Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

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.

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.

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.

2D geochemical imaging of biogenic marine carbonates using LA-TOF-ICP-MS at 1 and 2 μm pixel resolution

Many applications at the forefront of the study of the chemical composition of marine carbonates require in-situ micro-scale geochemical imaging. Such analyses are, however, challenging, requiring analytical techniques that are either expensive with limited accessibility (e.g. synchrotron X-Ray spectroscopy and secondary ion mass spectrometry), or time-consuming and able to only analyse a limited range of elements (e.g. electron microprobe). Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a tool for generating 2D images has grown in popularity, yet many analytical issues remain when generating high-spatial resolution geochemical images using this approach. Here we employ the imageGEO193 (ESL) fast wash-out laser ablation system coupled to the Nu Instruments Vitesse Time-of-Flight (TOF) ICP mass spectrometer, with its near-full mass spectra capabilities, to generate 2D geochemical images of a range of biogenic carbonates at ≤2 μm pixel resolution (pixel widths of either 1 or 2 μm) and at an unprecedented speed (200 pixels/s). We demonstrate sensitivity of ∼100 cps/μg g−1 at low mass rising to ∼1000 cps/μg g−1 at high mass based on analyses of reference materials JCp-1 (carbonate) and NIST SRM612 (silicate) with 1 μm wide square laser beams, and accuracy of ±7 % for elements present at concentrations >0.5 μg g−1 based on analyses of carbonate reference material JCt-1. By applying our quantitative method to a range of biogenic carbonates (coral skeletons, coralline algae, foraminifera), we demonstrate that considerable but coherent micron-scale compositional variability is the norm for nearly all quantified elements, including: Mg, Sr, Ba and U. This approach therefore has great potential to provide valuable insights into biomineralisation mechanisms and “vital effects”, ultimately facilitating more robust reconstructions of past environments.

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.

Paleobotanical Evidence for Mediterranean Climates in the Western Canadian Paleoarctic During the Late Middle Eocene

AbstractPaleogene age deposits east of the Fifteenmile River, northwest of Dawson City, Yukon, Canada preserve a diverse high‐latitude fossil flora. Here, we provide new data on the age of the fossil site based on laser ablation–inductively coupled plasma–mass spectrometry (LA‐ICP‐MS) U‐Pb dating of tephra zircons, paleobotanical paleoclimate reconstructions, and growing season length estimates based on photoperiod. These new data indicate an age of the Fifteenmile River fossil locality as late middle Eocene and likely within the Middle Eocene Climatic Optimum episode. The paleoflora‐based paleoclimate reconstruction indicates the region was relatively wet and warm with non‐freezing winters, but also experienced seasonal dryness, with an approximate 7 months long growing season as suggested by photoperiod. We interpret this paleoclimate as summer dry and winter wet—a climate analogous to modern day warm Mediterranean climates in the Köppen‐Geiger climate classification system. These findings provide a new perspective on the past climate and environment of high‐latitude ecosystems during warm greenhouse intervals and contribute to our understanding of the Earth's climate history and its potential future changes.

INTRATEST TRACE ELEMENT VARIABILITY IN POLAR AND SUBPOLAR PLANKTIC FORAMINIFERA: INSIGHTS INTO VITAL EFFECTS, ONTOGENY, AND BIOMINERALIZATION PROCESSES

ABSTRACT To use planktic foraminiferal tests as paleoproxy substrates, it is necessary to delineate environmental versus biological controls on trace element incorporation. Here we utilize laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to explore interspecies, chamber-to-chamber, and intratest trace element (i.e., Mg, Na, Sr, Ba, Mn, Zn) variability in thickly-calcified specimens of the polar and subpolar planktic foraminifera Neogloboquadrina incompta, N. pachyderma, and Turborotalita quinqueloba collected from plankton tows in the Northern California Current. Among the study taxa, test Mg/Ca, Na/Ca, and Sr/Ca are likely dominantly controlled by depth habitat. The neogloboquadrinids record higher Ba/Ca and Mn/Ca and also show positive covariance between these elements, possibly due to calcifying in an oxygen-depleted marine snow microhabitat. Trace elements are found to be more enriched in the lamellar calcite than the outer chamber wall dominated by gametogenic crust. The data presented herein provide insight into potential vital effects, paleoproxy considerations, ontogeny, and biomineralization processes.

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.

Explainable extreme gradient boosting as a machine learning tool for discrimination of the geographical origin of chili peppers using laser ablation-inductively coupled plasma mass spectrometry, X-ray fluorescence, and near-infrared spectroscopy

The spectroscopic discrimination of chili pepper samples according to geographical origin was executed using analytical techniques coupled with machine learning. First, laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray fluorescence (XRF), and near-infrared (NIR) spectroscopy were chosen for simple and rapid sample measurements. Second, to secure discrimination accuracy, eXtreme Gradient Boosting (XGBoost), a tree-based ensemble technique, was adopted as a potential classifier. Also, for explainable machine learning modeling, SHaply Additive exPlanation (SHAP) values of employed variables were calculated to assess how they contribute to the discrimination. The use of XGBoost improved discrimination accuracies in all three measurements compared to k-nearest neighbor (k-NN), support vector machine (SVM), and partial least squares-discriminant analysis (PLS-DA). The accuracy was 96.2 % using the LA-ICP-MS data. When the XRF and NIR data were combined, the accuracy improved to 97.5 %. The accuracy improvement was attributed to the combination of complementary atomic and molecular spectroscopic signatures of the samples.

Climate-driven versus anthropogenic induced erosion of the last 3000 years from an ancient lake in the Southern Phokis Plain (Desfina), Greece

The timing and causes for erosional events at the Kastrouli (Greece) archeological site – a Late Myceneaen with reuse in later periods – are presented. Two borehole sediment cores (max 6 m depth), collected from the footsteps of the settlement hill plain, were studied. Sedimentary analysis and luminescence dating techniques investigate and identify periods of soil aggradation in this record. Moreover, optically stimulated luminescence (OSL) dating confirmed the concept of an ancient lake during Kastrouli settlement times. Macroscopic overview of the stratigraphic structure for each core, included lithological and textural evaluation of the core sediments, assessments of grain size, and determination of the geochemical and mineralogical composition of the sediments. X-ray powder diffraction (XRPD), X-ray fluorescence (XRF), and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) techniques were applied for the mineralogical and geochemical analysis. OSL ages from seven sediment horizons spanned from the Ottoman period to archaic times. All lithological findings correlate with the results of the electrical tomography survey conducted in same area. Extrapolation of the Logarithmic fitting of the data back in time of prehistoric Late Mycenaean era of Kastrouli verifies a lake deeper than 10 m, with a considerable enhancement in soil aggradation of 1.2 cm/year. Attempts to dry out the area are evidenced by the hydraulic works found in two engineering sinkholes. Sedimentation changes had occurred in the local environment over the last 2500 years, and soil aggradation underwent significant fluctuations in the two studied cores. The Roman period (a wet period) and the Byzantine period experienced high aggradation rates. By contrast, soil aggradation rates in southern Phokis (Kastrouli region) have remained exceedingly low from the Ottoman era (circa 13th century) to the present. In the context of the Phokis case study, it appears that the sedimentation rates, driven by climate, have strengthened anthropogenic activities.

Li enrichment in peridotites and chromitites tracks mantle-crust interaction

The ultramafic massifs of the Serranía de Ronda in southern Spain are the Earth's largest exposures of subcontinental lithospheric mantle (SCLM) peridotites (∼450 km2). These ultramafic massifs experienced asthenosphere melt percolation during their crustal emplacement. Mixing of these mafic melts with anatectic melts and fluids led to the formation of a world's unique Ni-arsenide-rich chromitite ores (hereafter CrNi ores) associated with orthopyroxenite and/or cordieritite (i.e., > 90 % volume of cordierite) hosted within the peridotites. This study uses laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to investigate the Li in rock-forming minerals of peridotite and CrNi ores to evaluate the role of Li as crustal tracer. Clinopyroxene crystallized from asthenospheric melts exhibits high Li contents (up to 8.5 ppm), exceeding the average values of the upper mantle (∼ 0.7 ppm), whereas orthopyroxene, olivine, and Cr-spinel from peridotite are mostly Li-depleted. In contrast, all rock-forming minerals of CrNi ores have abnormally high Li contents, displaying an overall Li enrichment trend toward the external parts of ultramafic massifs, on the way to the crustal rocks. This trend is evident in Cr-spinel from the CrNi ores, which display 6.9–7.9 ppm Li in the deepest portions of the massif (Arroyo de la Cala CrNi ore) up to 1.4–8.5 ppm in the shallowest part (La Gallega CrNi ore), as well as in orthopyroxenes that have 31.3–44.7 ppm Li in Arroyo de la Cala, and 45.1–51.4 ppm Li in La Gallega. Cordierite is present only in the CrNi ores situated in the external part of the ultramafic massifs, exhibiting 113.15–160.82 ppm Li in the Barranco de las Acedías CrNi ore and 36.5–60.5 ppm Li in La Gallega CrNi ore. Similarly to Li, LREE, fluid-mobile elements (K, Rb, Ba), and Sr in orthopyroxenes from the CrNi ores display enrichment from the inner to the outer parts of the ultramafic massif. These geochemical variations suggest that Li enrichment in CrNi ores and host peridotites was a twofold process: (1) asthenospheric melt percolation slightly increased Li abundances in the SCLM peridotites by modal and cryptic metasomatism involving clinopyroxene; (2) additional infiltration of Li-bearing crustally-derived fluids during the intracrustal emplacement of the mantle section boosted the Li contents of minerals in the CrNi ores. Our results highlight that Li may effectively track the interaction of the SCLM with crustal components.

Isotopic spike 190Os as internal standard and empirical coefficient LA-ICP-MS combined with Sb fire assay for the determination of ultra-trace platinum group elements in geochemical samples

In this work, a novel method of antimony fire assay (Sb-FA) enrichment combined with laser ablation ICP-MS (LA-ICP-MS) for the determination of ultra-trace platinum group elements (PGEs) in geological samples was established. The purification and recycling technology of ultra-clean and high-purity fire assay collector Sb2O3 was proposed, in addition, high-purity quartz crucible was developed to replace the usual clay crucible, then the blank values of PGEs were as low as 0.0007–0.0028 ng g−1 (for 20 g sample). 190Os isotopic diluent was used as internal standard (IS) and quantitatively added into the fire assay ingredients, and fully mixed and balanced with the PGEs in the real samples by means of high temperature melting, cupellation and horizontal rotation of crucible and dish. Both 190Os and PGEs in the real sample were pre-concentrated in microgram level Sb granules (100 mg) through Sb-remaining cupellation. After grinding and polishing, 195Pt, 105Pd, 101Ru, 103Rh, 193Ir, total 189Os and 190Os enriched in Sb slices were determined by LA-ICP-MS, 190Os in the internal standard was calculated by isotope dilution equations. The Certified Reference Materials (CRMs) for PGEs were treated by the same procedure to obtain completely matrix matched Sb slices to solve the problem of no internationally recognized uniform PGEs standard materials for LA-ICP-MS determination. Due to the similar distribution trends of different PGEs in Sb slices by LA-ICP-MS imaging, then matrix-matched internal standard calibration strategy was used to reduce the element fractionation effect and improve the determination precision and accuracy of LA-ICP-MS. The laser frequency, energy density, denudation diameter and dwell times were optimized. Under the optimal conditions, empirical coefficient method was used to fit the standard curve and excellent curve fitting of PGEs were obtained with the correlation coefficient between 0.9990 and 0.9999. The method detection limits (LODs) for PGEs ranged from 0.00042 to 0.010 ng g−1. The established method was successfully applied to analyze real geochemical samples and various matrix Certified Reference Materials (CRMs) domestic and international, the determined values were in good agreement with the results of Sb-FA ICP-MS and the certified values.

The glass from the arrabal of Arrixaca (Murcia, 12th-13th centuries)

This article presents an assemblage of 36 glass samples excavated in the urban site of San Esteban, part of the arrabal of Arrixaca (Murcia) (in al-Andalus, an arrabal was a relatively dense urbanised area outside the city walls) in contexts securely dated to the 12th and early 13th century, spanning the rule of Ibn Mardanīš, and the early period of Almohad domination in the city. The samples were analysed by electron microprobe (EMPA) for major and minor elements and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for trace elements. The results are examined within the context of glass production, circulation, and consumption in al-Andalus and the Islamicate Mediterranean more broadly. The results show that some of the glasses found in San Esteban-Arrixaca may have been imported from other Islamicate regions (Egypt and Mesopotamia), but that the vast majority can be related to previously recognised compositional Iberian glass groups. At the same time, the identification of several fragments of production waste and raw glass suggest that some glass-working facility may have existed in the vicinity of San Esteban-Arrixaca. The compositional evidence also indicates that recycling (including of imported glass objects) may have been a fairly common practice in Andalusi glassmaking, but it is suggested that some of the usual chemical markers of recycling may, in the case of al-Andalus and perhaps also elsewhere in the medieval Mediterranean, be the result of the cross-breeding of glass- and glaze-making activities.

Paleoproterozoic ultrahigh-temperature metamorphism in the Helanshan Complex, North China Craton: New constraints from chloritized sapphirine-bearing pelitic granulites

Identifying ultrahigh-temperature (UHT) metamorphism in granulite-facies metamorphic terrains and determining its pressure-temperature-time (P-T-t) paths are crucial steps toward elucidating the anomalously hot geodynamic evolution process. This study presents the inaugural identification of chloritized sapphirine-bearing granulites in the Helanshan Complex, located in the western segment of the Khondalite Belt, North China Craton. Three stages of metamorphic evolution were identified based on petrographic analyses, mineral chemistry, and phase equilibrium modelling: the pre-Tmax stage involves the presence of rutile-stable phase assemblage, wherein rutile is partially substituted by ilmenite; the Tmax stage involves the assemblage of garnet + plagioclase + K-feldspar + sillimanite + spinel ± sapphirine + quartz + ilmenite + melt, as evidenced by microscale (<5 μm) blebs of variably chloritized sapphirine within spinel; and the retrograde cooling stage features the solidus assemblage of garnet + plagioclase + biotite + K-feldspar + sillimanite + cordierite + quartz + ilmenite + melt. Phase equilibrium modelling indicates Tmax conditions of 958–1055 °C and 6.4–7.8 kbar, suggesting UHT conditions accompanied by a high geothermal gradient of approximately 150 °C/kbar. Furthermore, a clockwise P-T trajectory was established, involving pre-Tmax decompression and post-Tmax near-isobaric cooling. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon and monazite U-Pb dating of UHT pelitic granulites produced ages clustering around 1.91 Ga, marking the era of UHT metamorphism within the Helanshan Complex. This discovery broadens the scope of UHT metamorphism and indicates that the entire Khondalite Belt experienced a regional UHT metamorphic event during 1.93–1.91 Ga, which was likely induced by an initial radiogenic heating synergy followed by an augmented mantle heat flux.

Newly discovered Early Cretaceous Au mineralization overprinting Late Jurassic Pb-Zn-Ag mineralization in the Qin-Hang metallogenic belt (South China)

Magmatic and mineralizing events in South China were traditionally thought to be limited between 150 Ma and 130 Ma despite the numerous Mesozoic-aged magmatic-hydrothermal deposits in the region. This viewpoint is being reevaluated in light of new age data. Kangjiawan is a representative Pb-Zn-Ag-Au deposit in the Hengyang Basin in the Qin-Hang metallogenic belt of South China that contains 1.96 Mt of Pb-Zn resource with 4.70% Zn, 6.02% Pb; 2280.5 t of Ag resource with 108.23 g/t of Ag; and 58 t of Au resource with 3.25 g/t of Au. Its mineralization can be divided into four stages: (I) pre-ore quartz−pyrite, (II) quartz−pyrite−galena−sphalerite, (III) quartz−galena−sphalerite, and (IV) calcite−pyrite. Multiple generations of pyrite were identified at Kangjiawan. Generation I pyrite (Py1, formed in Stage I) is coarse-grained, texturally homogeneous, and contains abundant silicate inclusions (e.g., K-feldspar and titanite). Generation II pyrite (Py2, formed in Stage II) is generally fine-grained and exhibits a core-rim texture, with the porous, sphalerite−galena inclusion-bearing core (Py2a) having replaced Py1 and the rim (Py2b) being homogeneous. Generation III pyrite (Py3, formed in Stage IV) is subdivided into Py3a and Py3b, with the homogeneous Py3a often replaced by the porous Py3b. The low Co/Ni ratio of Py1, along with the abundant silicate inclusions, is suggestive of intense fluid-rock interaction during Stage I. Py2a is As-Cu-Pb-Ag-Au−rich, Co-depleted, and has elevated Ag/Co (average 3.24) and As/Co (average 10,217.14) ratios, which are suggestive of extensive fluid boiling during the formation of Py2a. This is also supported by the ubiquitous Py2-cemented hydrothermal breccia. In contrast, Py2b is depleted in As-Cu-Pb-Ag-Au but enriched in Co, which is indicative of non-boiling conditions. Subsequent sealing of fractures by veins may have caused the formation of coarse-grained sphalerite and galena in Stage III. The similar 207Pb/206Pb values among Py1 (average 0.849), Stage II galena (average 0.849), Stage III galena (average 0.849), and the nearby Shuikoushan granodiorite stock (corrected average 0.848) suggests that mineralization in stages I−III may represent distal skarn-type Pb-Zn-Ag mineralization genetically related to the Shuikoushan stock. This interpretation is supported by the similar ages of mineralization Stage I (apatite U-Pb: 159.4 ± 1.0 Ma) and Stage II (fuchsite 40Ar-39Ar: 158.1 ± 0.4 Ma) to the age of Shuikoushan stock (zircon U-Pb age: ca. 158 Ma). As the primary Au-hosting mineral at Kangjiawan, the As- and Au-rich Py3a occurs in sharp contact with porous Co-Ni-Se-Bi-Mo-As−poor Py3b, which commonly contains abundant fine-grained galena and sphalerite inclusions. This suggests that Py3b formed via coupled dissolution−re-precipitation of Py3a. This coupled dissolution−re-precipitation reaction favors the remobilization of Au from within the Py3a structure and its re-enrichment as Au inclusions in Py3b; this is supported by the anomalous Au peaks in time-resolved signal profiles from laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS) and the abundant outliers for Au concentrations in Py3b. The markedly distinct trace-element geochemistry of Py3 compared to those of Py1 and Py2, and the U-Pb age of Stage IV calcite (ca. 138 Ma), are indicative of an Early Cretaceous Au mineralization event. Published calcite C-O isotope data, coupled with the narrow range of δ34S values (0.6‰−2.2‰) of Py3, suggest that the Kangjiawan Au mineralization may be associated with a concealed Early Cretaceous pluton. We propose that the Kangjiawan deposit formed via the overprinting of Late Jurassic distal skarn Pb-Zn-Ag mineralization by Early Cretaceous magmatic-hydrothermal Au mineralization, which demonstrates that 150−135 Ma may also be an important period for the formation of the magmatic-hydrothermal mineralization belt.

Dendrochemical Analysis as a Method to Identify Mineralized Zones: Insights from the Marathon Cu-PGE Deposit

The Marathon Cu-platinum-group element (PGE) deposit is located within the Eastern Gabbro Series of the Proterozoic Coldwell Alkalic Complex, 10 km north of Marathon, Ontario. The Cu-PGE mineralization occurs within the Two Duck Lake Gabbro, an olivine gabbro intrusion. This geochemical orientation study tested the trace element analysis of tree cores as a method of identifying mineralized versus background areas in the Marathon deposit, focusing on copper (Cu), sulfur (S), palladium (Pd), and silver (Ag). Tree core samples (n=25) were collected with an increment borer from black spruce (Picea mariana) trees and dated by counting growth rings. Fifteen cores, 12 near/overtop the deposit and three distal control samples, were analysed with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) over a 10-year interval (1992-2002). Data normalization to 88Sr like in other dendrochemical studies corrected for tree health and growth effects. 32S, 63Cu, and 105Pd were found to have the highest concentrations at 94.198, 2.224, and 0.055 ppm, respectively, in control sample 23KPA2-3004. This tree is located beside the Pic River and receives large amounts of run-off from the entire Eastern Gabbro Series, possibly enhancing the chemical composition of the tree core. Excluding this anomalous sample, significant concentrations of Cu and Ag were found moving SSW along the deposit, aligning with the direction of movement of the Pleistocene Laurentide Ice Sheet. While this study did not clearly identify mineralized zones in the Marathon deposit, it has identified the possibility of mineralized run-off in the Pic River affecting nearshore tree chemical composition. The influence of local terrain and glacial till must be also considered when using this method. Future research will continue to study the factors influencing the uptake of elements in trees and refine methods for detecting mineralization through tree core analysis.

Germanium distribution in Mississippi Valley-Type systems from sulfide deposition to oxidative weathering: A perspective from Fule Pb-Zn(-Ge) deposit, South China

Abstract Germanium (Ge) is a critical raw material for emerging high-tech and green industries, resulting in considerable recent interest in understanding its distribution and geochemical behavior in ore deposits. In this contribution, the distribution of Ge and related trace elements in the Fule Pb-Zn(-Ge) deposit, South China, is investigated to reveal the distribution of Ge in the hydrothermal ores and during sulfide weathering, using multiple microanalytical techniques, including scanning electron microscopy, electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In the Fule MVT deposit, sphalerite (ZnS) is the most significant Ge-carrier relative to other sulfides, though the five recognized textural types of sphalerite display progressive depletion in Ge from the first sphalerite generation to the late one. In the early stage, sphalerite with fine-grained chalcopyrite inclusions has the highest Ge concentrations, probably accounting for a significant proportion of the total Ge. We interpret that high Ge concentrations in the early sphalerite may be attributable to high Cu activity in the mineralizing fluids. During oxidative weathering, Ge was redistributed from its original host, sphalerite, to the weathering product willemite (Zn2SiO4) rather than smithsonite (ZnCO3), with high levels of Ge (up to 448 μg/g) present in the willemite. The formation of abundant willemite largely prevents the dispersion of Ge during weathering. In principle, willemite-hosted Ge should be fully recoverable, and the Zn-silicate ores may, therefore, be a potential target to meet future demand. This study provides new information on how Ge behaves from sulfide- to weathering-stage in MVT systems, which directly impacts Ge mobility and deportment changes and the development of metal-lurgical strategies for Ge recovery.