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Breast cancer (BC) is the leading cause of cancer death among women worldwide, making the discovery and quantification of new biomarkers essential for improving diagnostic and preventive strategies to limit dissemination and improve prognosis. Essential trace metals such as Fe, Cu, and Zn may play critical roles in the pathophysiology of both benign and malignant breast tumors. However, due to the high metabolic activity and reduced element selectivity of cancer cells, also non-essential elements may be taken up and may even be implicated with disease progression. This study investigates the spatial distribution and concentrations of both essential and non-essential elements in breast tissues, assessing their potential for diagnostic applications. Laser ablation (LA)-inductively coupled plasma-mass spectrometry (ICP-MS) with a time-of-flight (ToF) mass analyzer (LA-ICP-ToF-MS) was used to inquire the distribution of almost all elements across the periodic table and their abundance in metastatic (n = 11), non-metastatic (n = 7), and healthy (n = 4) breast tissues. Quantification was achieved using gelatine-based standards for external calibration to quantitatively map various elements. Overall, the Fe, Cu, Zn, Sr, and Ba levels were significantly increased in tumor samples with Sr and Ba showing strong correlation, likely due to their similar chemistry. Comparison of calibrated LA-ICP-ToF-MS data with a histologic staining demonstrated the possibility to clearly differentiate between various tissue types and structures in breast tissues such as tumor niche and stroma. The levels of the studied elements were significantly higher in the tumor niche areas compared to the stroma, and for Fe, a significant accumulation was observed in the tumor niche areas from the metastatic patient group relative to the levels found in the same areas of the non-metastatic group., Competing Interests: Declarations. Ethical approval: This study was conducted in accordance with national regulations and received approval from the Ethics and Investigation Committee of the Hospital de Jove Foundation (PI02/2018). Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

Innate immune systems alter the concentrations of trace elements in host niches in response to invading pathogens during infection. This work reports the interplay between d-block metal ions and their associated biomolecules using hyphenated elemental techniques to spatially quantify both elemental distributions and the abundance of specific transport proteins. Here, lung tissues were collected for analyses from naïve and Streptococcus pneumoniae-infected mice fed on a zinc-restricted or zinc-supplemented diet. Spatiotemporal distributions of manganese ( 55 Mn), iron ( 56 Fe), copper ( 63 Cu), and zinc ( 66 Zn) were determined by quantitative laser ablation-inductively coupled plasma-mass spectrometry. The murine transport proteins ZIP8 and ZIP14, which are associated with zinc transport, were also imaged by incorporation of immunohistochemistry techniques into the analytical workflow. Collectively, this work demonstrates the potential of a single instrumental platform suitable for multiplex analyses of tissues and labelled antibodies to investigate complex elemental interactions at the host-pathogen interface. Further, these methods have the potential for broad application to investigations of biological pathways where concomitant measurement of elements and biomolecules is crucial to understand the basis of disease and aid in development of new therapeutic approaches., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Determination of trace element concentrations in continuously growing biological structures such as otoliths, whiskers, and teeth can provide important insight into physiological and ontogenetic processes. We examined concentrations of 11 trace elements (Li, Mg, Mn, Cu, Zn, Se, Rb, Sr, Cs, Ba, Pb) in the annual dentine growth layer groups (GLGs) of teeth of 66 Eastern Canadian Arctic belugas (Delphinapterus leucas). Several of these trace elements displayed clear and consistent patterns in early life, though few longer term trends or signals were present in trace element data for either females or males. Large changes in Sr and Ba concentrations in fetal dentine reflected in utero shifts in element deposition in the teeth of developing belugas. Marked changes in these elements during the first years after birth were likely associated with the onset of nursing and subsequent weaning. Mg, Mn, and Zn also displayed clear and consistent patterns in early life that correlated strongly with dentine stable nitrogen isotope (δ 15 N) data, suggesting these elements merit further study as potential tools for studying nursing and weaning. Depositional patterns of Zn and Pb, which have been linked to sexual maturation in female Pacific walruses (Odobenus rosmarus divergens), were inconsistent in beluga teeth. Some individuals (including males) displayed patterns strongly resembling those observed in female walruses, whereas many animals did not, perhaps because they had not yet reached sexual maturity. The lack of clear patterns in trace element deposition after the first few years of life may have resulted from pooling samples from multiple populations/regions collected across more than two decades, but may also indicate that elemental concentrations are primarily driven by other, extrinsic processes later in life, and might be useful as biomonitors of environmental element concentrations or tools for delineating population structure., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

In this study, a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method for in-situ determination of yttrium and trace elements in yttrium-doped barium fluoride (BaF 2 : Y) crystals was proposed. A facile, micro-damage procedure for quantifying the segregation coefficient of doping elements was investigated, and it was found that the actual yttrium doping concentration increases from the seed end to the tail end in BaF 2 : Y crystals. In micro-area analysis, this method has higher mass sensitivity which was applied to quantify the impurity content and distribution during the growth of BaF 2 : Y crystals. Regression coefficient of calibration curve for each element ranged from 0.9918 to 0.9995. Detection limits (DLs) were 0.05, 0.03, 0.01 and 0.01 μg g -1 for Mg, Zn, Sr and Pb, respectively. The accuracy of the proposed method was verified by inductively coupled plasma mass spectrometry/atomic emission spectroscopy (ICP-MS/AES) with wet-chemical pretreatment. The objective of the presented work was to provide a less damaging and more novelty approach for crystal sample analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) studies on trace element concentration and their spatial distribution in CaC 2 O 4 -matrix urinary stones are important but powerfully rely on matrix-matched external calibration. In this work, CaC 2 O 4 precipitate CaOx-1 which was doped with Mg, Cr, Mn, Fe, Co, Cu, Zn, and Sr was prepared by the homogeneous co-precipitation method. It had a homogeneous distribution of major (RSD of 0.46%) and trace elements (RSD of 1.83-6.92%) due to the negligible concentration difference compared with that prepared by the heterogeneous co-precipitation method. Based on this, an analytical method for quantitative determination of elemental concentration in CaC 2 O 4 -matrix samples was established using CaOx-1 as a calibration standard, and the accuracy of this method was assessed by calibrating the elemental concentration in another synthetic CaC 2 O 4 precipitate CaOx-2 with relative deviation (D r ) from - 11.43% (Mn) to 9.76% (Mg). Finally, a methodology for quantitative imaging of Mg, Cr, Mn, Fe, Co, Cu, Zn, and Sr in urinary stones via LA-ICP-MS was developed. From the elemental distributional maps, an annular texture can be found for Mg, Cu, Zn, and Sr, which corresponds to the annular white and brown texture in the real urinary stone. A homogeneous distribution of Fe and low concentrations of Cr and Co were found throughout the stone, while Mn was highly concentrated in the margin of the stone. All these results demonstrate that quantitative distribution patterns of Mg, Cr, Mn, Fe, Co, Cu, Zn, and Sr can be obtained by LA-ICP-MS using CaOx-1 as a calibration standard, which can provide potential evidence for urological and other medical studies., (© 2023. Springer-Verlag GmbH Germany, part of Springer Nature.)

Element analysis in clinical or biological samples is important due to the essential role in clinical diagnostics, drug development, and drug-effect monitoring. Particularly, the specific forms of element binding, actual redox state, or their spatial distribution in tissue or in single cells are of interest in medical research. This review summarized exciting combinations of sophisticated sample delivery systems hyphenated to inductively coupled plasma-mass spectrometry (ICP-MS), enabling a broadening of information beyond the well-established outstanding detection capability. Deeper insights into pathological disease processes or intracellular distribution of active substances were provided, enabling a better understanding of biological processes and their dynamics. Examples were presented from spatial elemental mapping in tissue, cells, or spheroids, also considering elemental tagging. The use of natural or artificial tags for drug monitoring was shown. In the context of oxidative stress and ferroptosis iron, redox speciation gained importance. Quantification methods for Fe 2+ , Fe 3+ , and ferritin-bound iron were introduced. In Wilson's disease, free and exchangeable copper play decisive roles; the respective paragraph provided information about hyphenated Cu speciation techniques, which provide their fast and reliable quantification. Finally, single cell ICP-MS provides highly valuable information on cell-to-cell variance, insights into uptake of metal-containing drugs, and their accumulation and release on the single-cell level.

In November 2015, the collapse of the Fundão dam (Minas Gerais, Brazil) carried over 40 × 10 6 m 3 of iron ore tailings into the Doce river and caused massive environmental and socioeconomic impacts across the watershed. The downstream mudslide scavenged contaminants deposited in the riverbed, and several potentially toxic elements were further released through reduction and solubilization of Fe oxy-hydroxides under estuarine conditions. A turbidity plume was formed off the river mouth, but the detection of contaminants' dispersion in the ocean remains poorly assessed. This situation is specially concerning because Southwestern Atlantic's largest and richest reefs are located 70-250 km to the north of the Doce river mouth, and the legal dispute over the extent of monitoring, compensation and restoration measures are based either on indirect evidence from modeling or on direct evidence from remote sensing and contaminated organisms. Coral skeletons can incorporate trace elements and are considered good monitors of marine pollution, including inputs from open cut mining. Here, we studied a Montastraea cavernosa (Linnaeus 1767) coral colony collected 220 km northward to the river mouth, using X-rays for assessing growth bands and Laser Ablation Inductively Coupled Plasma Mass Spectrometry to recover trace elements incorporated in growth bands formed between 2014 and 2018. A threefold positive Fe anomaly was identified in early 2016, associated with negative anomalies in several elements. Variation in Ba and Y was coherent with the region's sedimentation dynamics, but also increased after 2016, akin to Pb, V and Zn. Coral growth rates decreased after the disaster. Besides validating M. cavernosa as a reliable archive of ocean chemistry, our results evidence wide-reaching sub-lethal coral contamination in the Abrolhos reefs, as well as different incorporation mechanisms into corals' skeletons., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Effective biomonitoring requires an understanding of the factors driving concentrations of the substances or compounds of interest in the tissues of studied organisms. Biomonitoring of trace elements, and heavy metals in particular, has been the focus of much research; however, the complex roles many trace elements play in animal and plant tissues can make it difficult to disentangle environmental signals from physiology. This study examined the concentrations of 15 trace elements in the teeth of 122 Pacific walruses (Odobenus rosmarus divergens) to investigate the potential for walrus teeth as biomonitors of trace elements in Arctic ecosystems. Elemental concentrations were measured across cementum growth layer groups (GLGs), thereby reconstructing a lifetime history of element concentrations for each walrus. The locations of GLGs were used to divide trace element time series into individual years, allowing each GLG to be associated with an animal age and a calendar year. The elements studied exhibited a great deal of complexity, reflecting the numerous factors responsible for generating tooth trace element concentrations. Generalized linear mixed models were used to investigate the importance of age and sex in explaining observed variation in trace element concentrations. Some elements exhibited clear physiological signals (particularly zinc, strontium, barium, and lead), and all elements except arsenic varied by age and/or sex. Pearson's correlations revealed that elements were more strongly correlated among calendar years than among individual walruses, and correlations of trace elements within individual walruses were generally inconsistent or weak. Plots of average elemental concentrations through time from 1945 to 2014 further supported the correlation analyses, with many elements exhibiting similar patterns across the ~70-year period. Together, these results indicate the importance of physiology in modulating tooth trace element concentrations in walrus tooth cementum, but suggest that many trace elements reflect a record of environmental exposure and dietary intake/uptake., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Trace element concentrations in the rhizosphere were quantified to better understand why soil liming often fails to reduce cadmium (Cd) uptake by plants. Maize seedlings were grown on a soil with natural background levels of Cd and zinc (Zn). Soil liming increased soil pH from 4.9 to 6.5 and lowered the soil solution free ion activities by factor 7 (Cd) and 9 (Zn). In contrast, shoot Cd concentrations were unaffected by liming while shoot Zn concentrations were lowered by factor 1.9. Mapping of labile soil trace elements using diffusive gradients in thin films (DGT) in combination with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) revealed an almost complete depletion of Cd in the rhizosphere in all soil treatments, showing that Cd uptake is controlled by diffusion. The flux of Cd from soil to the DGT, with direct contact between the soil and the binding gel, was unaffected by liming whereas it decreased by factor 3 for Zn, closely mimicking the contrasting effects of liming on Cd and Zn bioavailability. This evidence, combined with additional flux data of freshly spiked Cd and Zn isotopes in soil and with modelling, suggests that the diffusive transport of Cd in unsaturated soil is more strongly controlled by the labile adsorbed metal concentration than by its concentration in solution. This is less the case for Zn because of its inherently slower desorption compared to Cd., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) are widely accepted techniques for direct sampling of biological materials for elemental analysis, with increasing applications being reported over the recent years. This review is focused on the calibration materials used to quantify trace elements in different biological samples such as soft tissues (for instance brain, liver, hair) and hard tissues (bones and teeth). The design of a correct calibration strategy relies on the choice of an adapted reference material that can be commercially available or prepared in-house, which will be reviewed here. A large variety of methods has been approached and considered promising over the years, and the development of matrix-matched reference biological materials seems now closer than ever and gives hope to even better quantitation using LIBS and LA-ICP-MS.

Both essential and toxic metal contaminants impact agricultural crops by bioaccumulation in plants. The goal of this study was to evaluate the tissue-level spatial distribution of metal(loids) in corn seeds (Zea mays, L.) from contaminated corn fields near the Xikuangshan (XKS) antimony mine in Hunan, China, and compared them with corn (Zea mays everta L., popcorn) grown in a farm in Amherst, MA that practices sustainable farming as a control. How toxic and essential metals translocate through the roots and shoots during early stages of germination was also investigated. The cleaned corn seed samples were mounted in resin blocks and longitudinally dissected into thin sections. The laser ablation parameters were optimized, and the instrument was calibrated using tomato leaf standard reference material (NIST SRM 1573a) in a pellet form. Tissue level distributions of metal(loid)s As, Cd, Hg, Sb and Zn in corn seeds collected were determined using (LA-ICP-MS). Seeds from the control farm were germinated and their roots and shoots were analyzed to determine tissue level concentrations and their spatial distributions. It was found that seeds from the XKS mine region in China had higher overall concentration of all elements analyzed due to metal(loids) absorbed from contaminated mine soils. Metal(loids) concentrations were highest in the embryo (∼360 mg/kg) and pericarp (∼0.48 mg/kg) compared with the endosperm of corn seeds. Essential element Zn was found in the embryo and emerging coleoptile and radicle. Finally, in both roots and shoots, element concentrations were highest proximally to the tip cap compared to distal concentrations and later translocated to distal tissue regions. This study offers unique insights of metal(loid) bioaccumulation and translocation in corn and thus is better able to track metal(loids) contaminants trafficking in our food systems., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A novel calibration strategy for the accurate determination of essential and toxic elements in both plant-based and animal-based foods was developed by synthesizing spiked agarose gels as matrix-matched external standards and carbon as the internal standard (IS). Aqueous solutions of agarose (4%, m/v) with defined amounts of the analytes were cast on a mold and then dried to form the agarose-gel standards. The spatial distributions of the analytes in the gel were examined using surface- and depth-mapping laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) protocols, and the gel homogeneity was found to be excellent (i.e., relative standard derivation <10%). Recovery of the 19 spiked elements in the gel standards was in the range of 86.9-94.7%. The limits of detection (LODs) ranged from 0.0005 (Rb) to 33.7 μg g -1 (S). Analysis results were in good agreement with certified values for various certified reference materials (CRMs). Furthermore, a porous rubber sample supporter was developed to improve the analysis throughput by about 3-fold.

Although exogenous contamination and unreliable reference values have limited the utility of scalp hair as a biomarker of chemical elements exposure, its use in toxicological, clinical, environmental and forensic investigations is growing and becoming more extensive. Therefore, hair elemental analysis is reviewed in the current manuscript which spans articles published in the last 10 years. It starts with a general discussion of history, morphology and possible techniques for elemental analysis, where inductively coupled plasma-mass spectrometry (ICP-MS) is clearly highlighted since this technique is leading quantitative ultra-trace elemental analysis. Emphasis over sampling, quality assurance, washing procedures and sample decomposition is given with detailed protocols compiled in tables as well as the utility of hair to identify human gender, age, diseases, healthy conditions, nutrition status and contamination sites. Isotope ratio information, chemical speciation analysis and analyte preconcentration are also considered for hair. Finally, the potential of laser ablation ICP-MS (LA-ICP-MS) to provide spatial resolution and time-track the monitoring of elements in hair strands instead of conventional bulk analysis is spotlighted as a real future trend in the field., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The elemental content of fish scales is known to be a reliable biogeochemical tag for tracing the origin of fishes. In this study, this correlation is further confirmed to exist on the surface of fish scales using a novel environmental analytical method, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), which bypasses several complicated sample preparation procedures such as acid digestion and pre-concentration. The results suggest that the elemental ratios of Sr/Ca, Ba/Ca, and Mn/Ca on the surface of fish scales are strongly correlated with the geochemical environment of their original habitat. This correlation is further demonstrated to be sensitive to variation of water in the habitat due to the adsorbed inorganic ions. In this sense, the limitation of fish scales as a biogeochemical tag is the sensitivity of LA-ICP-MS toward the studied elements. Graphical abstract Illustration of the connection between element distribution pattern over the surface of fish scales and biogeochemical environment of its habitat.

In this work, a novel calibration approach for minor and trace element quantification in LA-ICP-MS imaging of biological tissues is presented. Droplets of aqueous standard solutions are deposited onto pre-cut pieces of filter paper, allowed to dry, and sputtered with a thin gold layer for use as pseudo-internal standard. Analysis of the standards using LA-ICP-MS is performed using radial line-scans across the filters. In contrast to conventionally used preparation of matrix-matched tissue standards, the dried-droplet approach offers a variety of advantages: The standards are easy to prepare, no characterization of the standards using acid digestion is required, no handling of biological materials is necessary, and the concentration range, as well the number of investigated analytes is almost unlimited. The proposed quantification method has been verified using homogenized tissue standards with known analyte concentrations before being applied to a human malignant mesothelioma biopsy from a patient who had not received any chemotherapeutic treatment. Elemental distribution images were acquired at a lateral resolution of 40 μm per pixel, limits of detection ranging from 0.1 μg g(-1) (Mn, Ni, Cu, Zn) to 13.2 μg g(-1) (K) were reached., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Microchemical analysis of otolith (calcified 'ear stones' used for balance and orientation) of fishes is an important tool for studying their environmental history and management. However, the spatial resolution achieved is often too coarse to examine short-term events occurring in early life. Current methods rely on single points or transects across the otolith surface, which may provide a limited view of elemental distributions, a matter that has not previously been investigated. Imaging by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) permits microchemical analyses of short-term events in early life with high (<10 μm) resolution, two-dimensional (2D) visualization of elemental distributions. To demonstrate the potential of this method, we mapped the concentrations of Sr and Ba, two key trace elements, in a small number of juvenile otoliths of neon damselfish (Pomacentrus coelestis) using an 8 μm beam diameter (laser fluence of 13.8 ± 3.5 Jcm(-2)). Quantification was performed using the established method by Longerich et al. (1996), which is applied to 2D imaging of a biological matrix here for the first time. Accuracy of >97% was achieved using a multi-point non matrix-matched calibration of National Institute of Standards and Technology (NIST) 610 and 612 (trace elements in glass) using Longerich's calculation method against the matrix-matched standard FEBS-1 (powdered red snapper [Lutjanus campechanus] otolith). The spatial resolution achieved in the otolith corresponded to a time period of 2 ± 1 days during the larval phase, and 4 ± 1 days during the post-settlement juvenile phase. This method has the potential to improve interpretations of early life-history events at scales corresponding to specific events. While the images showed gradients in Sr and Ba across the larval settlement zone more clearly than single transects, the method proved sample homogeneity throughout the structure; demonstrating that 2D scanning has no significant advantage over line scans., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Bioimaging using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) offers the capability to quantify trace elements and isotopes within tissue sections with a spatial resolution ranging about 10-100 μm. Distribution analysis adds to clarifying basic questions of biomedical research and enables bioaccumulation and bioavailability studies for ecological and toxicological risk assessment in humans, animals and plants. Major application fields of mass spectrometry imaging (MSI) and metallomics have been in brain and cancer research, animal model validation, drug development and plant science. Here we give an overview of latest achievements in methods and applications. Recent improvements in ablation systems, operation and cell design enabled progressively better spatial resolutions down to 1 μm. Meanwhile, a body of research has accumulated covering basic principles of the element architecture in animals and plants that could consistently be reproduced by several laboratories such as the distribution of Fe, Cu, Zn in rodent brain. Several studies investigated the distribution and delivery of metallo-drugs in animals. Hyper-accumulating plants and pollution indicator organisms have been the key topics in environmental science. Increasingly, larger series of samples are analyzed, may it be in the frame of comparisons between intervention and control groups, of time kinetics or of three-dimensional atlas approaches., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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]

Emeralds - the green colored variety of beryl - occur as gem-quality specimens in over fifty deposits globally. While digital traceability methods for emerald have limitations, sample-based approaches offer robust alternatives, particularly for determining the geographic origin of emerald. Three factors make emerald suitable for provenance studies and hence for developing models for origin determination. First, the diverse elemental chemistry of emerald at minor (<1 wt%) and trace levels (<1 to 100's ppmw) exhibits unique inter-element fractionations between global deposits. Second, minimally destructive techniques, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), enable measurement of these diagnostic elemental signatures. Third, when applied to extensive datasets, machine learning (ML) techniques enable the creation of predictive models and statistical discrimination with adequate characterization of the deposits. This study employs a carefully selected dataset comprising more than 1000 LA-ICP-MS analyses of gem-quality emeralds, enriched with new analyses. This dataset represents the largest available for global emerald deposits. We conducted unsupervised exploratory analysis using Principal Component Analysis (PCA). For machine learningbased classification, we employed Support Vector Machine Classification (SVM-C), achieving an initial accuracy rate of 79%. This was enhanced to 96.8% through the use of hierarchical SVM-C with PCA filters as our modeling approach. The ML models were trained using the concentrations of eight statistically significant elements (Li, V, Cr, Fe, Sc, Ga, Rb, Cs). By leveraging high-quality LA-ICP-MS data and ML techniques, accurate identification of the geographical origin of emerald becomes possible. These models are important for accurate provenance of emerald, and from a geochemical perspective, for understanding the formation environments of beryl-bearing pegmatites and shales. [ABSTRACT FROM AUTHOR]

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A unique Mn-, Cd-bearing sphalerite from quartz-calcite veins in the coal-bearing series (Visean C1v) marine sediments in a 50 km segment of the middle course of the Silova-Yakha River in the Arctic zone of the European part of Russia (Pai-Khoi Ridge) has been studied. The veins have a conformable and cross-cutting occurrence in two types of rocks: gray limestones and black siliceous-carbonaceous shales, the area is known as the Goniatite occurrence. The sulfide content in vein samples ranges from 0.1 to 2 vol.%. The chemical composition of 27 monomineral samples of Mn-, Cd-bearing sphalerites was studied, 82 points were analyzed. Correlations between typomorphic elements-impurities were revealed and correlation matrix was constructed. Cu, V, Ga, In, Sn, As, Sb, Bi, Pb, Tl, Se, Ag, Au, Ni are positively correlated with each other; Cd, Mn and Ge are negatively correlated with each other. The hydrothermal fluid involved in crystallization of sphalerite is characterized by low temperature (164-211 °С) and average salinity of 5-6 wt.% eq. NaCl. An updated “portrait” of typomorphic features (composition and properties) of sphalerite of the Pai-Khoi province was obtained. The features allowing to determine the type of impurity entering the sphalerite structure – in the form of isomorphic impurity or in the form of microinclusions of paragenetic association minerals – have been established. Submicron inclusions of sulvanite and colusite, invisible by other methods, were detected in sphalerite (by LA-ICP-MS method).The cathodoluminescence data of sphalerite from the Pai-Khoi province were typified. In contrast to other provinces, ZnS crystals here are characterized by almost complete absence of isomorphic iron. This allowed us to study pure isomorphism schemes of ZnS↔MnS, ZnS↔CdS, namely cathodoluminescence and other types of luminescence. The presence of a rare wurtzite-4H polytype in assemblage with sphalerite was revealed. High contents of strategic metals Cd, Ga, In, Ge in the ZnS matrix, as well as sulvanite (V, Cu) in a single paragenesis were found. A serious reassessment of the potential for industrial use of this mineralization will be required.

Porphyry indicator zircons (PIZ) are often used as an exploratory guide to distinguish fertile granitoid-hosted porphyry copper deposits (PCD). Alumina-saturated granitoids with higher zirconium (> 200 ppm) contents are often the hosts of PCD. REE profiling of zircon is used here to evaluate the chemistry of zircon from a blend of I- and A-type granitoids that hosts the 'Kaziranga' porphyry copper mineralization in the Karbi Hills of the Shillong Plateau. Zircon Hf(t) (1.69–9.88; av.4.65) and whole rock 87Sr/86Sr (0.703) of the Kaziranga granitoids suggest magma derivation in an intraplate or primitive island arc tectonic setting, in which the active mechanism of magma derivation was partial melting of a metasomatically enriched lithospheric mantle that was probably fertilized by an intraplate mantle plume. The fertility indicators with PIZ are grouped with respect to the distribution pattern of normalized REEs, as they exhibit low LREE and enriched HREE, large + Ce, and small -Eu anomalies. The hypogene alteration zones have developed on a regular basis, the potassic alteration zone being close to the central zone around Kuthori in the north Karbi Hills. Although the hosts demonstrate expansion and development of the hypogene alteration zones, the zircons from the mineralized granitoids of Kuthori central zone and granitoids of the nearby Panbari–Dallamara shear zone have similar REE pattern. The target zone's zircon has higher values of ΣHREE, U, Th, Y, Nb, and Hf. The admissible range of fertile PCD is matched by the cross plots of critical element ratios, demonstrating high calculated Ti in zircon temperature (up to 828 °C). [ABSTRACT FROM AUTHOR]

The Xicheng ore field in West Qinling contains numerous Pb‒Zn deposits of varying sizes and is one of the largest areas of Pb‒Zn mineral resources in China. The Xiejiagou Pb‒Zn deposit is in the central part of the southern belt of the Xicheng ore field. No research has been completed on the trace elements and origin of this deposit. To supplement the geochemical information for each deposit in the Xicheng ore field and provide a scientific basis for the exploration of critical metals in the region, the sulfide in the Xiejiagou deposit is selected as the subject of investigation in this study, and its trace element composition is examined using laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP‒MS), accompanied by fluid inclusion thermometry and sulfur isotope analysis, to elucidate the geochemical characteristics of the deposit and propose its genesis. The results showed that the compositions of the trace elements in different sulfides differ greatly, with sphalerite mainly enriched in Cd and relatively enriched in Ge, Mn and In; galena mainly enriched in Ag and relatively enriched in Se, Ge and Tl; chalcopyrite relatively enriched in Sn and Ge; and pyrite relatively enriched in Ni, Co, Ge and Tl. The critical metals are mainly in sphalerite. Zn and Cd mapping diagrams of sphalerite suggest a possible Zn2+ ↔ Cd2+ substitution mechanism; Fe and Mn are positively correlated, while Fe and Zn are negatively correlated, suggesting a possible Fe2+ + Mn2+ ↔ 2Zn2+-coupled substitution mechanism; and the positive correlation between Cu and Ge is strong, while the difference in the content is large, suggesting a substitution mechanism involving (n + 1)Zn2+ ↔ Ge2+ + nCu2+. The sulfur isotopes show obvious heavy sulfur characteristics; the sulfur source is likely Middle Devonian seawater sulfate or marine sulfate from the strata, and the production of reduced sulfur is closely related to thermochemical sulfate reduction (TSR). The trace element compositions of sulfides in the Xiejiagou Pb‒Zn deposit exhibit characteristics that are essentially consistent with those of Mississippi valley-type (MVT) deposits, which clearly distinguish them from sedimentary exhalative (SEDEX) deposits. Additionally, the homogenization temperatures of the fluid inclusions in this deposit are lower than those of the SEDEX deposits; they range between 120 and 160°C, with a mean value of 172°C. Overall, the results indicate that the deposit is classified as an MVT Pb‒Zn deposit, and in this article, a mineralization model diagram has been drawn for the Xiejiagou Pb–Zn deposit. [ABSTRACT FROM AUTHOR]

The Songshugang deposit is a large Ta–Nb deposit in South China, with Ta–Nb mineralization associated genetically with the granite and pegmatite. A diversity of quartz from topaz–albite granite, quartz–mica pegmatite, quartz–feldspar pegmatite, and quartz–fluorite pegmatite at Songshugang was studied by CL and LA–ICP–MS in order to constrain enrichment mechanisms of Nb and Ta and to find geochemical indicators of quartz for rare metal deposits. Cathodoluminescence image illuminates a canvas of complexity, the quartz from topaz–albite granite, quartz–mica pegmatite, quartz–feldspar pegmatite, and quartz–fluorite pegmatite, exhibits numerous dark CL streaks, patches, and a series of healed fractures. These textures suggest that the rocks were fractured because of deep crustal pressure, and underwent later hydrothermal metasomatism and quartz filling. The quartz from quartz–fluorite pegmatite present limited patches or fractures but distinct growth bands, indicating that the melt fluid composition during the formation of quartz at this stage varies greatly and is less affected by mechanical fragmentation. The LA–ICP–MS analysis of quartz shows that there is a positive correlation between Al and Li in the quartz from topaz–albite granite, quartz–mica pegmatite, quartz–feldspar pegmatite, to quartz–fluorite pegmatite, indicating that Al mainly enters the quartz lattice through charge compensation substitution mechanism with Li. However, our data deviate from the theoretical Li:Al mass ratio of ~ 1:3.89 in quartz, indicating that there may be competition between H+ and Li in a water-rich magmatic environment. The quartz from topaz–albite granite is enriched in K and Na elements, and the quartz from quartz–fluorite pegmatite is enriched in fluorite with a low Ca content in quartz, further elucidating that these rocks were subjected to hydrothermal metasomatism. From topaz–albitite granite to quartz–fluorite pegmatite, Al, Li and Ge content and Al/Ti, Ge/Ti, Sb/Ti ratios in quartz gradually increased, but Ti content gradually decreased, reflecting the high evolution of magma, which can enrich rare metal elements. Based on the characteristics of quartz CL textures and trace elements in topaz–albite granite, quartz–mica pegmatite, quartz–feldspar pegmatite, and quartz–fluorite pegmatite, combined with the albitization and K-feldspathization of rocks, it is suggested that the Nb–Ta mineralization in Songshugang may be influenced by the combined action of magmatic crystallization differentiation and fluid metasomatism. By comparing the quartz in the Songshugang pluton with the quartz in the granite type and pegmatite type rare metal deposits recognized in the world, the Songshugang pegmatite share similarities with the LCT-type pegmatite. Combined with previous studies, the Ge/Ti > 0.1 and Ti < 10 ppm, as well as Al, Li, Ge, Sb, K, Na contents and Al/Ti, Sb/Ti ratios in quartz have the potential to be a powerful exploration marker for identifying granite-like pegmatitic Nb–Ta deposits in other places. [ABSTRACT FROM AUTHOR]

The Cornubian Batholith (SW England) is an archetypal Variscan rare metal granite with potential for Li-mica mineralization. We present a petrographic, trace element and multivariate statistical study of micas from the Cornubian Batholith granite series and related hydrothermally altered units to assess the role of magmatic vs subsolidus processes and of fluxing elements (F and B) on the Li cycle during the evolution of the system. The mica types are as follows: (1) magmatic, which include Fe-biotite, protolithionite I and phengite-muscovite from the most primitive granites, and zinnwaldite I from more fractionated lithologies; (2) subsolidus, which encompass high-temperature autometasomatic Li-micas and low-temperature hydrothermal muscovite-phengite. Autometasomatic species include protolithionite II, zinnwaldite II and lepidolite, which were observed in the most fractionated and hydrothermally altered units, and occur as replacements of magmatic micas. Low-temperature hydrothermal Li-poor micas formed via alteration of magmatic and autometasomatic micas or as replacement of feldspars, and albeit occur in all studied lithologies they are best represented by the granite facies enriched in metasomatic tourmaline. The evolution of micas follows two major trends underlining a coupling and decoupling between the Li(F) and B fluxes. These include as follows: (1) a Li(F)-progressive trend explaining the formation of protolithionite I and zinnwaldite I, which fractionate Li along with Cs, Nb and Sn during the late-magmatic stages of crystallization, and of zinnwaldite II and lepidolite forming from the re-equilibration of primary micas with high-temperature Li-B-W-Tl-Cs-Mn-W-rich autometasomatic fluids; (2) a Li(F)-retrogressive trend explaining the low-temperature hydrothermal muscovitization, which represents the main Li depletion process. Trace element geochemistry and paragenesis of late muscovite-phengite support that muscovitization is a district-scale process that affected the upper parts of the granite cupolas through acidic and B(Fe-Sn)-saturated hydrothermal fluids associated with metasomatic tourmalinization, which were mixed with a low Eh meteoric component. [ABSTRACT FROM AUTHOR]

Emeralds – the green colored variety of beryl – occur as gem-quality specimens in over fifty deposits globally. While digital traceability methods for emerald have limitations, sample-based approaches offer robust alternatives, particularly for determining the geographic origin of emerald. Three factors make emerald suitable for provenance studies and hence for developing models for origin determination. First, the diverse elemental chemistry of emerald at minor (

Abstract In addition to his astronomical observations the famous Renaissance astronomer Tycho Brahe (1546–1601) was known also for his interest in alchemy. He equipped his castle Uraniborg on the island of Ven with a state-of-the-art alchemical laboratory when it was erected around 1580. After Brahe’s death Uraniborg was demolished upon a royal decree from 1601, a process which was completed around 1650. In the present study we have analysed four glass shards and one ceramic shard most likely from the alchemical laboratory and retrieved during an archaeological excavation in 1988–90. Cross sections of the shards have been analysed for 31 trace elements by Laser Ablation Inductively Coupled Plasma with Mass Spectrometry with the aim of detecting any traces of the chemical substances on the inside or outside of the shards used in the laboratory. Four of the elements found in excess on the exterior surfaces of the shards, Cu, Sb, Au, and Hg, are in accordance with the reconstructed recipes of the three Paracelsian medicines for which Brahe was famous—Medicamenta tria. This is the first experimental data casting light on the alchemical experiments that took place at Uraniborg 1580–1599.

We present a geochemical dataset and cathodoluminescence images of apatite from the Neoarchean (2610 Ma) glimmerite-carbonatite rocks from the Siilinjärvi complex, Eastern Finland. The subhedral, tapered prismatic grains are compositionally fluorapatite, with limited substitution of Ca by Sr, Na and low REE and Si contents. The Sr/Y ratios are among the highest in a global apatite comparison, comparable to those from other calcite carbonatites, dolomite carbonatites, and phoscorites. Some grains show evidence of late- or post-magmatic interaction with a carbonatite magma or a hydrothermal fluid, resulting in REE-rich overgrowth rims or recrystallized grains with abundant fluid inclusions. We interpret the high Sr/Y ratios combined with low REE contents and depleted heavy REE+Y to represent crystallization from a mantlederived carbonatite parental magma. We show that the Siilinjärvi apatite is chemically heterogeneous but with a limited range in compositions. There are noticeable compositional differences on all spatial scales from micrometer to tens of meters, i.e., within a single crystal, between crystals in a sample, between samples and the two individual sampling locations. We conclude that the intra-crystal geochemical variability in apatite is a suitable tracer of the magmatic and post-magmatic evolution of carbonatite complexes.

In addition to his astronomical observations the famous Renaissance astronomer Tycho Brahe (1546–1601) was known also for his interest in alchemy. He equipped his castle Uraniborg on the island of Ven with a state-of-the-art alchemical laboratory when it was erected around 1580. After Brahe's death Uraniborg was demolished upon a royal decree from 1601, a process which was completed around 1650. In the present study we have analysed four glass shards and one ceramic shard most likely from the alchemical laboratory and retrieved during an archaeological excavation in 1988–90. Cross sections of the shards have been analysed for 31 trace elements by Laser Ablation Inductively Coupled Plasma with Mass Spectrometry with the aim of detecting any traces of the chemical substances on the inside or outside of the shards used in the laboratory. Four of the elements found in excess on the exterior surfaces of the shards, Cu, Sb, Au, and Hg, are in accordance with the reconstructed recipes of the three Paracelsian medicines for which Brahe was famous—Medicamenta tria. This is the first experimental data casting light on the alchemical experiments that took place at Uraniborg 1580–1599. [ABSTRACT FROM AUTHOR]

The Jinchanghe Pb-Zn polymetallic deposit is a representative distal skarn deposit in the Baoshan block. Due to limited research on the sources of ore-forming metals and trace elemental geochemistry of sulfides, the sources and mineralization environments of the Jinchanghe skarn Pb-Zn polymetallic deposit are still controversial. In this study, copper and sulfur isotopes and trace elements of sulfides from the Jinchanghe Pb-Zn polymetallic deposit were analyzed to reveal the sources of ore-forming materials and the ore-forming environments. The trace elemental analysis results show abundant Co, Ni, Mn and Se elements, and less As, Tl and Sb elements dominantly enter pyrite by isomorphic substitution, except for some Zn and Cu that occur as sulfide inclusions in Py1. Abundant Fe and Mn elements could substitute Zn to enter the sphalerite crystal lattice by the isomorphic substitution mechanism of (Fe2+ + Mn2+) ↔ 2Zn2+, and less Ag and Sb elements could enter the sphalerite by the isomorphic substitution mechanism of (Ag+ + Sb3+) ↔ 2Zn2+. The Cu-S isotopic and trace elemental compositions jointly suggest that the Jinchanghe distal skarn Pb-Zn polymetallic deposit formed from magmatic hydrothermal fluids with a sedimentary host-rock contribution, under mesothermal conditions (260 °C on sphalerite). [ABSTRACT FROM AUTHOR]

This study presents the first comprehensive investigation of perovskite from its type locality (Mineral Mines of Southern Urals, Russia), where this mineral was first described by Gustav Rose in 1839. The new data includes results from precise chemical analyses (electron-probe microanalyzer, LA-ICP-MS) and U-Pb ages (SHRIMP-II) of perovskite. Perovskite occurs in silicate-carbonate veins that transect the marginal parts of the Middle Riphaean Kusinsko-Kopanskaya layered intrusion, previously thought to be skarns. The perovskite crystals range from micrometer-scale grains to up to 11 cm in size. Chemical investigations revealed a low content of trace elements (rare earth elements, Y, Nd, U, Th) compared to perovskites from alkaline ultramafic rocks, silica-undersaturated basic rocks, carbonatites, and kimberlites. The determined age of the perovskite, 535 ± 43 Ma, significantly differs from the 1379 ± 8 Ma age of the Kusinsko-Kopanskaya intrusion, challenging the skarn-origin hypothesis for perovskite. Instead, the findings suggest a carbonatite origin for the perovskite mineralization. This timing indicates a previously unknown stage of endogenic activity on the Western Slope of the Southern Urals. [ABSTRACT FROM AUTHOR]

Mafic layered intrusions constitute a natural laboratory to investigate petrogenetic processes using trace element variations in apatite chemistry. Although these intrusions are related to large igneous provinces, there is a wide range of parameters that can affect the chemistry of the primary melt (i.e. composition of the source, pressure, temperature, oxygen fugacity), followed by possible crustal contamination. In this study, we use a comprehensive dataset of analyses of cumulus and intercumulus apatite from a variety of mafic layered intrusions to demonstrate the use of apatite as a powerful petrogenetic indicator. The dataset (determined in this study and compiled from the literature) comprises electron microprobe and LA-ICP-MS analyses, as well as in-situ LA-MC-ICP-MS analyses of Sr isotopes in apatite from well documented layered intrusions (Sept-Iles, Skaergaard, Bushveld, Panzhihua) and the Sudbury Igneous Complex. For the first time, we show that high values of (La/Nd)N, Th, U, Pb, and As in apatite correlate with high (87Sr/86Sr)initial and are related to contamination with continental crust. An elevated (Gd/Yb)N ratio might indicate melting of a mantle source deep enough to retain Yb in garnet. We also confirm that increasingly negative Eu anomaly and decreasing Sr/Y ratio in apatite are indicators of fractional crystallisation of plagioclase, and that high Sr/Y is indicative of early saturation of apatite and/or delayed crystallisation of plagioclase. The reversal to more primitive compositions caused by magma mixing is expressed by higher Sr, V, Mg and Sr/Y ratio, and lower REE + Y, As and Na concentrations in apatite following magma replenishment. Lastly, we show that apatite signature can efficiently distinguish a mafic from a felsic intrusion using its REE and Sr content coupled to its Eu anomaly. It is also possible to further identify the more primitive from the more evolved parts of a mafic layered intrusion, using the Lu, Th, V and volatile (F/Cl) content to distinguish intercumulus from cumulus apatite, respectively. Finally, identifying a mafic magmatic system using detrital apatite in till will prove useful for provenance and mineral exploration studies. [ABSTRACT FROM AUTHOR]

The Makeng iron deposit in southwest Fujian is a significant iron polymetallic deposit containing various types of iron ore, including garnet magnetite, diopside magnetite, and quartz magnetite. The metallogenetic type of the deposit has been a subject of debate, particularly in relation to the genesis of magnetite and the source of iron. In situ microanalysis of trace elements in magnetite from different ores shows relatively low levels of V, Ti, Cu, and Zn, with higher concentrations of Ca and Si, indicating the characteristics of a skarn type deposit. The δ57Fe values of the magnetite range from −0.091‰ to 0.317‰. Combining these data, whole-rock iron isotope analyses, including Juzhou and Dayang granites, diabase, and the Lower Carboniferous Lindi Formation sandstone, suggest that Fe in the magnetite primarily originates from granitic pluton, with potential contributions from diabase and the Lower Carboniferous Lindi Formation sandstone. Combined with field work, these results indicate that Makeng iron deposit is a skarn-type magnetite deposit associated with Yanshanian granitic intrusions. Therefore, the initial ore-forming fluid is postulated to be a high-temperature magmatic hydrothermal fluid with high oxygen fugacity. This fluid infiltrates spaces such as interlayer fracture zones between the Upper Carboniferous Jingshe Formation–Middle Permian Qixia Formation carbonate rocks and the Lower Carboniferous Lindi Formation sandstone, resulting in diverse magnetite ores due to metasomatism. The mineralization process of the Makeng iron deposit is basically the same, as it is composed of typical skarn deposits. Magnetite was mainly formed during calcic skarn formation stage, and this process persisted until the initial phase of the retrograde alteration of skarns. In contrast, sulfide minerals, including molybdenite, sphalerite, and galena, precipitated during the quartz–sulfide stage. [ABSTRACT FROM AUTHOR]

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Regolith-hosted Ni-Cr prospects in the Nkonko serpentinized massif are located near Kananga city in the Democratic Republic of Congo (DRC). This serpentinized massif displays an underground regolith profile divided into three main layers: (1) unweathered serpentinite bedrock, (2) saprolite serpentinites, and (3) the pedozone top layer. The bedrock serpentinites consist of serpentine (including lizardite and antigorite "garnierite") as a major phase, with Cr-spinel and magnetite as a subsidiary phase. The rock contains rare pseudo-olivine relicts. Saprolite serpentinites contain serpentines (e.g., lizardite, chrysotile, antigorite "garnierite") and subordinate ferrochromite and Cr-magnetite. These saprolite serpentinites are crosscut by veins of "garnierite" phase, talc, brucite, magnetite, magnesite, and chlorite. The pedozone primarily consists of lateritic soils with red and yellow limonite. Saprolite serpentinites exhibit relatively higher Al2O3, FeO, Fe2O3, and volatiles (LOI: loss on ignition) compared to bedrock serpentinites, while maintaining similar SiO2 contents. For trace elements, saprolite serpentinites contain elevated Cr (up to 5.4 wt%) and Ni (up to 2.0 wt%) compared to bedrock samples (Cr up to 0.9 and Ni up to 0.3 wt%). The REE concentrations are low (total REE of about 2.0 ppm) and remain unchanged between the saprolites and bedrocks. Spinel is identified as the main host mineral for Cr, while secondary serpentine "garnierite" is the primary host phase for Ni. Plots of Al2O3/SiO2 versus MgO/SiO2 for bedrock and saprolite serpentinites, along with the REE patterns, suggest that the serpentine regolith originated from the alteration and weathering of harzburgite. [ABSTRACT FROM AUTHOR]

The diverse suite of trace elements incorporated into apatite in ore-forming systems has important applications in petrogenesis studies of mineral deposits. Trace element variations in apatite can be used to distinguish between fertile and barren environments, and thus have potential as mineral exploration tools. Such classification approaches commonly employ two-variable scatterplots of apatite trace element compositional data. While such diagrams offer accessible visualization of compositional trends, they often struggle to efectively distinguish ore deposit types because they do not employ all the high-dimensional (i.e., multi-element) information accessible from high-quality apatite trace element analysis. To address this issue, we use a supervised machine-learning-based approach (eXtreme Gradient Boosting, XGBoost) to correlate apatite compositions with ore deposit type, utilizing such high-dimensional information. We evaluated 8629 apatite trace element data from five ore deposit types (porphyry, skarn, orogenic Au, iron oxide copper gold, and iron oxide-apatite) along with unmineralized magmatic and metamorphic apatite to identify discriminating parameters for the individual deposit types, as well as for mineralized systems. According to feature selection, eight elements (Th, U, Sr, Eu, Dy, Y, Nd, and La) improve the model performance. We show that the XGBoost classifier eficiently and accurately classifies high-dimensional apatite trace element data according to the ore deposit type (overall accuracy: 94% and F1 score: 89%). Interpretation of the model using the SHAPley Additive exPlanations (SHAP) tool shows that Th, U, Eu, and Nd are the most indicative elements for classifying deposit types using apatite trace element chemistry. Our approach has broad implications for the better understanding of the sources, chemistry, and evolution of melts and hydrothermal fluids resulting in ore deposit formation. [ABSTRACT FROM AUTHOR]

Sedimentary pyrite has long been used as an archive of marine environments in Earth history. To capture reliable paleoenvironmental signals, however, we need to first evaluate pyrite in sedimentary strata as it can be altered and masked by later diagenetic and/or hydrothermal processes. Here, we trained two supervised machine learning algorithms on a large LA-ICP-MS pyrite trace element database to distinguish pyrite of different origins. The analysis validates that two models built on the co-behavior of 12 trace elements (Co, Ni, Cu, Zn, As, Mo, Ag, Sb, Te, Au, Tl, and Pb) can be used to accurately predict pyrite origins. Further statistical analysis suggests four trace element clusters behaving differently among sedimentary (syngenetic and early diagenetic), synsedimentary hydrothermal (syngenetic hydrothermal), and post-sedimentary hydrothermal (epigenetic hydrothermal) pyrite, which is probably driven by chemical and physical properties of source fluids, interactions between elements, competition among coprecipitating minerals, and pyrite growth rate. Armed with this initial success and aided by new LA-ICP-MS trace element data from 9 samples, we then demonstrated the efficacy of this approach in identifying the origins of pyrite from two Neoproterozoic sedimentary successions in South China. The first set of samples contain isotopically superheavy pyrite (i.e., whose bulk-sample δ34S values greater than those of contemporaneous seawater sulfate and whose origins remain controversial) from the Cryogenian Tiesi'ao and Datangpo formations. The second set of samples contain pyritic rims (associated with fossiliferous chert nodules and thought to be critical in exceptional fossil preservation) from the Ediacaran Doushantuo Formation. For the superheavy pyrite, the models consistently show high confidence levels (mostly > 80 % probability) in identifying its genesis type, and three out of four samples were given sedimentary origins. For the pyritic nodule rims, the models suggest that early diagenetic pyrite was subsequently altered by hydrothermal fluids and therefore shows mixed signals. The study highlights the importance of pyrite trace elements in deciphering and distinguishing the origins of pyrite in sedimentary strata. [ABSTRACT FROM AUTHOR]

The Caoziwa Pb–Zn deposit is one of the typical vein-type Pb–Zn deposits in the western part of the Tengchong block. Due to limited research, the genesis of these deposits is unknown. In this study, the sulfur isotopic and trace elemental compositions of sulfides from the Caoziwa Pb–Zn deposit were analyzed to trace the sources of ore-forming materials, and to reveal the genetic type of this deposit. The results show that abundant Co, Ni, As, and Se, and less Cu, Zn, Ag, Cd, Sn, Sb, Te, Pb, and Bi could enter pyrite by isomorphic substitution. Elemental Mn, Fe, Cd, Co, and Ni could substitute Zn to enter sphalerite, while the contents of Ag, Sn, and Sb are mainly controlled by the Pb-rich inclusions in sphalerite. Elemental Bi, Sb, Cd, Sn, Ag, and Tl mainly enter the galena grains via an isomorphic substitution mechanism of (Bi, Sb)3+ + (Cd, Sn)2+ + (Ag, Tl)+ ↔ 2Pb2+. Both sulfur isotopic compositions and trace elemental compositions indicate that the ore-forming materials and fluids of the Caoziwa Pb–Zn deposit mainly originate from magmatic hydrothermal fluid related to Paleocene granitic magmatism. Combined with the geological facts that some skarnizations developed in the northern part of the ore field near the Paleocene granite, the Caoziwa Pb–Zn deposit is suggested to be a magmatic hydrothermal vein-type deposit that probably belongs to a distal part of a skarn mineralization system developed by the intrusion of Paleocene granitic magmatism in the western part of the Tengchong block. [ABSTRACT FROM AUTHOR]

We present a geochemical dataset and cathodoluminescence images of apatite from the Neoarchean (2610 Ma) glimmerite-carbonatite rocks from the Siilinjärvi complex, Eastern Finland. The subhedral, tapered prismatic grains are compositionally fluorapatite, with limited substitution of Ca by Sr, Na and low REE and Si contents. The Sr/Y ratios are among the highest in a global apatite comparison, comparable to those from other calcite carbonatites, dolomite carbonatites, and phoscorites. Some grains show evidence of late- or post-magmatic interaction with a carbonatite magma or a hydrothermal fluid, resulting in REE-rich overgrowth rims or recrystallized grains with abundant fluid inclusions. We interpret the high Sr/Y ratios combined with low REE contents and depleted heavy REE+Y to represent crystallization from a mantlederived carbonatite parental magma. We show that the Siilinjärvi apatite is chemically heterogeneous but with a limited range in compositions. There are noticeable compositional differences on all spatial scales from micrometer to tens of meters, i.e., within a single crystal, between crystals in a sample, between samples and the two individual sampling locations. We conclude that the intra-crystal geochemical variability in apatite is a suitable tracer of the magmatic and post-magmatic evolution of carbonatite complexes. [ABSTRACT FROM AUTHOR]

The compositional zoning of the major divalent cations in metamorphic garnet is a useful tool in reconstructing the pressure–temperature path. However, trace elements can provide a better-preserved record of petrogenetic evolution due to their strong affinity in garnet and slow diffusion rates. In this study, three high-pressure micaschist samples of varying composition and garnet textures from the Krušné hory Mountains (Saxothuringian zone, Bohemian Massif) were examined. By utilizing electron probe micro-analysis and laser ablation inductively coupled plasma mass spectrometry, three distinct types of compositional zoning in garnet were identified by compositional mapping. The zoning types were classified as continuous core-to-rim change, concentric annular changes, and overprinting of a pre-existing distribution; all three provide information on the original mineral composition and texture before garnet overgrowth. The transition from overprint to annular zoning shows relation to temperature increment. The annular zoning allowed the identification of several coupled substitutions, including alkali (sodium and lithium) + yttrium and the alkali + phosphorus substitution which is typical of high- to ultra-high-pressure conditions. The formation of annuli zoning was interpreted to originate not only from the decomposition of trace element bearing phases, but also to be related to the availability of fluid medium during garnet growth. Two samples contained atoll texture garnets, interpreted to be originated from the dissolution of the garnet central part, chemically distinct from the new garnet growing coevally on the rim or replacing the original central part. This proposed process is evidenced by the mass balance calculation of yttrium and heavy rare earth elements between the dissolved garnet and newly formed parts. [ABSTRACT FROM AUTHOR]

BACKGROUND: Trace element information in carbonates provides key constraints for investigating ancient environments, paleoclimate evolution, shell-mantle interactions, diagenesis and mineralization processes. The accurate determination of trace element content in carbonate minerals have always been a primary focus. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) can provide detailed information on trace element content in carbonate minerals. However, the elemental concentrations in carbonate minerals are usually extremely low (from hundreds of pg/g to tens of ng/g). A large spot size (from 44 to 100μm) is often used for trace element measurements in carbonate minerals. Therefore, the detection capability of low-content elements in carbonate minerals and the spatial resolution of LA determination still need to be improved. OBJECTIVES: To develop a new analytical method for determination of low-content trace elements in carbonate minerals with LA-ICP-MS. METHODS: A new local aerosol extraction ablation cell was proposed in this study. Laser ablation was performed using high-repetition rates with the new designed ablation cell. The elemental contents in carbonate reference materials MACS-3, CGSP-A, CGSP-B, CGSP-C, and CGSP-D were determined with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. Here, NIST 610 glass was used as an external calibration material and Ca was used as an internal standard. RESULTS: The obtained peak height of a single laser shot was enhanced by a factor of 13 with the local aerosol extraction ablation cell because of the rapid washout time. The signal intensities were increased by 1.5 times under high-repetition rate laser ablation mode. Therefore, the detection limits of trace elements in carbonate minerals obtained from nanosecond laser ablation at high repetition rates (20Hz) were reduced by 5-8 times compared to conventional analysis (6Hz). The detection limits of trace elements were reduced by 5-10 times with the frequency of femtosecond laser ablation increased from 10Hz to 100Hz. The elemental contents in carbonate reference materials were measured with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. The obtained results of lithophile elements (e.g., Sc, Sr, Y, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Th) in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values. However, the measured results of siderophile and chalcophile elements (e.g., Ni, Cu, Zn, As, Cd, Sn, Sb, and Pb) showed systematic bias (>20%), which may be related to the “downhole” fractionation effect caused by the high-repetition rate laser ablation used in this study. CONCLUSIONS: The new designed local aerosol extraction ablation cell combined with high-repetition rate laser ablation mode significantly improved the spital resolution and determination ability of low-content elements in carbonate minerals. The obtained results of lithophile elements in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values using ns- and fs-LA-Q-ICP-MS with a spot size of 32µm. It is worth noting that the spatial resolution and the detection capability of ultra-low-content elements in carbonate minerals could be further improved with the proposed LA method combined with high-sensitivity magnetic sector mass spectrometry. [ABSTRACT FROM AUTHOR]

The Pusangguo deposit (1.42 Mt @ 1.42% Cu, 0.14 Mt @ 1.82% Zn, 0.08 Mt @ 1.01% Pb, and 285.8 t Co @ 140 g/t Co) is the first Co-rich Cu-Zn-Pb skarn deposit discovered in the Gangdese metallogenic belt. However, the trace and minor element geochemistry of the sulfides in this deposit has not been studied, limiting further understanding of elements' occurrence and mineralization. Here, we identified four ore stages, and two types of sphalerites (SpI and SpII) and pyrites (PyI and PyII), in this deposit. In this study, LA-ICP-MS in-situ trace element analyses were conducted on sphalerite and pyrite, to obtain their chemical compositions, elemental substitution mechanisms, and mineralization physicochemical conditions. The results indicate that two types of sphalerites are generally more enriched with Co than pyrite. SpI has higher concentrations of Co, Cr, Cu, Ag, and As compared to SpII. Both types of sphalerite have very low contents of Sn, Ge, and Ga. PyII has higher contents of most trace elements, such as Co, Ni, Mn, Zn, Cu, As, Sn, Se, Pb, Ag, and Bi, compared to PyI. Both types of pyrite are poor in Mn, Ga, Ge, and Cd, but enriched in As, Co, and Ni. The Mn, Fe, Co, and Cd in sphalerite, and Co, Ni, and Mn in pyrite are generally lattice-bound, while Cu, As, Ag, and Sb are usually present in both micro-inclusions and coupled substitution. Significant elemental correlations in sphalerite indicate the possible substitution mechanisms 2Fe2+ + Ga2+ ↔ 3Zn2+, 2Fe2+ + Ge4+ ↔ 4Zn2+, and (Sb3+, Sn3+) + (Cu+, Ag+) ↔ 2Zn2+. The correlation trends between trace elements in pyrite suggest the coupled substitution mechanisms of (Tl+ + Cu+ + Ag+) + (As3+ + Sb3+) ↔ 2Zn2+ and As3+ + Cu+ ↔ 2Zn2+. The mineralization temperature at Pusangguo, as determined by the GGIMFis sphalerite geothermometer, is 237–345 °C (avg. 307 °C), consistent with the high Zn/Cd ratio (avg. 203), low Ga/In (avg. 0.06), and high In/Ge (avg. 15.9) in sphalerite, and high Co/Ni ratio (avg. 24) in pyrite. These results indicate that the ore-forming fluid was high-temperature, with a low sulfur fugacity (fS2) (10−13.4 to 10−8.3) and low oxygen fugacity (fO2). The high temperature, and low sulfur fugacity and oxygen fugacity of the ore-forming fluid, and the fluid-mixing process, jointly controlled the sulfide precipitation, which caused the formation of the Pusangguo deposit. [ABSTRACT FROM AUTHOR]

The concentrations of trace elements in pyrite and enargite-luzonite from target 185 of the copper-gold high sulphidation Chelopech deposit were determined by LA-ICP-MS. Their average contents in ppm based on 12 analyses of pyrite and 10 analyses of enargite-luzonite are respectively: Ti (6548) > Cu (3449) > V (580) > Mn (299) > Pb (173) > As (157) > Se (149) > Te (122) > Zn (80) > Co (79) > Bi (41) > Cr (29) > W (25) > Sn (22) > Ni (17) > Au, Ga (15) > Ag (14) > Mo (9) > Sb (5) > Tl (4) > Hg (1) > In (0.2) for the first one and Fe (26531) > Zn (22140) > Sb (11014) > Bi (7956) > Se (1730) > Sn (1016) > Pb (995) > Te (326) > Mn (205) > Mo (170) > Hg (100) > Ge (88) > Ag (46) > Ti (42) > W (25) > Cd (24) > V (19) > Au (16) > In (4) > Tl (3) > Ga (1) for the second. [ABSTRACT FROM AUTHOR]

Dengjiashan is a large‐scale Pb–Zn deposit discovered in the western part of the Xicheng ore field within the West Qinling metallogenic belt. Information regarding the distribution and occurrence of trace elements in ore minerals and mineralization, as well as the genesis of this deposit, remains scarce. Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) analysis and elemental mapping were used to determine the distribution and occurrence of trace elements in the sulfide minerals of the Dengjiashan deposit, as well as delineate the process of its genesis. Our results showed that the trace elements enriched in the different sulfides were significantly different. Sphalerite is the main carrier mineral of the scattered elements Cd, Ge and Ga. Based on the trace element content and ratio, principal component analysis and colour of the sphalerite and pyrite, the deposit likely formed in a medium‐temperature environment. The comparative analysis of trace elements from multiple deposits of different origins, combined with the geological characteristics and distribution of sulfide trace elements, suggests that Dengjiashan is a sedimentary exhalative (SEDEX)‐type deposit. As the metallogenic process had a closer relationship to medium‐low temperature hot brine and later tectonic metamorphic hydrothermal fluid, than with magmatic hydrothermal fluid, the deposit is likely of non‐magmatic SEDEX–hot brine superimposed transition origin. This study provides additional insight on the distribution of trace elements in the sulfide minerals of the Dengjiashan deposit, as well as the processes that led to its formation, and may further facilitate ongoing and future key metal prospecting and exploration efforts. [ABSTRACT FROM AUTHOR]

A common issue in non-destructive surface analysis of historical silver coins is depletion of Cu from the near-surface areas, which in turn results in higher Ag content at a coin's surface. This paper reports a non-destructive analytical strategy using µXRF for identification of Ag and Cu surface enrichments and depletions by comparing peak intensity ratios of Ag Kα/Ag Lα, Cu Kα/Ag Kα and Cu Lα/Ag Lα for coins and Ag-Cu standards of similar composition. Our characterization of coins from different contexts and chronologies shows that a multi-standard approach provides the most reliable identification of surface enrichment of Ag and depletion of Cu. Coins possessing Ag surface enrichment were further analysed with LA-ICP-MS to determine any differences in trace element composition between the cores and surface of the coins. We show that the near-surface regions of these coins are enriched in Au and depleted in Co, Ni, As, and Pt relative to their cores. These systematics allow for a more robust assessment of the degree of silver coin surface alteration critically important in measuring the original composition of historical silver coins.

A common issue in non-destructive surface analysis of historical silver coins is depletion of Cu from the near-surface areas, which in turn results in higher Ag content at a coin's surface. This paper reports a non-destructive analytical strategy using µXRF for identification of Ag and Cu surface enrichments and depletions by comparing peak intensity ratios of Ag Kα/Ag Lα, Cu Kα/Ag Kα and Cu Lα/Ag Lα for coins and Ag-Cu standards of similar composition. Our characterization of coins from different contexts and chronologies shows that a multi-standard approach provides the most reliable identification of surface enrichment of Ag and depletion of Cu. Coins possessing Ag surface enrichment were further analysed with LA-ICP-MS to determine any differences in trace element composition between the cores and surface of the coins. We show that the near-surface regions of these coins are enriched in Au and depleted in Co, Ni, As, and Pt relative to their cores. These systematics allow for a more robust assessment of the degree of silver coin surface alteration critically important in measuring the original composition of historical silver coins.