Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

Mineralogical Characteristics and Purification Experiments of Quartz from a Pegmatite: A Case Study in the Lushi Region of the Qinling Orogenic Belt, Central China

This study uses a sample of pegmatite (LS-1) from the Longquanping deposit in Lushi County, Henan Province, to evaluate its potential as a valuable source of HPQ. This investigation uses various analytical techniques to assess the quality of quartz and its suitability for industrial applications. The methods used in this study include optical microscopy, scanning electron microscopy (SEM), Raman spectroscopy, X-ray fluorescence spectrometry (XRF), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and inductively coupled plasma mass spectrometry (ICP-MS) to analyze the petrographic, mineralogical, and trace element characteristics of quartz before and after purification and comprehensively evaluate the potential of quartz in these rocks as an HPQ raw material ore. The optical and scanning electron microscopic observations reveal several impurities and associated minerals in quartz, including feldspar, biotite, magnetite, sphene, and large number of fluid inclusions composed of both gas and liquid phases. The content of trace element in raw quartz ore in the LS-1 sample as determined by LA-ICP-MS analysis ranges from 41.61 to 256.13 ppm, with the main impurity elements being Al, Ti, Li, Na, K, and Ca. After purification, the SiO2 contents and total trace elements contents of the LS-1 refined quartz sand was 99.997 wt.% and 29.29 ppm, respectively, with Al (13.29 ppm), Ti (4.20 ppm), Li (1.15 ppm), and Na (10.32 ppm). The major trace element contents of Al and Ti in the quartz concentrates were lower than the upper limit of the HPQ standard and thus belonged to the high-end products (4N8). Results of this study show that quartz from a pegmatite in the Lushi region has the potential to be purified HPQ. This study underscores the importance of thorough mineralogical and elemental analyses in assessing the suitability of quartz raw material deposits for HPQ production.

Mobilization of grassland soil arsenic stores due to agronomic management

The fate of arsenic in mineral soil stores over time is poorly understood. Here we examined arsenic loss over five decades from a managed grassland soil profile through analysing archived material from a long-term slurry (LTS) experiment at Hillsborough, Northern Ireland. A randomized block experiment was established in 1970 where a perennial ryegrass sward was seeded onto the site and subjected to control (no fertilization) and fertilization treatments using conventional (i.e. at farmers recommended application rate) mineral NPK fertilizer, and pig and cow slurry treatments. Soil (0–5, 5–10 and 10–15 cm), slurry applied, and sward off-take was archived each year. A mass-balance calculation found that control soils lost no arsenic down the 15 cm depth soil profile, the NPK treatment had a 10 % loss, while cow slurry caused 25 % loss, and a 35 % loss was observed for pig slurry. For treatments with arsenic loss, removal was linear over the 50 years of study in 2 out of the 3 blocks, with the 3rd block showing little or no change. Principal Component Analysis (PCA) found that arsenic was most positively associated with soil magnesium, manganese and nickel, while negatively associated with pH, organic carbon, phosphorus and silicon. Laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) of soil found that arsenic association with lead mineralogy could potentially explain why there was a gradient in arsenic loss across the experimental plots. Slurry and atmospheric inputs, and sward off-take had little impact on the soil arsenic mass-balance. The findings suggest that leaching loss down the soil profile was the mechanism of loss of arsenic. The applicability of the LTS experimental site arsenic findings to other soils is discussed, as is the implication for the global biogeochemical cycling of those soils.

Scheelite texture and composition fingerprint skarn mineralization of the giant Yuku Mo-W deposit, Central China

Scheelite is widely used to reveal ore-forming redox environments and track hydrothermal evolution processes in W-bearing deposits. Yuku, situated in Central China, is a typical skarn Mo-W deposit discovered recently in the Luanchuan Mo-W-Zn-Pb ore district. This study determined the compositions of the Yuku scheelite via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and electron microprobe analysis (EMPA) techniques. Based on the textural characteristics and mineral assemblages, three types of scheelite were categorized, including Sch A1, Sch A2, and Sch B. In general, Sch A1 formed during the prograde stage, mostly occurring as euhedral grains that distributed discretely within the interstices of skarn minerals. Sch A2 predominantly formed as the rim of Sch A1 or crosscut Sch A1. It is commonly associated with sulfides, such as pyrrhotite, pyrite, and molybdenite. Sch B is primarily observed in the quartz-sulfide veins or within pyrrhotite crystals, occurring later than Sch A1 and Sch A2. Geochemically, Sch A1 contains a significantly higher Mo content (>14,300 ppm) and is characterized by a negative inclined chondrite-normalized rare earth element (REE) pattern, while Sch B has Mo contents lower than 10,300 ppm and exhibits an M-type tetrad REE pattern. Sch A2 contains a Mo content ranging from 146 ppm to 89,000 ppm (mean 27,900 ppm) and displays an intricate REE pattern that partially overlaps with Sch A1 and Sch B. The difference of REE concentrations among different scheelite generations is controlled by substitution mechanisms and also influenced by the precipitation of garnet and pyroxene. Sch A1 and Sch B exhibit a linear 1:1 trend between Na (atom) and ΣREE – Eu + Y (atom), indicating the important role of substitution via 2Ca2+ = REE3+ + Na+. The concentrations of Nb, Ta and V are notably low, supporting only a small amount of REE incorporation into Sch A1 through Ca2+ + W6+ = REE3+ + (Nb + Ta + V)5+. The REE patterns of Sch A1 and partly Sch A2 resemble those of the causative intrusions, indicating that substituting the site vacancy in scheelite lattice is another crucial mechanism. All three substitution mechanisms play roles in REE incorporation during the scheelite mineralization process. Negative Eu anomalies prevail in Yuku scheelite (mean δEu = 0.77), although positive Eu anomalies are also observed, particularly in Sch B (mean δEu = 1.11). Additionally, there is a conspicuous decreasing trend in the Mo content from the prograde to late stage, suggesting that the Mo-W mineralization at Yuku likely experienced a decrease in oxygen fugacity and/or temperature. Furthermore, in a comparative analysis of scheelite Mo content and Eu anomaly with other deposits, it was observed that Mo content in skarn deposits is generally higher than that in orogenic deposits (mostly <100 ppm), providing a tool for distinguishing deposit types utilizing scheelite geochemical characteristics.

Effects of iron overload in human joint tissue explant cultures and animal models.

Osteoarthritis (OA) is a prevalent degenerative joint disease affecting over 530 million individuals worldwide. Recent studies suggest a potential link between iron overload, a condition characterised by the excessive accumulation of iron in the body, and the onset of OA. Iron is essential for various biological processes, and any disruption in its homeostasis can trigger significant health effects, including OA. This study aimed to elucidate the effects of excess iron on joint tissue and the underlying mechanisms associated with excess iron and OA development. Human articular cartilage (n = 6) and synovium (n = 4) were collected from patients who underwent total knee arthroplasty. Cartilage and synovium explants were incubated with a gradually increasing concentration of ferric ammonium citrate for 3days respectively. The effects of iron homeostasis in tissue explants were analysed using a Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). To further study the effects of iron excess on OA initiation and development, male 3-week-old Hfe-/- and 5-week-old Tfr2-/- mice, animal models of hereditary haemochromatosis were established. Littermate wild-type mice were fed a high-iron diet to induce dietary overload. All animals were sacrificed at 8weeks of age, and knee joints were harvested for histological analysis. The LA-ICP-MS analysis unveiled changes in the elemental composition related to iron metabolism, which included alterations in FTH1, FPN1, and HAMP within iron(III)-treated cartilage explants. While chondrocyte viability remained stable under different iron concentrations, ex vivo treatment with a high concentration of Fe3+ increased the catabolic gene expression of MMP13. Similar alterations were observed in the synovium, with added increases in GAG content and inflammation markers. In vivo studies further supported the role of iron overload in OA development as evidenced by spontaneous OA symptoms, proteoglycan loss, increased Mankin scores, synovial thickening, and enhanced immunohistochemical expression of MMP13, ADAMTS5, and P21 in Hfe-/-, Tfr2-/-, and diet-induced iron overload mouse models. Our findings elucidate the specific pathways through which excess iron accelerates OA progression and highlights potential targets for therapeutic intervention aimed at modulating iron levels to mitigate OA symptoms. KEY MESSAGES: Iron overload alters joint iron metabolism, increasing OA markers in cartilage and synovium. High iron levels in mice accelerate OA, highlighting genetic and dietary impacts. Excess iron prompts chondrocyte iron storage response, signalling potential OA pathways. Iron dysregulation linked to increased cartilage degradation and synovial inflammation. Our findings support targeted therapies for OA based on iron modulation strategies.

Laser ablation inductively coupled plasma mass spectrometry measurements for high-resolution chemical ice core analyses with a first application to an ice core from Skytrain Ice Rise (Antarctica)

Abstract. Conventional methods of inorganic impurity analysis do not provide high enough depth resolution for many scientific questions in ice core science. In this study, we present a setup of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for high-resolution glacier ice impurity analysis to the sub-millimetre scale. This setup enables ice core chemical impurity analysis to a depth resolution of ∼182 µm while consuming only very small amounts of ice. The system performs simultaneous analysis of sodium, magnesium and aluminium incorporated in the ice matrix. In this case study within the framework of the WACSWAIN (WArm Climate Stability of the West Antarctic Ice Sheet in the last INterglacial) project, our method is applied to a selection of samples from the Skytrain ice core (West Antarctica) over a total length of 6.7 m consisting of about 130 single samples. The main goal of this study is to use the new LA-ICP-MS method to extract meaningful climate signals on a depth resolution level beyond the limits of continuous-flow analysis (CFA). A comparison between low-resolution CFA data and the high-resolution LA-ICP-MS data reveals generally good agreement on the decimetre scale. Stacking of parallel laser measurements together with frequency analysis is used to analyse the high-resolution LA-ICP-MS data at millimetre resolution. Spectral analysis reveals that despite effects of impurity accumulation along ice crystal grain boundaries, periodic concentration changes in the Skytrain ice core on the millimetre scale can be identified in ice from 26.8 ka (kiloyears before present, i.e. 1950 CE). These findings open new possibilities for climate data interpretation with respect to fast changes in the last glacial period and beyond, for example within the Beyond EPICA oldest-ice project.

Morphogenetic varieties of iron oxyhydroxides in shimmering smokers-diffusers of the Rainbow hydrothermal field (36°13′ N, 33°54′ W, Mid-Atlantic Ridge): LA-ICP-MS data for the development of halmyrolysis theory

Research subject. Iron oxyhydroxides covering and replacing the chimneys of shimmering water smokers-diffusers of the Rainbow hydrothermal field (MAR). Aim. To identify features of the concentration and associations of chemical elements in varieties of iron oxyhydroxides to recognize patterns of geochemical differentiation under conditions of halmyrolysis of sulfide chimneys-diffusers. Materials and methods. Samples were collected during a dive to a depth of 2300 m using the manual manipulator of the Mir-2 manned vehicle (travel No. 50, research vessel Akademik Mstislav Keldysh, 2005). Varieties of iron ohyhydroxides were identified using electron microscopes (REMMA-202М with LZ-5 Link system, Tescan Vega 3 sbu with an Oxford Instruments X-act energy-dispersive analyzer, and Jeol Superprobe 733 with an EDA Oxford Instruments INCAx-sight) and a powder X-ray diffractometer (SHIMADZU XRD-6000, CuK-α radiation with monochromator). Further, a mass spectrometry with inductively coupled plasma and laser ablation (LA-ICP-MS) analysis was conducted at the South Urals Federal Scientific Center of Mineralogy and Geoecology, Ural Branch of the Russian Academy of Sciences. Results. Microlayered goethite aggregates containing admixtures of barite, calcite, aragonite, native sulfur, covellite, sphalerite, and an X-ray amophoric oxyhydroxide phase of iron cover the shimmering diffusers. Towards the inner parts of the chimney walls, they are replaced by pseudomorphs of lepidocrocite after pyrite and pyrrhotite, and then by radial and bacteriomorphic crustifications of lepidocrocite. The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that goethite varieties have the increased contents of Zn and Co associated with other elements of medium-temperature hydrothermal fluids (Cd, Mn, Ni, Ga, Sn, Pb and Sb) in the absence of significant concentrations of a high-temperature hydrothermal association (Se, Bi, Te). The role of elements of seawater association (Mg, Na, K, Sr, U, V, As, Mo, Ni, P, B, W, Cs, REE) decreases from the surface layered goethite aggregates to crustification varieties of lepidocrocite. Different scenarios of accumulation under conditions of sulfide halmyrolysis and precipitation on local reduction barriers are proposed for elements with different valences (U, V, Mo, As, Cr, Eu). It is assumed that some of the microelements (Sr, V, As, P, REE) found in goethite are products of sorption on iron hydroxides or are part of invisible Fe-Ca hydroxyphosphates. Conclusion. The influence of sulfide halmyrolysis on the differentiation of chemical elements has been revealed.

Occurrence and enrichment of critical metals in ferromanganese deposits in the western Pacific

Co-rich ferromanganese nodules and crusts are economically valuable deep-sea ferromanganese deposits widely distributed in the western Pacific Ocean and are rich in critical metals such as Co, Ni, Cu and rare earth elements (REEs). However, the lack of fine delineation and systematic comparisons of the distributions of these critical metals in these ferromanganese deposits limits the understanding of the occurrence states of Co, Ni, Cu and REEs and the metallogenesis of ferromanganese deposits. Therefore, the authors selected one nodule and one crust from the western Pacific Ocean, and utilized high-resolution methods such as micro-area X-ray fluorescence spectrometry (μ-XRF), laser-ablation inductively-coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS), and laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) to depict elemental distribution and elemental profile.The results show that the ferromanganese deposits are predominantly composed of Fe-vernadite with low Mn/Fe ratios. Co, Ni and Cu exist primarily in the manganate octahedral layer of Fe-vernadite. REEs mostly exist in feroxyhite of Fe-vernadite, and manganate octahedral layer of Fe-vernadite also have high Ce content. Co, Ni and Cu contents of ferromanganese deposits are closely correlated with Mn/Fe ratios: Co, Ni and Cu contents increase with Mn/Fe ratios until the Mn/Fe ratios rises up to 4, and remain stable when Mn/Fe ratios > 6. The enrichment of Co, Ni and Cu in ferromanganese deposits is controlled by the redox conditions of seawater during accretion, whereas REEs enrichment is related to Mn and Fe fluxes in seawater during accretion. The coupling relationships between elemental distributions help to reveal the elemental occurrence state, and the geochemistry of ferromanganese deposits are analyzed to identify element enrichment mechanism.

New insights of emerald geographic origin determination based on the infrared spectroscopy of D2O and HDO molecules

Emerald geographic origin determination in laboratories typically relies on the microscopic features of inclusions, ultraviolet through visible and near-infrared (UV-Vis-NIR) spectroscopy, and trace element chemistry measured by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS). Infrared (IR) spectroscopy, a non-destructive technique, has played a minor role in this process. This work conducts a systematic examination of emerald samples from twelve origins, encompassing spectroscopic, and trace element analyses. For the first time, IR absorptions related to D2O and HDO molecules within the 2600–2850 cm–1 range from multiple origins (333 emerald samples) were recorded, assigned, and classified. These IR absorptions, controlled by the concentrations of deuterium (D) and alkali metals (primarily sodium) within channels, reveal three distinct patterns and derived four groups that serve as strong evidence for origin determination. Emeralds from Zambia group display the most prevalent HDO-dominant IR-pattern I characterized by the pronounced absorption peak of Type II HDO at 2672 cm–1; Panjshir (Afghanistan) and Swat (Pakistan) emeralds exhibit the transitional type IR-Pattern II with overall five peaks and obvious 2808 cm–1 peak; D2O-dominant IR-Pattern III is featured by marked absorption band at 2740 cm–1, and can be further subdivided into two subtypes (IIIa and IIIb). IR-Pattern IIIb is currently only found in Nigerian emeralds, characterized by strong broad band of Type I D2O due to enriched deuterium and obvious absorption of Type I HDO at 2685 cm–1 due to depleted sodium. Furthermore, this research updates the classification of UV-Vis-NIR spectra, unveils the trace element features, and presents effective compositional diagrams. This contribution enriches and expands existing techniques and provides new insights for emerald origin determination.

Genesis of the Wangu Au deposit in the Jiangnan orogenic belt: Constraints from texture, trace element, and in-situ Sr isotope of scheelite

Scheelite occurs widely in quartz vein-type Au deposits and serves as an indicator mineral for ore deposit genesis. The Wangu Au deposit, situated in the central part of the Jiangnan orogen belt, South China, is one of the largest Au deposits, with reserves exceeding 85 tonnes. Scheelite has been well-recognized within the Au-bearing quartz veins with a significant amount. To further elucidate the genesis of the Wangu deposit, this study focuses on scheelite to delineate the nature of ore-forming fluids and ore-forming material, by conducting TESCAN Integrated Mineral Analyzer (TIMA), cathodoluminescence (CL), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) for texture, trace elements, and in-situ Sr isotope analyses.Scheelite from the Wangu Au deposit exhibits three texture-types: early homogeneous (Sch-I-1), oscillatory zones (Sch-I-2), and late veinlet (Sch-II). These different texture-type scheelites show a relatively flat to slightly MREE-enriched chondrite-normalized fractionation pattern, predominantly governed by the substitution mechanism of Ca2+=2REE3++□Ca (□Ca is a Ca site vacancy). Most positive and few negative europium (Eu) anomalies are observed for these different types of scheelite (0.5 to 46.7, mean 5.0), indicating Eu2+ is predominant over Eu3+. Together with the presence of methane in fluid inclusions within scheelite, indicating reduced nature of ore-forming fluids during its precipitation. All texture-types of scheelite have high Sr (383 to 12558 ppm, mean 3408 ppm) and low Mo (<1.7 ppm, mean 0.1 ppm) contents. In-situ Sr isotope data reveal that the 87Sr/86Sr ratios for Sch-I-1 range from 0.74601 to 0.76920, for Sch-I-2 ranging from 0.76485 to 0.76673, and for Sch-II ranging from 0.75627 to 0.75620. This high radiogenic Sr isotope composition of scheelite implies that fluid-rock interaction process is key to mineralization, and this process will add ore-forming materials from wallrock to the ore-forming system. Combined with the contribution of deep magmatic fluid inferred from the published isotope compositions such as H-O and He-Ar, we propose that W mineralization of Wangu deposit is associated with magmatic fluid, which is different from the classical orogenic Au deposit that formed from metamorphic fluid.

Gold and antimony metallogenic relationship of the Awanda Au (Sb) deposit, South Tianshan, NW China: Constraints from textures, in-situ trace elements and s-pb isotope systematics

The Tianshan is one of the most important gold ± antimony metallogenic province in the world. However, the relationship between Au and Sb mineralization remains poorly understood, largely due to lacking of systematic investigation on typical Au-Sb deposits. Here, we reported in-situ trace elements and S-Pb isotopic dataset on the Awanda Au (Sb) deposit, which is currently the second largest gold deposit in Chinese South Tianshan, and contain highly antimony (Sb) by our new petrographic observations. Sulfide from two minelization stages, i.e., Stage Ⅰ (arsenopyrite, pyrite, pyrrhotite, and minor chalcopyrite) and Stage II (gudmundite, aurostibite and stibnite), were analyzed using laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Trace element compositions reveal that ore minerals display positive correlations between As and Au-Sb-Cu-Zn-Pb, implying a common source for these elements. In situ δ34S values of sulfides that cluster in the range of − 2.94 to + 0.8 ‰, suggesting that sulfur contained in Au-As-Sb-bearing fluids were most likely derived from Upper Paleozoic sediments (δ34S = − 1.6 to + 0.3 ‰) during regional metamorphism. In-situ 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios (17.882 to 18.002, 15.467to 15.620 and 37.831 to 38.344) from sulfides are also support that the Upper Paleozoic strata may have supplied substantial metals. Combined with published electron microprobe and fluid inclusions data, our textural and chemical data suggest that fluid-rock interaction and decrease in pressure, temperature, and oxygen-sulfur fugacity were the main cause for Au-As and Au-Sb minelization, respectively. In summary, we propose that the Awanda Au (Sb) deposit fits the crust metamorphic model with Au-As and Au-Sb mineralization occur at mesozonal and epizonal depths, respectively.

Role of As in the formation of giant Au deposits: Insights from sulfur isotope and geochemistry of pyrite from the Shuangwang Au deposit, West Qinling, central China

The Shuangwang Au deposit (SWGD), located in the Feng-Tai ore district, is one of the largest Au deposits in the West Qinling orogen, central China. Au orebodies in this deposit are mainly hosted in the Upper Devonian Xinghongpu Formation. The source of the fluids and metals ore-forming processes and the enrichment mechanism of Au in this ore deposit remain equivocal. Here we present results from geochemical studies of pyrite from the SWGD to address these issues through the application of Scanning electron microscopy (SEM), electron probe microanalysis (EPMA), in-situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and LA-MC-ICP-MS analyses. Based on detailed petrographic studies of the mineralization and host rocks, we identify seven generations of pyrite. Among these, the pre-ore syn-sedimentary pyrite (Py0) is characterized by relatively elevated concentrations of As, Co, Ni and Au compared to the Py1 in the albite-ankerite veins and Py2 in the quartz-ankerite-pyrite veins, and has positive δ34S values of + 6.00 to + 10.48 ‰, whereas Py3 forms as veinlets or aggregates in the pyrite-tourmaline veins and is enriched in As, Co, Cu, Se and Au. Py4 occur as coarse-grained subhedral to euhedral crystals or aggregates in the ankerite-pyrite veins and exhibit oscillatory zones. Py5 comprises fined-grained subhedral to anhedral grains in the fluorite-ankerite-pyrite cements, and is relatively depleted in trace elements when compared to the other pyrite types. The δ34S values of the different types of pyrite from the SWGD have significant differences, indicating a multiple and mixed source for sulfur and, by inference, for the ore-forming fluid(s). Two periods of Au mineralization are identified in the SWGD: the early NW-trending mineralization sourced from the metamorphism of the metasedimentary sequences in a compressional environment and the late NE-trending mineralization probably exsolved from an unexposed and coeval granitoid pluton at depths in a post-collisional extensional setting. The coupled geochemical behavior of Au and As can be explained by mixing-induced cooling. Our results also indicate that arsenic might have played an important role in the enrichment of Au and the formation of this hydrothermal Au deposit.

Triple-oxygen isotopes of stony micrometeorites by secondary ion mass spectrometry (SIMS): Olivine, basaltic glass and iron oxide matrix effects for sensitive high-mass resolution ion microprobe-stable isotope (SHRIMP-SI).

Micrometeorites are extraterrestrial particles smaller than ~2mm in diameter, most of which melted during atmospheric entry and crystallised or quenched to form 'cosmic spherules'. Their parentage among meteorite groups can be inferred from triple-oxygen isotope compositions, for example, by secondary ion mass spectrometry (SIMS). This method uses sample efficiently, preserving spherules for other investigations. While SIMS precisions are improving steadily, application requires assumptions about instrumental mass fractionation, which is controlled by sample chemistry and mineralogy (matrix effects). We have developed a generic SIMS method using sensitive high-mass resolution ion micro probe-stable isotope (SHRIMP-SI) that can be applied to finely crystalline igneous textures as in cosmic spherules. We correct for oxygen isotope matrix effects using the bulk chemistry of samples obtained by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and model bulk chemical compositions as three-component mixtures of olivine, basaltic glass and Fe-oxide (magnetite), finding a unique matrix correction for each target. Our first results for cosmic spherules from East Antarctica compare favourably with established micrometeorite groups defined by precise and accurate but consumptive bulk oxygen isotope methods. The Fe-oxide content of each spherule is the main control on magnitude of oxygen isotope ratio bias, with effects on δ18O up to ~6‰. Our main peak in compositions closely coincides with so-called 'Group 1' objects identified by consumptive methods. The magnitude of SIMS matrix effects we find is similar to the previous intraspherule variations, which are now the limiting factor in understanding their compositions. The matrix effect for each spherule should be assessed quantitatively and individually, especially addressing Fe-oxide content. We expect micrometeorite triple-oxygen isotope compositions obtained by SIMS to converge on the main clusters (Groups 1 to 4) after correction firstly for magnetite content and secondarily for other phases (e.g., basaltic glass) in each target.

Do probiotics and iron supplementation have any impact on element distribution in rat kidneys? – bioimaging by laser ablation inductively coupled plasma mass spectrometry

This study investigates the influence of multistrain probiotics and iron supplementation on the distribution and interaction of trace elements in the kidneys of Wistar rats using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) bioimaging. Forty 6-week-old female Wistar rats were divided into five groups, each fed an AIN-93 M diet with varying additions or deficiencies of iron and probiotics, which included a control, an iron-deficient diet, an iron-deficient diet with probiotics, an iron-deficient diet with iron supplementation, and an iron-deficient diet with both probiotics and iron supplementation. The obtained two-dimensional maps of the distribution of elements reveal distinct locations of Cu, Fe, Mn, and Zn in specific tissues of rat kidneys. Specifically, Cu and Fe were co-localized in the renal cortex, while Zn was mostly absent from regions where Cu and Fe accumulated. Fe supplementation alone increased Fe in the renal cortex, while probiotics enhanced this effect, suggesting a synergistic role in Fe absorption. The total content of elements in the kidneys of all groups was determined after digestion: Cu 13.3–24.7 mg kg−1, Fe 218–509 mg kg−1, Mn 0.87–1.29 mg kg−1, and Zn 28.6–40.1 mg kg−1. Competitive interactions among Cu, Fe, and Zn were observed, with probiotics modulating their concentrations and distribution, highlighting their role in trace element homeostasis. Our research provides insights into the interactions between dietary supplements, probiotics, and trace element distribution in kidneys, paving the way for targeted nutritional interventions. This study highlights the need for further research on trace element functions in organisms and their impact on health.

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.

Multistage fluid mixing events induced Sn polymetallic super-enrichment at Dulong in Yunnan Province, South China

Dulong Sn polymetallic deposit is a world-class skarn tin deposit situated at the Youjiang basin with a reserve of 0.4 Mt Sn at 0.56 %, 5.0 Mt Zn at 5.12 %, together with 7 kt In. The deposit predominantly occurs within the Neoproterozoic Xinzhaiyan Formation and is controlled by NS-trending faults. Based on elaborate field and petrographic observations, the Dulong Sn polymetallic deposit was divided into four mineralization stages: stage 1 (prograde stage), stage 2 (retrograde stage), stage 3 (quartz-sulfide stage) and stage 4 (carbonate stage). Tin mineralization primarily occurs as cassiterite during stage 2, with additional cassiterite-stannite formation noted in stage 3. Analysis of fluid inclusions across these stages reveals the evolutionary history of the mineralizing fluids and the precipitation mechanisms at Dulong. During stage 1, diopside hosts both daughter-bearing multiphase inclusions and vapor-rich inclusions. The daughter-bearing multiphase inclusions exhibit homogenization temperatures ranging from 510 to 574 °C and salinities between 44.7 and 49.6 wt% NaCl equiv., whereas the vapor-rich inclusions display homogenization temperatures of 573–586 °C and salinities from 2.9 to 4.0 wt% NaCl equiv., indicating a boiling fluid process. Cassiterite (stage 2) features primarily liquid-rich two-phase inclusions, with homogenization temperatures of 351–410 °C and salinities of 6.3–9.6 wt% NaCl equiv. These inclusions document the mixing of magmatic fluid with meteoric water, which is likely the principal mechanism driving initial tin mineralization. Similarly, the same type of inclusions is also recorded in cassiterite of stage 3. The homogenization temperature of the inclusions in cassiterite is 290–334 °C and the salinities of the inclusions is 3.4–8.4 wt% NaCl equiv. Comparatively, the temperature continued to decrease in stage 3, indicating that fluid mixing may have persisted during this stage which could also explain the occurrence of cassiterite and stannite in this stage. In addition, redox reaction where CO2 and/or As (III) serve as oxidants may also be another mechanism to exact cassiterite from ore-forming fluid. Our Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data suggests that cassiterite of the Dulong deposit involves a variety of complex substitutional mechanism. Due to the differing geochemical properties of the elements and variations in their concentrations, there is an indication that two phases distinct mineralizing fluids may have been present. The varying geochemical properties and concentrations of elements such as Nb, Ta, Zr, Fe, In, and Ga align with microthermometric results, indicating a reduction in magmatic hydrothermal fluid contribution and/or a transition from high to low temperatures in the hydrothermal system. This variation is also likely attributable to fluid mixing processes.

Genetic relationship between W mineralization and granitic intrusion in Nanling Region, South China: Constraints from zircon and cassiterite u-pb age from new drill holes in Shangping deposit

The Nanling metallogenic belt is known for the widely development of typical quartz vein type W deposit. These quartz veins that contain wolframite are frequently located in close proximity to granitic intrusions. The genetic relationship between tungsten mineralization and the associated granitic rocks is still a subject of controversy. The Shangping deposit stands out as a historically significant W deposit with a quartz vein type in the region of Nanling. However, the specific time that W mineralization occurred remains enigmatic. Granitic intrusions are absent from the mine and only granite porphyry dike is exposed, so the link between tungsten mineralization and magmatic activity remains unclear. Fortunately, in recent years, a concealed granite intrusive has been exposed in drill holes in the southeastern of the Shangping W deposit. To comprehensively address the connection between granitic magma activity and W mineralization, it is vital to make up a relative deficiency of geochronological information on granite and ore mineral. Here, in order to get the first direct age constraints on the origin of the Shangping W deposit, we use a combination of different techniques, incorporating the Hf isotope geochemistry of zirconium and cassiterite U-Pb assessment using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Based on these robust data, we tentatively evaluated the connection between W mineralization and granitic intrusion.For the granite porphyry, the majority of representative U-Pb zircon assays establish a206Pb/238U age of 150.2 ± 0.5 Ma. An inferred emplacement age of ca. 151 Ma for the concealed granite in Kengweiwo is supported by a U-Pb isochron age from zircon. Combined with Hf isotopic characterization, it illuminates the mineralization potential of the Kengweiwo concealed granite. Cassiterite grains from hydrothermal quartz vein are subhedral to anhedral and have a lower intercept 206Pb/238U age of 153.9 ± 1.0 Ma. For the Shangping W deposit, all of these new geochronological dates provide well-constrained mineralization ages of 150–154 Ma. The dates of the concealed granite in the Kengweiwo area and the tungsten mineralization in the Shangping area are extremely concordant, indicating that they occurred roughly concurrently. The vein type tungsten mineralization in Shangping deposit may has a genetic link with crystallization of uncovered granite present at depth, which requires further investigation. These results emphasize the significance and potential of concealed granitic intrusion to host disseminated W mineralization in the deep part of Shangping deposit.

Effects of Thermal Annealing and Chemical Abrasion on In-situ U-Pb Dating of Complex Ancient Zircons by Laser Ablation ICP-MS

Effects of Thermal Annealing and Chemical Abrasion on In-situ U-Pb Dating of Complex Ancient Zircons by Laser Ablation ICP-MS

Geochronology and petrogenesis of Early Mesozoic Rb-mineralized granitic rocks from the Liuzhangshan Rb, West Qinling Orogen Belt, China

ABSTRACT The newly discovered Liuzhangshan (LZS) Rb deposit is a large granite-type deposit in the West Qinling Orogenic Belt (WQOB), spatially associated with biotite monzogranite. Previous research has focused on the geological characteristics and metallogenic conditions of the LZS Rb deposit; however, its geochronology and petrogenesis remain unclear. In this study, monazite U-Pb dating of biotite monzogranite in the LZS deposit yielded a U-Pb age of 200.8 ± 0.9 Ma via laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Combined with the age of magmatic rocks in the WQOB, we propose a potential mineralization event related to Rb around 200 Ma in the WQOB. The biotite monzogranite belongs to weakly peraluminous, high-K calc-alkaline serious, containing high SiO2, Na2O, K2O, and low FeO, MgO, CaO, and P2O5. Compared with primitive mantle and relatively unfractionated granodiorites found in the WQOB, the biotite monzogranite enriched in Rb, Th, U, and Pb, deleted in Ba, Sr, and Ti, and showed negative Eu anomalies, a high Rb/Sr ratio, and a low K/Rb ratio, an ∑REE of 31.3 ppm, an LREE/HREE ratio of 6.48, a LaN/YbN ratio of 2.59, an Mg# of 4.15, and a crystallization temperature of 760°C, the biotite monzogranite also had a high differentiation index (DI = 98.2), apparent tetrad effect (TE 1,3 = 1.12 ~ 1.15), characteristic of highly fractionated I-type granite. Monzoite from the biotite monzogranite in the LZS deposit has negative εNd(t) values ranging from −12.45 to −11.17, and TDM1 of 1569 ~ 2018 Ma, indicating that the LZS biotite monzogranite originated from the partial melting of a Mesoproterozoic ancient basement material, with a minor contribution from mantle-derived melts. Highly differentiated, low Sr and Yb contents, Sr/Yb ratios, and low crystallization temperature magma facilitated the enrichment of Rb.

Variation in lifetime movements of an Ariidae species in an eastern Australian river revealed by otolith microchemistry

Ariids, or sea catfishes, inhabit marine, estuarine, and occasionally freshwater habitats circumtropically. They are most often locally abundant and are important in artisanal and commercial fisheries, particularly in developing countries. Detailed information on the ecology and habitat preferences of many of the genera within the family is lacking. We analysed the otolith of 57 blue catfish, Neoarius graeffei, collected from the lower reaches of the Clarence River, NSW, Australia with the aim of better understanding the species movement ecology, including its ability to respond to environmental change. Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) was used to quantify Sr:Ca, Ba:Ca and 87Sr:86Sr ratios in otoliths and infer lifetime movement patterns. Otolith microchemistry revealed inter-individual variation in the movement patterns of N. graeffei. A strong affinity for estuarine waters was evident among most individuals, with movement into upstream freshwater habitats for extended periods discernible in some individuals. Variation in movement patterns was identified by changes in Ba:Ca, Sr:Ca and 87Sr:86Sr otolith profiles, although Sr:Ca lacked clear patterns. Furthermore, both Ba:Ca and 87Sr:86Sr otolith transects revealed estuarine residence by juveniles, as well as multiple movements among chemically distinct areas throughout the lifetime of some individuals. Otolith microchemistry enabled elucidation of long-term movement patterns of N. graeffei in our study. Uncovering the variable movement patterns of a single species identifies the potential adaptable nature of other species within the Ariidae family and indicates N. graeffei is resilient to environmental changes and anthropogenic impacts.

Evidence of glass bead‐making in the early Islamic Iberian Peninsula

AbstractGlass beads from two Islamic archaeological sites in the Tagus valley in central Spain were selected and analysed by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS), and a subset of samples (n = 6) was analysed for Pb isotopes by multicollector thermal ionization mass spectrometry (MC‐TIMS). The analytical and isotopic data of the beads from Ciudad de Vascos (Toledo) and Albalat (Cáceres) demonstrate beyond reasonable doubt that glass beads were produced in the Iberian Peninsula during the Islamic period using local Pb‐silica and soda‐rich plant‐ash glass. The bead workshops in al‐Andalus were evidently part of an efficient system of glass collection and recycling, and used only relatively simple bead‐making techniques such as winding and folding. At present it is unclear to what extent the Islamic bead‐makers in the Iberian Peninsula were involved in the international trade in glass beads or whether their products were mainly destined for a regional market. Despite local production, some samples show compositional and typological features that suggest the import of finished glass beads, perhaps from Central Asia.