2+, Pb2+, and Tl3+ can substitute Zn2+ in sphalerite through isomorphism. In sphalerite, Cd2+ and Hg2+ together or Mn2+, Pb2+, and Tl3+ together can replace Zn2+, i.e., ((3Mn, 3Pb, 2Tl)6+, 3(Cd, Hg)2+) ↔ 3Zn2+. Moreover, there is a mechanism of Ge4+ with Cu+ or Ga3+ with Cu+ replacing Zn2+ in the Nanmushu deposit, i.e., Ge4+ + 2Cu+ ↔ 3Zn2+ or 2Ga3+ + 2Cu+ ↔ 4Zn2+. Furthermore, the trace element compositions indicate that the Nanmushu Zn mineralization occurred under low-temperature conditions (<200 °C) and should be classified as a Mississippi Valley-type (MVT) deposit. This study provides new insights into the occurrence and substitution mechanisms of trace elements in sphalerite and the metallogenic constraints of the Nanmushu deposit. [ABSTRACT FROM AUTHOR]

The goal of accurately quantifying trace elements in ultrapure silicon carbide (SiC) with a purity target of 5N (99.999% purity) was addressed. The unsuitability of microwave-assisted acid digestion followed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis was proved to depend mainly on the contamination induced by memory effects of PTFE microwave vessels and by the purity levels of acids, even if highly pure ones were used in a clean environment. A new analytical protocol for the direct analysis of the solid material by laser ablation coupled with ICP-MS (LA-ICP-MS) was then exploited. Different samples were studied; the best results were obtained by embedding SiC (powders or grains) in epoxy resin. This technique has the great advantage of avoiding any source of external contamination, as grinding, pressing and sintering pretreatments are totally unnecessary. Two different laser wavelengths (266 and 193 nm) were tested, and best results were obtained with the 266 nm laser. The optimized protocol allows the determination of elements down to the sub-mg/kg level with a good accuracy level. [ABSTRACT FROM AUTHOR]

The metal-rich Vazante-Paracatu Mineral Belt, in central Brazil, hosts the Zn-Pb sulfide Morro Agudo District in the Mesoproterozoic (1.3–1.1 Ga) upper carbonate sequence of the Vazante Group. The Morro Agudo district is comprised of the Morro Agudo deposit and the Bento Carmelo, Sucuri, and Morro do Capão occurrences. This carbonate sequence also hosts the Fagundes, Ambrósia and Bonsucesso Zn-Pb sulfide deposits (northern part) and the zinc silicate Vazante and North Extension deposits (southern part). The structurally controlled, stratabound and stratiform styles of mineralization in the Morro Agudo orebodies have been variably classified as sedimentary exhalative, Irish-type and Mississippi Valley-type. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot analyses of sphalerite and galena from the Morro Agudo district revealed that red sphalerite (interpreted as the last stage) has higher Fe and Mn and lower Bi, Co, Cu, Ge, Hg, Tl compared to the other types of sphalerite, whereas the first generation of galena (Gn-I) is enriched in Ag, Cd, and Se and depleted in Cu and Mn relative to later galena (Gn-II). Mineral paragenesis and principal component analysis (PCA) of ore mineral composition suggest that the Morro Agudo, Sucuri and Morro do Capão mineralized zones formed by similar processes involving Zn-Pb mineralizing fluids with various compositions, comprising two main elemental associations: (1) Fe, As, In, Mn, Sb, Ag; and (2) Cd, Bi, Co, Ga, and Se. Bento Carmelo is distinguished in PCA by its unique dolomite-hosted sphalerite composition with elevated concentrations of Cu, Ge, Hg and likely formed from distinct fluids or processes. Temperatures of the mineralizing fluids for the Morro Agudo district range from 82 to 320 °C, calculated based on the trace element composition of sphalerite. The styles of mineralization and ore compositions are consistent with MVT deposits; however, fluid temperatures are hotter than typical MVT mineralizing fluids and may reflect a higher geothermal gradient or active advective fluid flow during the Brasiliano orogeny. [ABSTRACT FROM AUTHOR]

Pb–Zn deposits supply a significant proportion of critical metals, such as In, Ga, Ge, and Co. Due to the growing demand for critical metals, it is urgent to clarify the different types of Pb–Zn deposits to improve exploration. The trace element concentrations of sphalerite can be used to classify the types of Pb–Zn deposits. However, it is difficult to assess the multivariable system through simple data analysis directly. Here, we collected more than 2200 analyses with 14 elements (Mn, Fe, Co, Ni, Cu, Ga, Ge, Ag, Cd, In, Sn, Sb, Pb, and Bi) from 65 deposits, including 48 analyses from carbonate replacement (CR), 684 analyses from distal magmatic-hydrothermal (DMH), 197 analyses from epithermal, 456 analyses from Mississippi Valley-type (MVT), 199 analyses from sedimentary exhalative (SEDEX), 377 analyses from skarn, and 322 analyses from volcanogenic massive sulfide (VMS) types of Pb–Zn deposits. The critical metals in different types of deposits are summarized. Machine learning algorithms, namely, decision tree (DT), K-nearest neighbors (KNN), naive Bayes (NB), random forest (RF), and support vector machine (SVM), are applied to process and explore the classification. Learning curves show that the DT and RF classifiers are the most suitable for classification. Testing of the DT and RF classifier yielded accuracies of 91.2% and 95.4%, respectively. In the DT classifier, the feature importances of trace elements suggest that Ni (0.22), Mn (0.17), Cd (0.13), Co (0.11), and Fe (0.09) are significant for classification. Furthermore, the visual DT graph shows that the Mn contents of sphalerite allow the division of the seven classes into three groups: (1) depleted in Mn, including MVT and CR types; (2) enriched in Mn, including epithermal, skarn, SEDEX, and VMS deposits; and (3) DMH deposits, which have variable Mn contents. Data mining also reveals that VMS and skarn deposits have distinct Co and Ni contents and that SEDEX and DMH deposits have different Ni and Ge contents. The optimal DT and RF classifiers are deployed at Streamlit cloud workspace. Researchers can select DT or RF classifier and input trace element data of sphalerite to classify the Pb–Zn deposit type. [ABSTRACT FROM AUTHOR]

Precious metals can be mobilized during supergene processes, which are important for the formation of high-grade or high-purity ores. The world-class Linglong gold deposit has high-grade ores that have undergone supergene processes in the near-surface zone. Under which conditions the supergene modification occurred and how Au and Ag behaved during the supergene processes have been poorly studied in this deposit. Here, we performed scanning electron microscope (SEM) and laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) analyses on samples from the supergene enrichment zone of the Linglong gold deposit. The results show that secondary minerals were formed sequentially from magnetite-goethite-limonite to marcasite-acanthite, and finally to siderite after the primary minerals of pyrite-pyrrhotite-chalcopyrite. These mineral assemblages and variations indicate that the supergene modification by groundwater occurred under oxidative and weakly acidic conditions in the near-surface zone and evolved to reductive and near neutral conditions in the supergene enrichment zone. The newly formed marcasite has much higher Au (0.003–23.5 ppm, mean of 1.33 ppm) and Ag (81.7–6021 ppm, mean of 1111 ppm) concentrations than those of the primary pyrite (Au of 0.004–0.029 ppm and Ag of 0.22–4.14 ppm), which together with the formation of independent Ag–S mineral (acanthite), indicates that Au and Ag were significantly mobilized and fractionated during the supergene processes. These processes improved the Au and Ag grades in the supergene enrichment zone and thus facilitate their extraction. [ABSTRACT FROM AUTHOR]

The Gacun deposit is a typical Volcanic Hosted Massive Sulfide (VHMS) associated with Late Triassic seafloor calc-alkaline felsic volcanics. Studies of zircon ages, petrology, major and trace element geochemistry, and Sr-Nd-Hf isotope geochemistry of volcanic rocks from the Northern Yidun arc were undertaken in this paper. We reshaped the Gacun magmatic system activity time, defined the origin of magma evolution, and proposed a metallogenic model of the deposit. Whole-rock major element compositions of the magmatic rocks in the Northern Yidun island arc indicate that they are a complete basalt–andesite–dacite–rhyolite assemblage, showing three obvious stages of composition evolution. They are enriched in large-ion lithophile and light rare earth elements, but depleted in high field-strength and heavy rare earth elements, with weak-to-negligible Eu anomalies (obvious in rhyolite). These geochemical features indicate that the Northern Yidun island arc is a magmatic arc based on ancient continental crust. The Ganzi–Litang oceanic subduction induced mantle melting and produced calc-alkaline basaltic magma, while the MASH processes at the bottom of the crust produced andesitic magma. Part of the andesite magma erupted to form andesite lava. The remaining part was mixed with magma produced via anatexis of ancient crust (approximately 20%–40% of the ancient crustal component), forming the ore-bearing rhyolite. Zircon U-Pb age data defines Gacun magmatic–hydrothermal mineralization sequence of events: At 238 Ma, arc magmatism led to the formation of andesite in the eastern part of the deposit. At 233 Ma, in the arc zone (the western part of Gacun deposit), a large-scale bimodal magmatism formed the main ore-bearing rock series of Gacun deposit, rhyolitic volcanic rocks. At 221 Ma, volcanic eruptions tended to end and sub-volcanic intrusion occurred, forming a lava dome, which was located under the ore-bearing rhyolitic volcanic rocks. The lava dome acted as a thermal engine and promoted hydrothermal circulation. The hydrothermal activity reached a peak at 217 ± 1 Ma, and the Gacun VHMS deposit was formed. [ABSTRACT FROM AUTHOR]

Halmyrolysis, as one of the global processes of alteration of seafloor hydrothermal sediments, needs to be recognized in terms of mineral and trace element evolution to elaborate new criteria for metallogenic and geoecological forecasts with respect to ocean exploration. The purpose of this paper is to explain trace elements' behavior during the halmyrolysis of sulfide deposits. This task is resolved using an LA-ICP-MS analysis of iron oxyhydroxides (IOHs) on examples of oxidized pyrrhotite-rich diffusers of the ultramafic-hosted Pobeda-1 hydrothermal field (Mid-Atlantic Ridge). The IOHs formed after the sulfides were enriched in seawater-derived trace elements (Na, K, Mg, Ca, Sr, P, U, Mo, V, REE, Cr). Six trace element assemblages (TEAs) are statistically recognized for the IOHs. TEA-I (Cu, In, Sn, Bi, Se, Te) is inherited from chalcopyrite, isocubanine and bornite microinclusions. TEA-II is typical of Zn sulfides (Zn, Cd, Sb, Tl, Ag) interacted with seawater (Mg, U, Mo, Ni, Na, K) and hydrothermal fluid (Eu). TEA-III (Ca, Sr, Cu, Si, Se, P, As) reflects the inclusions of aragonite, opal, atacamite and possibly native selenium, while P and As occur as absorbed oxyanion groups on IOHs or Ca–Fe hydroxyphosphates. TEA-IV (Al, Ga, Ge, Tl, W, Ti ± Mn, Co, Ba) indicates the presence of minor clays, Co-rich Mn oxyhydroxides and barite. TEA-V with Pb and V is closely related to TEA-VI with REEs except for Eu. The halmyrolysis of sulfides includes two stages: (i) oxidation of S(II) of primary sulfides and the formation of supergene sulfides, which scavenge the redox-sensitive elements (e.g., U, Mo, Ni, Eu), and (ii) oxidation of Fe (II) to Fe (III) and absorption of most elements of TEAs III, IV, V and VI by IOHs. [ABSTRACT FROM AUTHOR]

The Daocaowan antimony (Sb) deposit is a newly discovered Sb deposit located outside the northeast Xikuangshan ore field. In the absence of geochemical data, the metallogenic mechanism of the Daocaowan Sb deposit and its relationship with the Xikuangshan ore field remains unclear. Using high-resolution LA-ICP-MS technique, this study quantitatively determined the in-situ S isotope values and trace element composition of stibnite from the Daocaowan Sb deposit in South China to investigate the source of ore-forming materials and genesis of this deposit. The trace element compositions of stibnite from the Daocaowan Sb deposit revealed the form of occurrence and substitution mechanism of trace elements in stibnite, providing new constraints for explaining the genesis of Sb deposits. The relatively smooth LA-ICP-MS profiles indicate that As, Cu, Hg, and Pb primarily occur as solid solutions in stibnite. Therefore, we speculate that the substitution 3Sb3+↔As3+ + 2Cu+ + Hg2+ + Pb2+ may be the reason for the enrichment of As, Cu, Hg, and Pb in stibnite. A comparison with the Xikuangshan Sb deposit reveals the metallogenic mechanism of the Daocaowan Sb deposit, and the relationship between the two. With the exception of higher content of Fe in Stibnite from the Daocaowan deposit as compared to the Xikuangshan deposit, other trace elements are similar between the two deposits. The results show that the Daocaowan and Xikuangshan Sb deposits may have the same source of ore-forming fluids. We propose that the ore-forming fluid flowed through the Xikuangshan Sb deposit along the F75 fault and dissolved pyrite in the wall rock. Subsequently this fluid containing a high concentration of Fe precipitated and mineralized at Daocaowan. Meanwhile, the S isotope value of the Daocaowan Sb deposit (+6.65 to +9.29‰) is consistent with that of the Xikuangshan, proving that the ore-forming materials of the two deposits are from the same source, probably the basement strata. We propose that the Daocaowan Sb deposit is part of the Xikuangshan ore field, indicating a great prospecting potential in the northeast of the Xikuangshan ore field. [ABSTRACT FROM AUTHOR]

As an important part of the northern Huaiyang tectonic belt, the Mesozoic Xiaotian basin hosts a series of gold and alunite deposits. However, the ages of these deposits remain unclear, constraining the further understanding of the genesis of these deposits. In this work, zircon LA–ICP-MS and alunite 39Ar/40Ar isotopic dating studies were carried out on the andesitic porphyrite and alunite of the Saozhouhe alunite deposit, respectively. LA–ICP-MS zircon U–Pb dating for the Saozhouhe andesitic porphyrite yields a weighted average age of 122.8 ± 0.9 Ma (MSWD = 1.8), indicating that these volcanic rocks were formed in the Early Cretaceous period. The alunite 39Ar/40Ar dating yields a plateau age of 121.0 ± 1.1 Ma (MSWD = 4.4) and an isochron age of 121.2 ±1.9 Ma (MSWD = 8.5), indicating that the alunite was also formed in the Early Cretaceous period. Our finding confirms that the formation of the Saozhouhe alunite deposit is genetically related to the Cretaceous volcanic magmatism, which has great significance in the metallogenetic regularity of and further ore prospecting in the Xiaotian basin. [ABSTRACT FROM AUTHOR]

Whole-rock geochemical analysis is a standard method to measure the chemical composition of ores. Analysis of refractory ore metals such as Ta and W typically requires fused bead and acid digestion followed by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled mass spectrometry (ICP-MS). Since these techniques are time-consuming and expensive, there is a demand for methods that can quantitatively measure low elemental concentration of refractory ore metals using a less expensive and simple approach. This paper evaluates preparation and analytical procedures developed to obtain whole-rock element concentrations of ore samples and mineral concentrates. It shows that the production of nano-particulate pressed-powder pellets followed by LA-ICP-MS analysis of W and Ta ores can be used to determine, within the error margin, the concentrations of the refractory metals W, Ta, Nb, and Sn compared to a reference values obtained by solution analysis. The results have implications for developing a commercially viable method for analysis of refractory elements to benefit mineral processing given the simplicity and resource-efficiency of the combined pressed pellet production and laser ablation analytical methodology. [ABSTRACT FROM AUTHOR]

The Proterozoic Athabasca Basin hosts a large number of high-grade, large-tonnage unconformity-related uranium (U) deposits, many of which are also enriched in rare earth elements (REE). The basin also contains hydrothermal REE mineralization unassociated with U. Previous studies postulated that U and REE were derived from either the basin or the basement; however, the exact source of the metals remains ambiguous. This study provides evidence of U- and REE-rich fluids throughout the Athabasca Basin through laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) mapping of barren sandstone distal to mineralized areas. The results indicate that elevated U and REE concentrations mainly occur in the matrix; there are strong positive correlations between U and REE, Th, P and Sr, and moderate positive correlations between U and Zr, Ba, Fe, Al, K and Ca, but the few spots with the highest U are unrelated to these elements. Quantitative evaluation of the element correlations, together with scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analysis, suggests that most of the elevated U and REE are hosted in aluminum phosphate sulfate (APS) minerals rather than apatite and monazite. As the APS minerals are of diagenetic-hydrothermal origin, the results testify to the presence of U- and REE-rich fluids within the Athabasca Basin. The elevated Th/U ratio (~10) and REE pattern (strong heavy rare earth element (HREE) depletion) are consistent with a model in which large amounts of U and REE (especially HREE) were leached from the sandstone within the Athabasca Basin and contributed to U and REE mineralization near the unconformity between the sedimentary rocks in the basin and underlying basement rocks. This study demonstrates that LA-ICP-MS mapping can be effectively used to evaluate microscale distribution of elements and their mobility in sedimentary rocks to address mineralization related problems. [ABSTRACT FROM AUTHOR]

The Liaohe Group, which is a significant lithostratigraphic unit within the Paleoproterozoic Jiao-Liao-Ji Belt situated between the Longgang and Liaonan-Nangrim blocks, comprises the Langzishan, Li'eryu, Gaojiayu, Dashiqiao, and Gaixian formations, which are characterized mainly by a clastic-rich sequence with an interlayered bimodal-volcanic sequence, carbonate-rich sequence, and (meta-)pelite-rich sequence. Currently, the tectonic background and evolution of the Liaohe Group remain contentious. Based on the study of detrital zircon geochronology and the zircon trace element characteristics in the Langzishan and Li'eryu formations in the North Liaohe Group in the Lianshanguan area, NE China, this paper reveals the formations' provenances, depositional ages, and relationships with Paleoproterozoic granitoids (the Liao-Ji granites). The present results, in conjunction with previous studies, indicate that the depositional age of the Langzishan Formation is 2136 Ma and that of the Li'eryu Formation is 1974 Ma. The provenances of the Langzishan Formation and the Li'eryu Formation are mainly characterized by Neoarchean-to-early-Paleoproterozoic basement rocks (~2.6–2.4 Ga) and the Liao-Ji granites (~2.2–2.0 Ga), respectively. Moreover, the coeval mafic and metasedimentary rocks of the Liaohe Group exhibit characteristics of an extensional environment, which is represented by the tectonic setting of a back-arc basin. Notably, the Upper Langzishan Formation records a prominent shift in sedimentary environment from a passive continental margin to an active continental margin. In terms of the tectonic evolution of the North Liaohe Group and the Jiao-Liao-Ji Belt, our proposed model suggests that the Archean basement rocks in the northern part of the continental block, along with a limited contribution from the Paleoproterozoic Liao-Ji granites, served as the primary sources for the Langzishan Formation. Subsequently, the rapid deposition of the Li'eryu Formation was influenced by intense magmatism and subsequent erosion of the subduction-related magmatic arc (the Liao-Ji granites) within a back-arc basin environment. Lastly, the deposition of clastic materials from the Longgang blocks and the Liao-Ji granites resulted in the formation of the Gaojiayu, Dashiqiao, and Gaixian formations. [ABSTRACT FROM AUTHOR]

The mineralogical studies of rare-element (REL) pegmatites are important for unraveling the ore-forming process and evaluating REL mineralization potential. The Chinese Altai orogenic belt hosting more than 100,000 pegmatite dykes is famous for rare-metal resources worldwide and diverse REL mineralization types. In this paper, we present the results of EMPA and LA-ICP-MS for muscovite from the typical REL pegmatite dykes of the Chinese Altai. The studied pegmatites are Li-Be-Nb-Ta, Li-Nb-Ta, Nb-Ta, Be-Nb-Ta, Be and barren pegmatites. The Li+ accompanied with Fe, Mg and Mn substitute for Al3+ at the octahedral site in muscovite from the REL pegmatites, and the substitution of Rb by Cs at the interlayer space is identified in muscovite from the Be pegmatites. The P and B contents increase with evolution degree and the lenses from the Nb-Ta pegmatite are produced at late fluid-rich stage with high fluxes (P and B). The enrichment of HFSE in muscovite indicates a Nb-Ta-Sn-W rich pegmatite magma for the Be-Nb-Ta pegmatite. From barren pegmatite, beryl-bearing zone, to spodumene-bearing zone, the evolution degrees of pegmatite-forming magmas progressively increase. In the Chinese Altai, the possible indicators of muscovite for REL mineralization types include Rb (ca. 400–600 ppm, barren pegmatite; ca. 1200–4000 ppm, Be pegmatite; >4500 ppm, Li pegmatite), Cs (ca. 5–50 ppm, barren pegmatite; ca. 100–500 ppm, Be pegmatite; >300 ppm, Li pegmatite) and Ge (<3 ppm, barren pegmatite; ca. 4–6 ppm, Be pegmatite; ca. 6–12 ppm, Li pegmatite) coupled with Ta, Be (both <10 ppm, barren pegmatite) and FeO (ca. 3–4 wt%, Be pegmatite; ca. 1–2.5 wt%, Li pegmatite). The plots of Nb/Ta vs. Cs and K/Rb vs. Ge are proposed to discriminate barren, Be- and Nb-Ta-(Li-Be-Rb-Cs) pegmatites. The Li, Be, Rb, Cs and F concentrations of forming liquid are evaluated based on the trace element compositions of muscovite. The high Rb and Cs contents of liquid and lower Be contents than beryl saturation value indicate that both highly evolved pegmatite magma and low temperature at emplacement contribute to beryl formation. The liquids saturated with spodumene have large variations of Li, possibly related to metastable state at Li unsaturation–supersaturation or heterogeneous distribution of lithium in the system. [ABSTRACT FROM AUTHOR]

As a major constituent in magmatic–hydrothermal ore deposits, cassiterites, with moderate amounts of U and low Pb, can be dated with U–Pb geochronology. The tetragonal lattice structure makes cassiterites capable of incorporating dozens of elements within its crystal lattice (e.g., Fe, Ti, W, Zr, Hf, Ta, Nb, Mn, Sc, V, and Sb). Variations of these elements record information of potential elemental substitution mechanisms and precipitation environments of cassiterites. In this study, we collected cassiterite grains from four different ore styles of the Gejiu tin polymetallic deposit to perform LA–ICP–MS U–Pb dating, multiple element mapping, and in situ trace element analysis on these cassiterites. Systematic U–Pb dating yielded Tera–Wasserburg lower intercepted ages at around 85 Ma, coinciding with zircon U–Pb ages of regional Late Yanshanian granitoids, within their respective analytical uncertainties. Such age coincidence, combined with the spatial association, suggests that tin mineralization may be genetically related to the Late Cretaceous granitic magmatism. Multielemental mapping shows that the distribution of Nb, Ta, and Ti in the cassiterite grains correlates well with the regular oscillatory zoning patterns in cathodoluminescence (CL) images. The relatively high Sb, Fe, W, Ga, and U concentrations control the dark luminescing domains in these cassiterite grains. The systematic variations in chemical compositions suggest that trace elements such as Sc, V, Fe, and Ga incorporate in cassiterites via coupled substitutions of Sc3+ + V5+ ↔ 2 (Sn, Ti)4+, Fe3+ + Ga5+ ↔ 2 (Sn, Ti)4+ and Fe3+ + OH– ↔ Sn4+ + O2– or Fe3+ + H+ ↔ Sn4+. The covariation of redox sensitive elements such as W, U, Fe, and Sb indicates that the "tin-granite" type of cassiterites were formed under an oxidized state whereas cassiterites from skarn, massive sulfide, and oxidized ore styles were precipitated in a reducing environment. [ABSTRACT FROM AUTHOR]

The newly discovered Erdaodianzi gold deposit in southern Jilin Province, Northeast China, is located in the eastern segment of the northern margin of the North China Craton (NCC). It is a large-scale gold deposit with reserves of 38.4 tons of gold. Gold mineralization in the ore district primarily occurs in gold-bearing quartz–sulfide veins. The gold ore occurs mainly as vein, veinlet, crumby, and disseminated structures. The hydrothermal process can be divided into three stages: stage I, characterized by quartz, arsenopyrite, and pyrite; stage II, featuring quartz, arsenopyrite, pyrite, pyrrhotite, chalcopyrite, sphalerite, and native gold; and stage III, consisting of quartz, pyrite, sphalerite, galena, electrum (a naturally occurring Au–Ag alloy), and calcite. Electrum and native gold primarily occur within the fissures of the polymetallic sulfides. To determine the enrichment mechanism of the Au element and the genetic types of ore deposits in the Erdaodianzi deposit, sourcing in situ trace element data, element mapping and sulfur isotope analysis were carried out on sphalerites from different stages using LA-ICP-MS. Minor invisible gold, in the form of Au–Ag alloy inclusions, is present within sphalerites, as revealed by time-resolved depth profiles. The LA-ICP-MS trace element data and mapping results indicate that trivalent or quadrivalent cations, such as Sb3+ and Te4+, exhibit a strong correlation with Au. This correlation can be explained by a coupled substitution mechanism, where these cations (Sb3+ and Te4+) replace zinc ions within the mineral structure, resulting in a strong association with Au. Similarly, the element Pb exhibits a close relationship with Au, which can be attributed to the incorporation of tetravalent cations like Te4+ into the mineral structure. The positive correlation between Hg and Au can be attributed to the formation of vacancies and defects within sphalerite, caused by the aforementioned coupled substitution mechanism. A slight positive relationship between Au and other divalent cations, including Fe2+, Mn2+, and Cd2+, may result from these cations simply replacing Zn within the sphalerite lattice. The crystallization temperatures of the sphalerite, calculated via the Fe/Zn ratio, range from 238 °C to 320 °C. The δ34S values are divided into two intervals: one ranging from −1.99 to −1.12‰ and the other varying from 10.96 to 11.48‰. The sulfur isotopic analysis revealed that the ore-forming materials originated from magmatic rock, with some incorporation of metamorphic rock. Comparative studies of the Erdaodianzi gold deposit and other gold deposits in the Jiapigou–Haigou gold belt have confirmed that they are all mesothermal magmatic–hydrothermal lode gold deposits formed at the subduction of the Paleo-Pacific Plate beneath the Eurasian Plate during the Middle Jurassic. The Jiapigou–Haigou gold belt extends northwest to the Huadian area of Jilin province. This suggests potential for research on gold mineralization in the northwest of the belt and indicates a new direction for further gold prospecting in the region. [ABSTRACT FROM AUTHOR]

Immunochemical methods are used not only in clinical practice for the diagnosis of a wide range of diseases but also in basic and advanced research. Based on the unique reaction between the antibody and its respective antigens, it serves to specifically recognize target molecules in biological complex samples. Current methods of labelling antibodies with elemental labels followed by detection by inductively coupled plasma mass spectrometry (ICP-MS) allow detection of multiple antigens in parallel in a single analysis. Using the laser ablation (LA) modality (LA-ICP-MS), it is also possible to monitor the spatial distribution of biogenic elements. Moreover, the employment of metal nanoparticle-labeled antibodies expands the applicability also to molecular imaging by LA-ICP-MS. In this work, conjugates of model monoclonal antibody (DO-1, recognizing p53 protein) with various metal nanoparticles-based labels were created and utilized in dot-blot analysis in order to compare their benefits and disadvantages. Based on experiments with the p53 protein standard, commercial kits of gold nanoparticles proved to be the most suitable for the preparation of conjugates. The LA-ICP-MS demonstrated very good repeatability, wide linear dynamic range (0.1-14 ng), and limit of detection was calculated as a 1.3 pg of p53 protein.

The Songpan–Ganzi Orogenic Belt (SGOB) is bounded by the South China, North China, and Qiangtang blocks and forms the eastern margin of the Tibetan Plateau. The Tiechanghe Granite is located at the junction of the southeast margin of the SGOB and the western margin of the Yangtze Block. To elucidate the genetic relationship between the Tiechanghe Granite and the surrounding molybdenum deposits in Western Sichuan, in this study, we conducted zircon U-Pb and molybdenite Re-Os isotopic dating. The results indicate that the Tiechanghe Granite predominantly consists of monzogranite, with minor occurrences of syenogranite, while the molybdenum deposits are mainly found in skarn and quartz veins. The laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U-Pb ages of the Tiechanghe Granite range from 162.9 ± 0.7 Ma (MSWD = 0.31, n = 25) to 163.4 ± 0.6 Ma (MSWD = 0.85, n = 26), and the LA-ICP-MS zircon U-Pb age of the pegmatite veins is 164.1 ± 0.9 Ma (MSWD = 1.3, n = 19). These ages are consistent with the weighted average Re-Os age of the Ziershi molybdenite (160.3 ± 1.6 Ma, n = 2) within the error margins. These findings and previously obtained magmatic and metallogenic ages for the region suggest that a magmatic and mineralization event involving granite, molybdenum, tungsten, and copper occurred at around 162–164 Ma in the study area. This discovery broadens the exploration perspective for mineral resources in the Jiulong area of Western Sichuan and the entirety of Western Sichuan. [ABSTRACT FROM AUTHOR]

The Xiong'ershan district is situated on the southern margin of the North China Craton (NCC) and located within the Qinling–Dabieshan Orogen's orogenic zone. It is adjacent to the XiaoQinling mining district and exhibits very favorable geological conditions for mineralization, as the district contains numerous gold deposits, positioning it as one of the key gold-producing areas of China. The Miaoling gold deposit is a hydrothermal deposit and is controlled by the Mesozoic nearly NS-trending fault. The ore bodies are hosted in the Mesoproterozoic Xiong'er Group of the Changcheng System of volcanic rocks, with reserves reaching large-scale levels. Pyrite is the main gold-bearing mineral and can be classified into four generations: early-stage fine- to medium-grained euhedral to subhedral cubic pyrite (Py1); medium- to coarse-grained euhedral to subhedral cubic granular pyrite in quartz veins (Py2a); fine-grained subhedral to anhedral disseminated pyrite in altered rocks (Py2b); and late-stage anhedral granular and fine-veinlet pyrite in later quartz veins (Py3). Through in situ trace element analysis of the pyrite using LA-ICP-MS, a positive correlation between Au and As was observed during the main mineralization stage; gold mainly exists as a solid solution within the pyrite lattice, and the ablation signal curve reflecting the intensity of trace element signals showed that gold also occurs as micron-scale mineral inclusions. The trace element content suggested a gradual increase in oxygen fugacity from Stage 1 to Stage 2, followed by a decrease from Stage 2 to Stage 3. The Co/Ni values in the pyrite (0.56 to 62.02, with an average of 12.34) exhibited characteristics of magmatic hydrothermal pyrite. The in situ sulfur isotope analysis of the pyrite using LA-MC-ICP-MS showed δ34S values of 4.24‰ for Stage 1, −6.63‰ to −13.79‰ for Stage 2, and −4.31‰ to −5.15‰ for Stage 3. Considering sulfur isotope fractionation, the δ34S value of the hydrothermal fluid during the main mineralization stage was calculated to be between 0.31‰ and 2.68‰. [ABSTRACT FROM AUTHOR]

Stannite group minerals (ferrokësterite and stannite) occur in small amounts in association with sulfides in hydrothermal Pb-Zn deposits in Kosovo. The chemical composition of sphalerite co-existing with Sn-bearing minerals has been investigated using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS). Flat Sn-spectra suggest that Sn is bound in the sphalerite lattice or as nanoincluions. Sphalerite from Stan Terg, overgrown by ferrokësterite, contains the lowest Sn content (few ppm) and have been precipitated before Sn-enrichment in the fluids. The highest value of Sn (520 ppm) of Stan Terg sphalerite was obtained directly close to the ferrokësterite rim, and indicates a rapid increase of Sn in the hydrothermal fluids. Significantly higher values of Sn in sphalerite were obtained from other deposits: 1600 ppm (Artana), up to 663 ppm (Kizhnica), up to 2800 ppm (Drazhnje). Stannite-sphalerite geothermometry revealed the following ore-forming temperatures for the Kosovo mineralization: 240-390 °C for Stan Terg, 240-370 °C for Artana, >340 °C for Kizhnica, and 245-295 °C for Drazhnje. Sphalerite and stannite group minerals precipitated simultaneously during cooling from reduced hydrothermal fluids and under low-sulfidation fluid states. Fluctuations in physico-chemical fluid conditions are evidenced by the presence of stannite group minerals along growth zones in sphalerite and may be related to short interval of magmatic pulses during ore deposition. [ABSTRACT FROM AUTHOR]

This document is a correction notice for an article titled "U-Pb LA-ICP-MS Zircon Dating of Crustal Xenoliths: Evidence of the Archean Lithosphere Beneath the Snake River Plain." The correction addresses three errors in the original publication. The errors include the insertion of the letters 'ITT' in the geologic background section, the modification of the first sentences in the results section, and a small edit in the discussion section. The authors state that these errors do not affect the scientific conclusions of the study. [Extracted from the article]

Zircon (ZrSiO4) is the most commonly used mineral in U-Pb geochronology. Although it has proven to be a robust chronometer, it can suffer from Pb-loss or elevated common Pb, both of which impede precision and accuracy of age determinations. Chemical abrasion of zircon involves thermal annealing followed by relatively low temperature partial dissolution in HF acid. It was specifically developed to minimize or eliminate the effects of Pb-loss prior to analysis using Thermal Ionization Mass Spectrometry (TIMS). Here we test the application of chemical abrasion to Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) by analyzing zircons from both untreated and chemically abraded samples. Rates of ablation for high alpha-dose non-treated zircons are up to 25% faster than chemically abraded equivalents. Ablation of 91500 zircon reference material demonstrates a ca. 3% greater down-hole fractionation of 206Pb/238U for non-treated zircons. These disparities necessitate using chemical abrasion for both primary reference material and unknowns to avoid applying an incorrect laser induced fractionation correction. All treated samples display a marked increase in the degree of concordance and/or lowering of common Pb, thereby illustrating the effectiveness of chemical abrasion to LA-ICP-MS U-Pb zircon geochronology. [ABSTRACT FROM AUTHOR]

The giant Beiya Au skarn deposit and Machangqing porphyry Cu-Mo-(Au) deposit are located in the middle part of the Jinshajiang-Ailaoshan alkaline porphyry metallogenic belt. The Beiya deposit is the largest Au skarn deposit in China, whilst the Machangqing deposit comprises a well-developed porphyry-skarn-epithermal Cu-Mo-(Au) mineral system. In this paper, we present new allanite U-Th-Pb ages and trace element geochemical data from the two deposits and discuss their respective skarn metallogenesis. Based on the mineral assemblage, texture and Th/U ratio, the allanite from the Beiya and Machangqing deposits are likely hydrothermal rather than magmatic. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) allanite U-Th-Pb dating has yielded Th-Pb isochron ages of 33.4 ± 4.6 Ma (MSWD = 0.22) (Beiya) and 35.4 ± 9.8 Ma (MSWD = 0.26) (Machangqing), representing the retrograde alteration and magnetite skarn mineralization age of the two deposits. The Beiya and Machangqing alkali porphyry-related mineralization are synchronous and genetically linked to the magmatic hydrothermal activities of the Himalayan orogenic event. Major and trace element compositions reveal that the Beiya allanite has higher Fe3+/(Fe3+ + Fe2+) ratios, U content and Th content than the Machangqing allanite, which indicate a higher oxygen fugacity and F content for the ore-forming fluids at Beiya. Such differences in the ore-forming fluids may have contributed to the different metallogenic scales and metal types in the Beiya and Machangqing deposit. [ABSTRACT FROM AUTHOR]

The large Yongping Cu deposit is situated in the eastern Qin-Hang Metallogenic Belt, Southeast China and on the southern side of the Yangtze--Cathaysia suture zone, and is characterized by large stratiformorebodies. Garnet represents themain non-metallicmineral at Yongping, and shows variations in color from dark red to green to light brown with distance from the Shizitou porphyritic biotite granite stock. An in situ elemental analysis using EPMA and LA-ICP-MS and fluid inclusions microthermometric measurement on the Yongping garnet were conducted to constrain the hydrothermal and physicochemical mineralization conditions and the ore origin. The Yongping garnet ranges from nearly pure to impure andradite, is characterized by low concentrations of MnO (0.11-0.71 wt %) with a wide range of Y/Ho (2.1-494.9) and does not exhibit any melting inclusions or fluid-melt inclusions, indicating that they are likely to be resulted from hydrothermal replacements. The Yongping garnet is rich in LREEs, Cs, Th, U and Pb; relatively depleted in HREEs, Rb, Sr and Ba; but exhibits distinct Eu anomalies (δEu of the dark red, green and light brown garnet range 2.12-20.54, 0.74-1.70 and 0.52-0.85, respectively) with the homogenization temperatures and salinities of the fluid inclusions principally ranging from 387-477 °C and 7.8-16.0 wt % NaCl equivalent, respectively. The distinct trace elements and microthermometric characteristics reveal that the garnet was formed in a physicochemical conditions of medium-high temperature, 44-64 MPa pressures, mildly acidic pH levels, and unstable oxygen fugacity, and indicate that they were primarily formed by infiltration metasomatism, quite fitting with the scenario that the preferential entrance of magmatic-hydrothermal fluids derived from the Shizitou stock into the relatively low-pressure fracture zones between the limestone and quartz sandstone in the Yejiawan Formation, and further led to the formation of the Yongping stratiform mineralization. [ABSTRACT FROM AUTHOR]

To characterize the trace-element characteristics of chrysoberyl, we studied twenty-six chrysoberyl samples from various localities by using laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS), photoluminescence (PL), and ultraviolet–visible–near-infrared (UV–Vis–NIR) spectroscopy. Chemical analysis has confirmed the existence of trace elements, including Fe, Ti, Ga, Sn, B, Cr, and V. The phenomenon of ionic isomorphic substitution frequently occurs at lattice sites within chrysoberyl. Notably, the isomorphic substitution of Al3+ in octahedral sites is significant, with the primary substituting elements being Fe, Ti, Cr, V, Ga, and Sn. The PL spectra of chrysoberyl samples exhibit sharp peaks at 678 and 680 nm, which are attributed to Cr3+, even in samples in which the Cr concentration is below the detection limit of LA-ICP-MS. This demonstrates the high-sensitivity feature of PL spectroscopy. The UV–Vis–NIR spectra of chrysoberyl samples consistently exhibit a band at 440 nm, and strong double narrow bands near 367 nm and 375 nm are observed. These spectral features are associated with Fe3+ chromophores—specifically, Fe3+-Fe3+ pairs or clusters and Fe3+ ions, respectively. By combining LA–ICP–MS analysis and PL mapping on a sample exhibiting color zoning, it has been found that the darker sections contain a higher concentration of Cr compared to the lighter sections, while the concentrations of other elements remain largely consistent. In other words, subtle variations in Cr concentration may be the underlying cause of color zoning in chrysoberyl. [ABSTRACT FROM AUTHOR]