Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

Mineralogical Characteristics of Color-Changing Garnet and the Effect of Light Path Length on Color

The color-changing garnet displays the “alexandrite effect”, changing from green in daylight to purplish-red under incandescent light. The mineralogical characteristics of color-changing garnet is analyzed using Raman spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, an electron probe, and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The color of garnets with different thicknesses was calculated using the International Commission on Illumination (CIE 1976) L*a*b* uniform color system. The results revealed the presence of rutile inclusions in color-changing garnet. Strong absorption in both the blue-violet zone and orange-yellow zone was the main cause for the color-changing effect of garnet. The distribution pattern of rare earth elements (REE) was left-leaning, showing the enrichment of heavy rare earth elements (HREE) and depletion of light rare earth elements (LREE). As the total Cr and V concentrations increased, the area of the 574 nm absorption peak in the UV-Vis spectrum also increased, leading to a more significant variation in color ΔE*ab. The light path length of the gemstone had a significant impact on the extent of the color-changing effect. The color difference reached a maximum and the color-changing effect was most visible when the thickness of the gemstone was 5 mm.

From ID-TIMS U-Pb dating of single monazite grain to APT-nanogeochronology: application to the UHT granulites of Andriamena (North-Central Madagascar)

Monazite and zircon grains from the ultra-high temperature (UHT) granulite of the Andriamena unit in the centre north of Madagascar, previously investigated using micro-drilled single grain isotopic dissolution geochronology and in-situ electron microprobe chemical dating by Paquette et al. (2004), are reinvestigated using high spatial resolution techniques: atom probe tomography (APT), transmission electron microscopy (TEM), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The dated grains are located in quartz, garnet belonging to the peak UHT metamorphic assemblage and in retrograde coronitic texture composed of biotite, cordierite and orthoamphibole. Monazite grains show complex discordant trends with several radiogenic Pb (Pb*) loss dispersions, that were previously interpreted as recording at least four geologic episodes occurring from the Archean (~2.7 Ga) to the Proterozoic-Cambrian (~0.5 Ga). Multiscale investigations with SIMS, TEM and APT have been carried out on monazite and LA-ICP-MS on zircon. Zircon grains hosted in garnet and those in quartz record concordant ages at 2758 ±28 Ma and 2609 ±51 Ma, respectively. Monazite grains show age dispersion and a Pb*-loss trend correlated with the grain petrographic position. Grains located in garnet and quartz present less Pb*-loss than those located in the coronitic texture. The discordia indicates a crystallisation age at 2555 ±71 Ma and monazite grains hosted in quartz and garnet record a disturbance event at 1053 ±246 Ma. TEM investigations show that monazite located in quartz and garnet contain numerous Pb-bearing nanophases compared to monazite located in coronitic texture. There is an inverse correlation between the number of Pb-bearing nanophases and the percentage of Pb*-loss in monazite grains. 232Th/208Pb ratio obtained with APT in monazite matrix (i.e. excluding Pb-bearing nanophases) located in quartz and garnet indicated a mean age of 1092 ±127 Ma. This date is interpreted as a hitherto undetected geochronological record in Andriamena unit.

Late Carboniferous–Early Permian sedimentary–tectonic evolution in the eastern Qaidam Basin, Western China: Insight into the zircon U–Pb geochronology of ash-fall tuffs and sandstones

The Late Carboniferous–Early Permian period is a significant transitional phase within the late Paleozoic ice age and to investigate the sedimentary–tectonic evolution of the Qaidam Basin in this period is crucial for comprehensively understanding the tectonic history of the northeastern Paleo-Tethys Ocean and the related response to energy and mineral resources. This paper focuses on the Carboniferous–Permian strata of the Wanggaxiu-Dongdagou outcrop that was taken to represent the southern Oulongbruk terrane in the eastern Qaidam Basin. We determined the ages of tuff interbeds within the Zhabusagaxiu Formation originally identified as the upper Carboniferous and obtained the crystallization age spectra of detrital zircon grains from Carboniferous to lower Permian sandstones using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) isotope geochemical techniques. The origin of the volcanic ash and the sedimentary–tectonic evolution in this period were analyzed. The results indicate that the original Zhabusagaxiu Formation can be divided into two chronostratigraphic units: the upper Carboniferous Zhabusagaxiu Formation and the lower Permian. The earliest age obtained from tuffaceous layers within the dark shale interval is 297.8 ± 3.0 Ma (mean square weighted deviation (MSWD) = 0.87), which suggests a stratigraphic boundary between the Carboniferous and Permian periods. Detrital zircons from Carboniferous–Permian samples in the southern Oulongbruk terrane predominantly originated from the Qaidam block-North Qaidam ultrahigh-pressure belt continental island arc to the south. The ultrahigh-pressure belt had a significantly increased contribution to the detrital source supply system from the Late Carboniferous to Early Permian, while the Qaidam block experienced frequent volcanic eruptions from 298 to 293 Ma, dispersing volcanic ash only northward to the Oulongbruk back-arc basin and the Zongwulong Trough. The upper Carboniferous Zhabusagaxiu Formation was marked by siliceous clastic rock–carbonate rock interbedding in an epicontinental sea, while the lower Permian was characterized by shallow to bathyal marine shelf to subaqueous sedimentation. The Early Permian transgression potentially represents the largest transgression during the late Paleozoic ice age, indicating an enriched hydrocarbon-generating interval.

Trace element concentrations and chemical zoning of spodumene from magmatic and hydrothermal origins

Spodumene is a major lithium ore mineral mined from granitic pegmatites and can crystallize (1) from magma, (2) from hydrothermal fluid in miarolitic cavities or fracture-filling units, or (3) as a product of petalite breakdown. Although spodumene’s purity influences the economic value of lithium ore, its trace-element geochemistry is not entirely understood. This study investigated 24 unaltered spodumene samples from 21 localities formed through each of these three modes of origin. The chemical zoning of each spodumene sample was characterized using cathodoluminescence (CL), micro-X-Ray fluorescence mapping (µXRF), and/or qualitative laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) line scans, whereas the concentrations of trace elements were quantified using LA-ICP-MS point analyses. Intra-crystalline chemical zoning was present in all three spodumene types as either oscillatory growth bands and/or sector zoning. For the four most abundant transition and post-transition metals analyzed (Fe, Mn, Ga, Sn), the concentrations ranged from below detection to 10510 ppm (Fe), 1850 ppm (Mn), 300 ppm (Ga), 320 ppm (Sn), whereas Rb and Cs were below detection. Magmatic spodumene had the highest mean concentrations of Fe (2345 ppm) and Sn (94 ppm), hydrothermal spodumene had the highest mean concentrations of Mn (641 ppm) and Ga (94 ppm), and spodumene formed from the breakdown of petalite consistently had the lowest mean concentrations, though there was significant overlap in the datasets. In addition, texturally similar spodumene-quartz intergrowths of primary and secondary origins were distinguished via trace-element geochemistry. Principle component analysis of Fe, Mn, Ga, Sn, Ti, and Zn values from all 325 LA-ICP-MS measurements showed discrimination by CL color, as well as color in handsample for gem-varieties of hydrothermal spodumene.

Tissue-specific deposition, speciation and transport of antimony in rice.

Rice (Oryza sativa) as a staple food is a potential intake source of antimony (Sb), a toxic metalloid. However, how rice accumulates this element is still poorly understood. Here, we investigated tissue-specific deposition, speciation, and transport of Sb in rice. We found that Sb(III) is the preferential form of Sb uptake in rice, but most Sb accumulates in the roots, resulting in a very low root-to-shoot translocation (less than 2%). Analysis of Sb deposition with laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) showed that most Sb deposits at the root exodermis. Furthermore, we found that Sb is mainly present as Sb(III) in the root cell sap after uptake. Further characterization showed that Sb(III) uptake is mediated by Low silicon rice 1 (Lsi1), a Si permeable transporter. Lsi1 showed transport activity for Sb(III) rather than Sb(V) in yeast (Saccharomyces cerevisiae). Knockout of Lsi1 resulted in a significant decrease in Sb accumulation in both roots and shoots. Sb concentration in the root cell sap of two independent lsi1 mutants decreased to less than 3% of that in wild-type rice, indicating that Lsi1 is a major transporter for Sb(III) uptake. Knockout of Lsi1 also enhanced rice tolerance to Sb toxicity. However, knockout of Si efflux transporter genes, including Lsi2 and Lsi3, did not affect Sb accumulation. Taken together, our results showed that Sb(III) is taken up by Lsi1 localized at the root exodermis and is deposited at this cell layer due to lack of Sb efflux transporters in rice.

Characteristics, preservation mechanisms, and significance of aragonite in lacustrine shale: A case study from the Jiyang Depression, Bohai Bay Basin

Aragonite is a metastable mineral, which is easily transformed into calcite, and generally difficult to preserve in the stratum. However, large amounts of aragonites were found in the Paleogene shale of the Jiyang Depression. The characteristics and preservation mechanisms of these aragonites were analyzed through a series of analytical methods, including cathodoluminescence, field-emission scanning electron microscopy (FESEM), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), micro-area carbon and oxygen isotopes, Sr isotopes, and dissolution simulation experiments under high temperature and high pressure. The research results show that: ①Aragonite in the Paleogene shale of the Jiyang Depression is related to algal microbial fossils, primarily composed of coccoliths and characterized by two emission peaks at 420 nm and 480 nm in cathodoluminescence; ②The primary factor allowing biological aragonite to be preserved is the immaturity of the organic matter and the deficiency of abundant organic acids necessary for its dissolution or transformation, which is confirmed by the evidence of organic matter maturity and simulation experiments of organic acid dissolution on aragonite under high-temperature and high-pressure conditions. Additional factors that may aid in the preservation of aragonite are the ideal sedimentation conditions, the defense of organic coating, and the enclosed environment with tiny pores, low porosity, and low permeability; ③These aragonite-rich shales, characterized by coccolithophores, provide a solid evidence for seawater intrusion into terrestrial lake basin, and have a significant implication for the source and storage of shale oil.

Examining differences in the uptake of corrosive gases in polymer films and its dependence on temperature and relative humidity using a novel procedure combining sample weathering and LA-ICP-MS analysis

In polymer coating applications for technological products exposed to harsh environmental operating conditions, it is essential to provide and extend the protection capability of the coating material against corrosive gases, such as hydrogen sulfide or sulfur dioxide. Therefore, applied materials are subject to ongoing developments to improve their properties. Such developments aiming to establish improved polymer materials can only be performed accompanied by suitable testing procedures and analysis methods, for which a versatile approach is proposed in the presented work.We developed a testing approach, combining a mixed flowing gas setup (MFG) that allows flexibly adjustable exposure conditions for weathering experiments, and laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) for subsequent sample analysis, allowing quantitative and spatially resolved determination of the sulfur uptake derived from H2S or SO2 weathering with high sensitivity. The testing procedure is demonstrated on four different polymer types – polyimide (PI), polyvinylpyrrolidone (PVP), polystyrene (PS), and polyvinylacetate (PVA). Results from bulk measurements showed a significantly higher uptake of SO2 compared to H2S, and that the uptake increases with higher exposure temperatures and relative humidity levels. Further, quantitative sulfur depth profile measurements reveal diffusion profiles into the polymer films. The gas uptake was observed mostly withing the uppermost 1–2 µm of the surface, with quickly decreasing concentrations into the bulk of the materials. However, strong variations of the spatial distribution of sulfur between the different polymer types and between different exposure conditions were determined. The results provided give a good insight into what possibilities the proposed investigation procedure opens up for specifically dedicated research compared to standard methods that are used to determine gas permeation.

Simultaneous U–Pb and U–Th Dating Using LA-ICP-MS for Young (<0.4 Ma) Minerals: A Reappraisal of the Double Dating Approach

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

Origin of Color and Spectral Characteristics of Nanhong Agate from Northeast Yunnan, China

Nanhong agate has attracted public attention as the most distinctive gemstone in China. Owing to the limited data on Nanhong agates from a new production area in northeastern Yunnan, this paper presents the first data from gemological studies on these agates. Complex investigations using Fourier-transform infrared (FTIR) spectrometry, ultraviolet–visible (UV–VIS) luminescence spectrometry, Raman spectroscopy, polarizing microscopy, scanning electron microscopy (SEM), electron microprobe (EPMA), and laser ablation–inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses were carried out to obtain basic data concerning the gemological properties, microstructure, and spectroscopic and geochemical characteristics of this interesting material. The results illustrate that Nanhong agates from northeastern Yunnan are mainly composed of α-quartz and also contain certain amounts of moganite, illite, goethite, and hematite. The typical red (yellow) and white appearance can be attributed to the microstructure of the agates, the contents of Fe and Al impurities, and trace elements. The Raman spectra, microstructure, and chemical composition of the unique “yellow-skinned” agates from northeastern Yunnan are significantly different from those of other types of Nanhong agate. This work lays a foundation for the future identification and research of this type of Nanhong agate.

Mapping elemental solutes at sub-picogram levels during aqueous corrosion of Al alloys using diffusive gradients in thin films (DGT) with LA-ICP-MS

A novel approach using diffusive gradients in thin films (DGT) with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for two-dimensional mapping of elemental solute release at sub-picogram levels during aqueous corrosion of Al alloys is presented. Evaluation of different DGT gels with mixed micro-sized binding phases (polyacrylamide-Chelex-Metsorb, polyurethane (PU)-Chelex-Metsorb, PU-Chelex-Zr(OH)4) demonstrated the superior performance of PU gels due to their tear-proof handling, low shrinkage, and compliance with green chemistry. DGT devices containing PU-Chelex-Zr(OH)4 gels, which have not been characterized for Al sampling before, showed quantitative uptake of Al, Zn, and Cu solutes over time (t = 4–48 h) with higher Al capacity (ΓDGT = 6.25 µg cm−2) than different gels. Application of PU-Chelex-Zr(OH)4 gels on a high-strength Al-Cu alloy (Al2219) exposed to NaCl (w = 1.5%, pH = 4.5, T = 21 °C) for 15 min in a novel piston-type configuration revealed reproducible patterns of Al and Zn co-solubilization with a spatial expansion ranging between 50 and 1000 µm. This observation, together with complementary solid-state data from secondary electron microscopy with energy-dispersive X-ray spectroscopy, showed the presence of localized pitting corrosion at the material surface. Detection limits for total solute masses of Al, Zn, and Cu were ≤0.72 pg, ≤8.38 pg, and ≤0.12 pg, respectively, for an area of 0.01 mm2, demonstrating the method’s unique capability to localize and quantify corrosion processes at ultra-trace levels and high resolution. Our study advances the assessment of Al alloy degradation in aqueous environments, supporting the design of corrosion-resistant materials for fostering technological safety and sustainability.Graphical

Multistage evolution of gold mineralization in the Kibali gold district: Insights from pyrite analyses

The Kibali gold district, located on the Congo Craton, comprises a Neoarchean gold resource exceeding 28.7 Moz. The district is located within a westerly-verging stacked fold-and-thrust belt associated with a compressional tectonic regime active from ca. 2.64–2.60 Ga. Deposits are hosted by a major fault zone that consists of a complex series of smaller thrust faults, shear zones, and folds, which extend over 60 km. Gold deposits are primarily hosted in BIF and clastic sedimentary rocks. The gold and associated sulfides are in veins and disseminated in NE-to NNE-trending ore shoots within the deformed and metamorphosed volcanosedimentary rocks. Pyrite is the dominant sulfide mineral and hosts both solid solution gold and free gold. Because of its strong association with the gold mineralization, our study focusses on unravelling the metallogeny of the area by considering pyrite textural analyses, in situ trace element analyses using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), and S isotopic composition (δ34S) analyses using Secondary Ion Mass Spectrometry (SIMS).Eight distinct pyrite types were identified, including microcrystalline sooty (py-0a), small grains (<40 μm) (py-0b), aggregate recrystallized (py-1), core-rich inclusion (py-2), vein-like (py-3), non-zoned (py-4a), oscillatory As-bands zoned (py-4b), and cubic euhedral (py-5) pyrite. The ore-forming processes occurred over a polyphase evolution. Syn-diagenetic pyrite py-0a in volcaniclastic layers of older basin sediments served as the primary repository of Au (15.6 ppm median) with a near-zero δ34S value. Late diagenetic or early metamorphic pyrite (py-0b) was found in younger basin sediments. Py-1 resulted from solid-state recrystallization of py-0a and py-0b. During the early ore stage, porous py-2 with high Au concentrations (3.1 ppm) and various trace element enrichments precipitated due to fluid-rock interaction. Metal precipitation occurred through sulfidation and carbonation of wall rock with a relatively reduced fluid undergoing 34S-depletion. However, py-3 displayed notable trace element depletion and a complex mineral association. In a second ore stage, py-4a and zoned py-4b deposition occurred, dominated by an over-pressured fluid fracturing brittle rock. Py-4b, rich in Au (5.5 ppm) concentrated in oscillatory zoned As-rich bands, resulted from interactions during pulsed fluid flow. This process involved fluid phase separation, non-equilibrium conditions, 32S-depletion, and precipitation of py-4b with a high δ34S value (6.4 ‰ mean). Subsequently, pyrite (0–4) generations underwent deformation during a later ductile deformation event, leading to the remobilization and concentration of invisible gold into adjacent gold grains within the high-grade shoot plunging NE. This process involved shearing, boudinaging, and folding ore minerals in tightly folded structures. Late-stage py-5 formed under gold-poor fluid conditions or inefficient gold depositional conditions. Brittle fracturing of these grains later provided local sites for remobilized gold. The study contributes insights into the origin and evolution of gold mineralization in the Kibali gold district, supporting a multistage ore-forming fluid system.

Timing of Hydrothermal Alteration and Au-Sb-W Mineralization, Stibnite-Yellow Pine District, Idaho

Abstract The Stibnite-Yellow Pine district of central Idaho was mined from the early 1900s until the 1990s, extracting gold, antimony, tungsten, and mercury from veins and disseminated and replacement ores in mountainous terrain along the headwaters of the Salmon River. Mining during the two World Wars supplied critical antimony and tungsten to the war efforts. Recent exploration has delineated mineral resources of over 187 metric tons Au, 274 metric tons Ag, and 93,000 metric tons Sb. Mineralization is hosted in Cretaceous Idaho batholith granitic rocks and a sequence of Neoproterozoic to Paleozoic metasedimentary strata of carbonate and siliciclastic compositions. Historic studies outlined some of the complex paragenesis but debated the absolute age of mineralization. New petrographic and geochronologic work documents a sequence of five hydrothermal events in the Stibnite-Yellow Pine district. Event 1 is related to Cretaceous magmatic and hydrothermal activity and includes events ranging in age from 86 to 75 Ma, including sparse quartz-molybdenite veins dated at 86 Ma. Disseminated gold mineralization of Event 2 is associated with sericitic alteration and sulfidation of igneous biotite and replacement of plagioclase by potassium feldspar, largely in granodiorite. Gold is present in zoned arsenian pyrite in both disseminated ores and in crosscutting carbonate-quartz veins containing pyrite and arsenopyrite. The large Yellow Pine deposit, localized at a dilatant bend in the Meadow Creek fault, hosts such disseminated and vein gold. Event 2 is interpreted as the major gold-forming event; 40Ar/39Ar ages of sericite and potassium feldspar alteration range, respectively, from 70 to 59 and 66 to 56 Ma. The long span is interpreted to reflect the age of gold mineralization and local overprinting by Event 3. A narrower range from 66 to 61 Ma is interpreted to date the peak of gold mineralization and alteration. Event 3, tungsten mineralization with scheelite, is texturally later than Event 2 gold and localized along the Meadow Creek structure. Event 3 scheelite has been dated by isotope dilution-thermal ionization mass spectrometry (ID-TIMS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb methods at 57 Ma. Event 4, best developed in the West End area, includes gold-silver–bearing quartz-carbonate-pyrite veins and breccias with epithermal textures and potassium feldspar alteration envelopes. Adularia from Event 4 yields 40Ar/39Ar plateau ages of 52 to 51 Ma. Event 5 antimony and mercury mineralization consists of stibnite veins and breccia cements at the Yellow Pine and Hangar Flat deposits as well as cinnabar veins and replacements at the peripheral Fern and Hermes deposits; it is constrained by an LA-ICP-MS U-Pb date on scheelite (ca. 47 Ma) intergrown with stibnite. Minor propylitic and argillic alteration is evident in 47 Ma igneous dikes, which do not contain economic mineralization. The Au-Sb-W ores in the Stibnite-Yellow Pine mining district formed over an extended time period from about 70 to 45 Ma in multiple pulses that were localized along the Meadow Creek fault zone. Each event corresponds to episodes of magmatism and/or hydrothermal activity in the region. Insignificant Event 1 skarn and molybdenum mineralization is similar in age to the Thompson Creek porphyry molybdenum deposit in central Idaho. Event 2 gold mineralization occurred during a magmatic gap in central Idaho but was synchronous with magmatism in the Bitterroot lobe further north; Event 2 is similar in age to orogenic gold-arsenic mineralization at the Beartrack mine in eastern Idaho. Event 3 scheelite mineralization coincides with tungsten mineralization at the Quartz Creek deposit, late magmatism in the Bitterroot lobe, and rapid exhumation of the Atlanta lobe of the Idaho batholith. Event 4 gold mineralization is coincident with the onset of regional Challis magmatism and extension. Event 5 antimony and mercury mineralization is time-equivalent to epithermal gold mineralization in the nearby Thunder Mountain volcanic field and the peak of Challis magmatism.

The emperor's new glass: The introduction of Carolingian wood ash glass in North Sea trade

AbstractMicro‐X‐ray fluorescence (XRF) screening of 244 glass sherds from Ribe, Denmark, identified 23 wood ash glasses. The closely dated finds pinpoint the arrival of the earliest wood ash glass produced in Western Europe in this important North Sea trading hub. This glass type was absent among glass from 700 to 790 CE but feature strongly from 790 to 810 CE. Electron microprobe analysis (EMPA) and laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) analysis of 24 glasses show the presence of four types. We show the strengths of classifying wood ash glass based on the glass‐producing sands and conclude that the earliest production took place on a considerable scale and had a major impact on glass circulation in Northern Europe in the ninth century.

U–Pb LA-ICP-MS and Re–Os dating of wolframite and molybdenite: Constraints on multiple mineralization and cooling history (40Ar/39Ar) for the magmatic–hydrothermal system at Borralha, northern Portugal

The Borralha area (Iberian Massif, Portugal) reflects a long-lived and multiphase magmatism (ca. 316 to 300 Ma), characterized by three types of granite emplacement during two different extensional events (E1 and E2) and one compressional event (C3) within the Variscan orogeny. The W (Cu) mineralization styles correspond to veinlets and quartz veins (i.e., São António and Santa Helena), and disseminations in the Santa Helena breccia pipe. Molybdenite coexists with an Fe-bearing wolframite–quartz assemblage in the Venise breccia pipe and quartz veins (i.e., São José and São Paulo).The geochemistry and geochronology of wolframite and molybdenite samples were studied by electron probe microanalysis (EPMA), in-situ U–Pb laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) and Re–Os thermal ionization mass spectrometry (TIMS). The wolframite yields a U–Pb age (sample WBV1) of 315.2 ± 4.7 Ma (2σ), representing the first recognized episode of W deposition in the Iberian Massif. Wolframite samples (WBV1, WB1, and WB4) have a ferberite composition with a hübnerite/ferberite ratio of < 29. High amounts of Nb (up to 3703 ppm) with low Ta (up to 123 ppm) and REEs (up to 11.4 ppm) and conversely, low amounts of Nb (up to 471 ppm) with high Ta (up to 190 ppm) and REEs (up to 53.7 ppm) were measured in wolframite samples. The REEs normalized patterns of the wolframite samples record a mixed signature. Large and positive Eu/Eu* and Er/Er* anomalies were identified (sample WBV1), whereas negative Ce/Ce* and Nd/Nd* anomalies were observed in samples WB1 and WB4.Molybdenite Re–Os dating yields absolute ages ranging from 305.1 to 303.8 ± 2.2 Ma (2σ), which are coeval with the emplacement of E2 biotite granite (Penedos; I-type; <305 Ma). Low amounts of Re (<1 ppm), W, Co, Ni, As, Cu, Bi, Fe, Mn V and Se (<0.005 wt%) were detected in the molybdenite structure.Constraints between the timing of W- and Mo-deposition and a protracted cooling history of the host rocks are confirmed by 40Ar/39Ar white mica dating. The 40Ar/39Ar ages obtained for secondary white micas collected from Mo veins (Venise breccia pipe; 277 ± 3 and 287 ± 4 Ma 2σ) and W (Cu) dissemination (Santa Helena breccia pipe; 287 ± 2 and 279.0 ± 6 Ma 2σ) record the isotopic resetting by later hydrothermal overprints and cooling /exhumation history after E2 Gerês biotitic granite emplacement.The W-ore deposition did occurred during the final E1 extensional tectonic stage (315 Ma) and E2 extensional tectonic stage for Mo-ore deposition, where a temporal offset was needed for the adjustment of tectonic conditions after the C3 compressional and E2 extensional stage started.

Quantitative Insights on Impurities in Ice Cores at the Micro‐Scale From Calibrated LA‐ICP‐MS Imaging

AbstractUnderstanding the microscopic variability of impurities in glacier ice on a quantitative level has importance for assessing the preservation of paleoclimatic signals and enables the study of macroscopic deformational as well as dielectric ice properties. Two‐dimensional imaging via laser‐ablation‐inductively‐coupled‐plasma‐mass‐spectrometry (LA‐ICP‐MS) can provide key insight into the localization of impurities in the ice. So far, these findings are mostly qualitative and gaining quantitative insights remains challenging. Recent advances in LA‐ICP‐MS high‐resolution imaging now allow ice grains and grain boundaries to be resolved individually. These resolutions require new adequate quantification strategies and, consequently, accurate calibration with matrix‐matched standards. Here, we present three different quantification methods, which provide a high level of homogeneity at the scale of a few tens of microns and are dedicated to imaging applications of ice cores. One of the proposed methods has a second application, offering laboratory experiments to investigate the displacement of impurities by grain growth, with important future potential to study ice‐impurity interactions. Standards were analyzed to enable absolute quantification of impurities in selected ice core samples. Calibrated LA‐ICP‐MS maps indicate similar spatial distributions of impurities in all samples, while impurity levels vary distinctly: Higher concentrations were detected in glacial periods and Greenland, and lower levels in interglacial periods and samples from central Antarctica. These results are consistent with ranges from complementary meltwater analysis. Further comparison with cm‐scale melting techniques calls for a more sophisticated understanding of the ice chemistry across spatial scales, to which calibrated LA‐ICP‐MS maps now contribute quantitatively.

Dose-Dependent Effect on Plant Growth of Exposure to Metal-Organic Framework MIL-101(Cr).

With the increasing use of metal-organic frameworks (MOFs), they will inevitably enter the environment intentionally or unintentionally. However, the effects of MOFs on plant growth are poorly understood. Here, we investigated the effects of exposure of the rhizosphere to MOFs on plant growth. MIL-101(Cr) was selected as a research model due to its commercial availability and wide use. Soybean plants at the two-leaf stage were subjected to various durations (1-7 days) and concentrations (0-1000 mg/L) of exposure in hydroculture with a control group treated with ultrapure water. We found that MIL-101(Cr) had a positive effect on soybean growth at a lower dose (i.e., 200 mg/L); however, at higher doses (i.e., 500 and 1000 mg/L), it exhibited significant toxicity to plant growth, which is evidenced by leaf damage. To investigate the mechanism of this effect, we used Cr as an indicator to quantify, track, and image MIL-101(Cr) in the plant with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Results indicated that MIL-101(Cr) primarily accumulated in the cortex of roots (up to 40 times higher than that in stems), with limited translocation to stems and negligible presence in leaves and cotyledons. In addition, metabolomic analysis of soybeans indicated that low-dose MIL-101(Cr) could increase the sucrose content of soybean roots to promote plant growth, while a high dose could induce lipid oxidation in roots. This study provides valuable insights into the ecological toxicology of MOFs and underscores the importance of assessing their environmental impact for sustainable agricultural practices.

Metallogenic Difference between the Late Aptian Nansu and Aishan Pluton in Jiaodong: Constraints from in Situ Apatite Elemental and Nd Isotopic Composition

A series of Mo-polymetallic deposits have been developed in the Jiaodong Peninsula. Notably, these Mo-dominant deposits formed essentially during the same period as the well-known world-class Au deposits in this area, hinting at a potentially unique geological correlation between them. Therefore, conducting thorough research on Mo deposits in Jiaodong holds significant importance in exploring the area’s controlling factors of Mesozoic metal endowments. To reveal the petrogenesis and metallogenic potentials of Mo-fertile and ore-barren granitoid, apatite grains from the Late Aptian Nansu granodiorite and Aishan monzogranite are investigated in this study. Detailed petrographical observations, combined with in situ analysis of electron probe micro-analyzer (EPMA) and Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), have been conducted on apatite grains from the Nansu and Aishan plutons. This comprehensive analysis, encompassing both major and trace elements as well as isotopic characteristics of apatite, aims to elucidate the metallogenic differences within the late Early Cretaceous granitoids of Jiaodong. The results reveal that the apatite grains across all samples belong to fluorapatites, suggesting their magmatic origin. Additionally, chondrite-normalized rare earth element (REE) patterns of apatites in ore-fertile and ore-barren granitoids exhibit a “right-leaning” trend, characterized by relative enrichments in light REEs and depletions in heavy REEs. Both the Nansu and Aishan plutons exhibit moderately negative Eu anomalies (with averages δEu values of 0.44 and 0.51, respectively), along with slightly positive Ce anomalies (averaging δCe values of 1.08 and 1.11, respectively). A negative correlation is observed between their δEu and δCe values, indicating that the parental magmas of ore-fertile and ore-barren granitoids were formed in a relatively oxidizing environment. The calculated apatite OH contents for the Nansu pluton range from 0.26 to 1.38, while those for the Aishan pluton vary between 0.24 and 1.51, indicating comparable melt H2O abundances. Consequently, the results suggest that neither the oxygen fugacities nor the water contents of the parental magma can account for the metallogenic differences between Nansu and Aishan plutons. The apatite in the Nansu pluton exhibits a higher Ce/Pb ratio and a relatively lower Th/U ratio, indicating the involvement of a greater volume of fluids in the magmatic evolution process of this ore-bearing granitoid. Apatite grains sourced from the Nansu and Aishan plutons exhibit εNd(t) values ranging from −16.63 to −17.61 (t = 115.7 Ma) and −17.86 to −20.86 (t = 116.8 Ma), respectively. These results suggest that their parental magmas primarily originated from the partial melting of Precambrian metamorphic basement rocks within the North China Craton, with a minor contribution from mantle-derived materials. Additionally, the presence of mafic microgranular enclaves in both the Nansu and Aishan plutons indicates that both have undergone magma mixing processes. The binary diagrams plotting the ratios of Ba/Th, Sr/Th, and U/Th against La/Sm demonstrate that apatite grains of ore-fertile granitoid exhibit a distinct trend towards sediment melting. This suggests the potential incorporation of sedimentary materials, particularly those rich in molybdenum, into the magmatic source of the Nansu pluton, ultimately leading to the occurrence of molybdenum mineralization.

Minimizing the effects of Pb loss in detrital and igneous U–Pb zircon geochronology by CA-LA-ICP-MS

Abstract. Detrital zircon geochronology by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) is a widely used tool for determining maximum depositional ages and sediment provenance, as well as reconstructing sediment routing pathways. Although the accuracy and precision of U–Pb geochronology measurements have improved over the past 2 decades, Pb loss continues to impact the ability to resolve zircon age populations by biasing affected zircon toward younger apparent ages. Chemical abrasion (CA) has been shown to reduce or eliminate the effects of Pb loss in zircon U–Pb geochronology but has yet to be widely applied to large-n detrital zircon analyses. Here, we assess the efficacy of the chemical abrasion treatment on zircon prior to analysis by LA-ICP-MS and discuss the advantages and limitations of this technique in relation to detrital zircon geochronology. We show that (i) CA does not systematically bias LA-ICP-MS U–Pb dates for 13 reference materials that span a wide variety of crystallization dates and U concentrations, (ii) CA-LA-ICP-MS U–Pb zircon geochronology can reduce or eliminate Pb loss in samples that have experienced significant radiation damage, and (iii) bulk CA prior to detrital zircon U–Pb geochronology by LA-ICP-MS improves the resolution of age populations defined by 206Pb/238U dates (Neoproterozoic and younger) and increases the percentage of concordant analyses in age populations defined by 207Pb/206Pb dates (Mesoproterozoic and older). The selective dissolution of zircon that has experienced high degrees of radiation damage suggests that some detrital zircon age populations could be destroyed or have their abundance significantly modified during this process. However, we did not identify this effect in either of the detrital zircon samples that were analyzed as part of this study. We conclude that pre-treatment of detrital zircon by bulk CA may be useful for applications that require increased resolution of detrital zircon populations and increased confidence that 206Pb/238U dates are unaffected by Pb loss.

Metallomic mapping of gut and brain in heavy metal exposed earthworms: A novel paradigm in ecotoxicology

This study explored the uptake of lead in the epigeic earthworm Dendrobaena veneta exposed to 0, 1000, and 2500 μg Pb/g soil. The soil metal content was extracted using strong acid digestion and water leaching, and analysed by means of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to estimate absolute and bioavailable concentrations of metals in the soil. The guts and heads of lead-exposed earthworms were processed into formalin-fixed and paraffin embedded sections for high-resolution multi-element metallomic imaging via Laser Ablation ICP-MS (LA-ICP-MS). Metallomic maps of phosphorus, zinc, and lead were produced at 15-μm resolution in the head and gut of D. veneta. Additional 4-μm resolution metallomic maps of the earthworm brains were taken, revealing the detailed localisation of metals in the brain. The Pb bioaccumulated in the chloragogenous tissues of the earthworm in a dose-dependent manner, making it possible to track the extent of soil contamination. The bioaccumulation of P and Zn in earthworm tissues was independent of Pb exposure concentration. This approach demonstrates the utility of LA-ICP-MS as a powerful approach for ecotoxicology and environmental risk assessments.

Olivine in ultramafic rocks from the Polaris Alaskan-type intrusion: A geochemical record of open-system crystallization, diffusional re-equilibration, mantle source, and redox conditions in primitive arc magmas

Olivine in cumulates from the Early Jurassic Polaris Alaskan-type ultramafic-mafic intrusion in the North American Cordillera displays a wide range of textures and compositions produced in a dynamic crystallization environment as part of a transcrustal arc magmatic system. Major, minor, and trace element analyses of olivine were determined using combined electron probe microanalysis (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to assess the utility of olivine as a petrogenetic indicator in ultramafic intrusions. High forsterite contents (>Fo87) of olivine from dunite, olivine wehrlite, and wehrlite indicate that the parent melts were primitive in composition and that they may represent intrusive analogues to extrusive arc picrites found elsewhere in the Cordillera. Forsterite-Ni systematics (Fo92–80, Ni = 3000–300 ppm) show fractional crystallization-controlled evolution from dunite to olivine wehrlite to wehrlite through olivine clinopyroxenite. Low-Ni olivine (Fo84–80, 500–300 ppm) in magnetite-olivine clinopyroxenite indicates the effects of sulfide melt saturation and Ni-depletion of the residual magma. Entrainment of high-Fo olivine in evolved melts and mixing between fractionated and primitive magmas explains olivine compositions with Ni concentrations (1000–3000 ppm) in excess of those predicted by fractional crystallization models. Extensive subsolidus diffusion of Mg, Fe, Ni, Mn, Ca, Cr, Al, and Li occurred during crystallization and cooling of olivine. Uniform concentrations of Mg, Fe, Ni, and Mn in individual samples and across crystals of olivine indicate complete equilibration in the consolidating cumulate pile. Calcium, Cr, and Al from Polaris olivine (e.g., typically <1000 ppm Ca, <100 ppm Cr and Al), and from plutonic olivine in general, are depleted relative to volcanic olivine as the result of diffusional re-equilibration with interstitial melt and other co-crystallizing phases (Cr-spinel, clinopyroxene). Ratios of first-row transition elements (Mn, Zn, Fe, Co, Ni) in olivine were modified during intracrustal processes (e.g., fractional crystallization, diffusion), however, ratios from the most primitive olivine are indicative of primary mantle signals. Lithium concentrations in olivine (2–12 ppm) show evidence for subsolidus diffusive re-equilibration with Li-enriched melts. Ratios of V/Sc (0.03–0.5) are consistent with relatively oxidized parent magmas and arc mantle sources to Polaris and Alaskan-type intrusions. The Polaris parent magmas ascended through the uppermost mantle and lowermost crust on sufficiently short timescales to avoid significant magmatic differentiation prior to emplacement at a depth of ≤15 km. The findings of this microanalytical study highlight the utility of olivine as a petrogenetic recorder of primary magmatic and high-temperature diffusional processes in ultramafic plutonic rocks and contribute to our understanding of the evolution of primitive arc magmas.