Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

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

The causes of U-Pb isotopic discordance documented by Paquette et al. (2004) in monazite grains from the ultra-high temperature (UHT) granulite of the Andriamena unit of Madagascar are re-evaluated in the light of nanoscale crystal-chemical characterization utilising Atom Probe Tomography (APT) and state-of-the-art Scanning Transmission Electron Microscopy (STEM). APT provides isotopic (208Pb/232Th) dating and information on the chemical segregation of trace elements (e.g., Pb) in monazite at nanoscale. Latest generation of STEM allows complementary high-resolution chemical and structural characterization at nanoscale. In situ isotopic U–Pb dating with Secondary Ion Mass Spectrometry (SIMS) on 25 monazite grains and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) on zircon have been employed to refine the age spectra. Monazite and zircon grains located in quartz and garnet formed with the peak UHT metamorphic assemblage, which is partially overprinted by retrograde coronitic textures. Zircon grains hosted in garnet and in quartz yield concordant U–Pb ages at 2758 ± 28 Ma and 2609 ± 51 Ma, respectively whereas monazite grains hosted in quartz and garnet show a discordant Pb* loss trend on the Concordia diagram recording disturbance at 1053 ± 246 Ma that is not seen by the zircon, underlining the importance of combining the use of monazite and zircon to understand the history of polymetamorphic rocks. The Pb*-loss trend of monazite is related to petrographic position, with less Pb* lost from monazite hosted in quartz and garnet than monazite hosted in the coronitic reaction texture domains. STEM shows that the garnet- and quartz-hosted monazite grains contain more Pb-bearing nanophases than monazite grains located in the coronitic textures. An inverse correlation between the number of Pb-bearing nanophases and the percentage of Pb*-loss in monazite grains demonstrates that Pb* is retained in the grain in the form of nanophases. The formation of Pb-bearing nanophases limits Pb*-loss at the grain scale and therefore allows the preservation of early events. 208Pb/232Th ratios obtained with APT in monazite located in quartz and garnet and excluding Pb*-bearing nanophases indicate a mean age of 1059 ± 129 Ma corresponding to a disturbance event hitherto undetected in the geochronological record of the Andriamena unit. Thus, geochronology with APT allows access to information and the definition of events that may be blurred or obscured when examined at lower spatial resolution.

Quantitative determination and subcellular mapping of Pt-based drugs in single breast tumour cells via laser ablation-ICP-mass spectrometry.

For years, cancer has been the second cause of death worldwide, preceded by cardiovascular diseases only. The number of research groups focusing on the discovery of new drugs to treat cancer is growing and the aim is to look for more effective compounds that cause less severe side effects and do not suffer from therapeutic resistance. The metal complexes cisplatin and carboplatin are widely used in the chemotherapeutic treatment of various types of cancer, including triple-negative breast cancer (TNBC). Both compounds are essential in modern chemotherapy and continue to be the subject of research to optimize their therapeutic properties and minimize adverse effects. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) allows obtaining both quantitative data and information on the spatial distribution of elements in biological tissues and populations of single cells. In this work, the content of Pt and its distribution in TNBC MDA-MB-231 cells were determined via LA-ICP-MS analysis after incubation with different Pt-containing drugs. The quantitative analysis of single cells and the elemental maps revealing the distribution of Pt over and within the cells provide an enhanced insight into the potential mechanism of action of these Pt-containing drugs and their efficacy against TNBC.

An exploratory study of “large‐n” detrital zircon geochronology of the Book Cliffs, UT via rapid (3 s/analysis) U–Pb dating

AbstractDetrital zircon (DZ) U–Pb geochronology has improved the way geologists approach questions of sediment provenance and stratigraphic age. However, there is debate about what constitutes an appropriate sample size (i.e., the number of dates in a DZ sample, n), which depends on project objectives, sample complexity, and, critically, analytical budget. Additionally, there is ongoing concern about bias introduced by zircon grain size. We tested a recently developed rapid (3 s/analysis) data acquisition method by multicollector laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) that incorporates an automated selection routine and calculates two‐dimensional grain geometry from polished sample surfaces. Eleven samples were analysed from below and above the Late Cretaceous (Campanian) basal Castlegate unconformity of the Book Cliffs, Utah, in a down‐depositional‐dip transect including Price, Horse, Tusher, and Thompson canyons. 12,448 new concordant dates were generated during two measurement sessions. Results are consistent with recent studies suggesting there is no major provenance change and little time (1–2 Myr) represented across the unconformity. Grain size and sample size both exert a strong control on sample dissimilarity. Age distributions constructed from subsamples of large grains are systematically less similar to whole samples; age distributions composed of small grains are overall more similar to whole samples. As such, North American sediment sources that produce large grains such as the Grenville and Yavapi‐Mazatzal belts can bias age distributions if only large grains are analysed. A sample size of n = 100 is inadequate for characterizing age distributions as complex as those of the Book Cliffs, whereas a sample size of n = 300 provides good characterization. Sample size of n ≈ 1000 or more is unnecessary unless project objectives include scanning for subordinate age groups, such as when identifying the youngest grains for calculating a maximum depositional age (MDA). Dates used in MDA calculations acquired with rapid acquisition are best re‐analysed with longer LA‐ICP‐MS acquisition methods or isotope dilution thermal ionization mass spectrometry for increased accuracy and precision. We include new MATLAB code and open‐source software programs, DZpick and DZmda, for automated spot picking and calculating MDAs.

Polymerized ionic liquid Co-catalysts driving photocatalytic CO2 transformation.

Photocatalytic production of CO from CO2 has the potential for safe and atom-economic production of feedstock chemicals via in situ carbonylation chemistry. We developed novel ionic liquid-based polymeric materials through radical copolymerisation of 1-butyl-3-vinylimidazolium chloride and photocatalytically active Re- and Ru-complexes that serve as the CO2 reduction catalyst and photosensitiser, respectively. The crosslinked polymeric framework allows for the facile immobilisation of molecular organometallic complexes for use as heterogenised catalysts; moreover, the involved imidazolium core units co-catalyze the reduction of CO2 via covalent interaction. The ratio of sensitiser and catalyst was analysed by laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) and set in relation to results from photocatalytic experiments. Ultimately, the heterogenous polymeric framework showed high selectivity for CO formation on photocatalytic CO2 reduction with improved stability to the corresponding homogenous system.

Imaging of Subcellular Distribution of Platinum in Single Cells Using Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

Laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a well-established and sensitive analytical technique, which provides high-resolution imaging of endogenous elements, element tagged-markers, metal-containing nanoparticles, and metallodrugs within cells. Here we describe a protocol for imaging the subcellular distribution of platinum within A549 cells, following their incubation with the platinum-based anticancer agent, Oxaliplatin. We outline the essential steps in sample preparation and instrumental setup and discuss how the current generation of low-dispersion instruments facilitates new approaches to data acquisition and image processing. The protocol described herein can be easily adapted for other cell lines and metal-containing labeling agents.

Gadolinium Presence in Rat Skin: Assessment of Histopathologic Changes Associated with Small Fiber Neuropathy.

Background The presence of gadolinium traces in the skin after administration of gadolinium-based contrast agents (GBCAs) raised safety concerns regarding a potential association with small fiber neuropathy (SFN). Purpose To investigate signs of SFN in rat foot pads by quantification of the intraepidermal nerve fiber density (IENFD) after multiple GBCA administrations and to evaluate gadolinium concentration, chemical species, and clearance. Materials and Methods Fifty rats received eight intravenous injections of either gadodiamide, gadobutrol, gadoterate, gadoteridol (8 × 0.6 mmol per kilogram of body weight), or saline (1.2 mL per kilogram of body weight), within 2 weeks and were sacrificed 5 days or 5 weeks after the last injection. IENFD was determined with protein gene product (PGP) 9.5 immunofluorescent staining and blinded and automated image analysis. The gadolinium and GBCA concentrations were measured with inductively coupled plasma mass spectrometry (ICP-MS), laser ablation ICP-MS, and matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI). P values were calculated using linear contrasts of model analysis. Results The IENFD (measured as geometric mean [SD] and in number of nerve fibers per millimeter of epidermis) was not significantly altered after 5 days (saline, 8.4 [1.1]; gadobutrol, 9.7 [1.2]; gadoterate, 9.2 [1.2]; gadoteridol, 9.9 [1.3]; gadodiamide, 10.5 [1.2]) or 5 weeks (saline, 19.7 [1.4]; gadobutrol, 16.4 [1.6]; gadoterate, 14.3 [1.6]; gadoteridol, 22.2 [1.8]; gadodiamide, 17.9 [1.4]). Gadolinium skin concentrations were highest for gadodiamide after 5 days (16.0 nmol/g [1.1]) and 5 weeks (10.6 nmol/g [1.2], -33%). Macrocyclic agents were lower at 5 days (gadoteridol, 2.6 nmol/g [1.2]; gadobutrol, 2.7 nmol/g [1.1]; and gadoterate, 2.3 nmol/g [1.2]) and efficiently cleared after 5 weeks (gadoteridol, -95%; gadobutrol and gadoterate, -96%). The distribution of gadolinium and IENF did not visually overlap. For macrocyclic agents, gadolinium was found in sweat glands and confirmed to be intact chelate. Conclusion There were no signs of SFN in rat foot pads using multiple dosing regimens at two time points after administration of GBCAs. Macrocyclic GBCAs exhibited lower levels of gadolinium in the skin and were effectively eliminated within 5 weeks compared with linear gadodiamide, and intact macrocyclic GBCA was detected in sweat glands. © RSNA, 2024 Supplemental material is available for this article. See also the editorial by Clement in this issue.

A zircon LA-ICPMS reverse depth profiling analysis method and its geological application

A new LA-ICPMS analysis method for zircon U–Pb age and trace element composition and its geological application.

A comparison of calibration strategies for quantitative laser ablation ICP-mass spectrometry (LA-ICP-MS) analysis of fused catalyst samples

Alternative calibration approaches relying on either aqueous standard solutions or a single solid standard measured under different LA settings, were evaluated in the context of quantitative LA-ICP-MS bulk analysis of fused catalyst samples.

Integrated Experimental Phase Equilibria and Thermodynamic Modelling Research and Implementation in support of progress of process pyrometallurgy towards sustainability

Responding to the many sustainability challenges facing the metallurgical industry, we report progress that has been made on the development of predictive tools that can be applied to a wide range of technologies. The aim is to provide accurate, fundamentally-based thermodynamic tools that can be used by industry to improve process efficiencies, metal recoveries and productivities, and reduce energy requirements of pyrometallurgical systems. The program involves an integrated experimental and thermodynamic modelling research on phase equilibria in complex multi-component, multi-phase gas-slag-matte-speiss-metal-solids system with the Cu2O-PbO-ZnO-FeO-Fe2O3-CaO-Al2O3-MgO-SiO2-S major and As-Sn-Sb-Bi-Ag-Au-Ni-Co-Cr-Na minor elements. The experiments involve high temperature equilibration in controlled gas atmospheres, rapid quenching and direct measurement of equilibrium phase compositions with quantitative microanalytical techniques, including electron probe X-ray microanalysis and Laser Ablation ICP-MS. The thermodynamic modelling is undertaken using FactSage software package with advanced thermodynamic solution models. The continuing development of analytical and research methodologies has resulted in significant advances in predictive capability. Implementation of the results of fundamental studies involves ongoing collaboration of researchers and industry technologists, and the provision of advanced professional training. An overview of recent progress in research, implementation and applications in industrial practice will be presented in the paper.

Modes of occurrence of gallium in Al-Ga-rich coals in the Jungar Coalfield, Ordos Basin, China: Insights from LA-ICP-MS data

Owing to the concern about supply of Ga, it has been attracted much attention for the modes of occurrence of Ga in Al-Ga-rich coal-hosted deposits. However, the modes of occurrence of Ga in coal were mainly investigated using indirect methods, which may cause uncertainties. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot and mapping analysis were used to directly characterize the concentration of Ga within the host minerals including kaolinite and boehmite, and to investigate the distribution of Ga in organic matter in the Carboniferous Al-Ga-rich coal from the Haerwusu Mine in the Jungar Coalfield of the Ordos Basin, North China. Microscope observation and scanning electron microscope - energy dispersive spectrometry (SEM-EDS) analysis were performed, along with petrographical and mineralogical investigations. Eight types of kaolinite and three types of boehmite particles from coal, erosional-sourced mudstone, and tonstein were identified, classified, and selected for the determination of in-situ elemental compositions.The results showed that the concentration of Ga in the selected minerals varies, with the following order from highest to lowest: colloidal boehmite (90.38 ppm), low-Al (Al2O3/SiO2) clastic kaolinite (84.67 ppm), high-Al clastic kaolinite (55.49 ppm), Na-bearing kaolinite (49.94 ppm), fine-grained boehmite (47.13 ppm), high-Al cryptocrystalline kaolinite (40.25 ppm), low-Al cryptocrystalline kaolinite (38.78 ppm), and low-Al vermicular kaolinite (29.67 ppm), high-Al vermicular kaolinite (28.37 ppm), K-bearing kaolinite (19.44 ppm), and clastic boehmite and cell-filling kaolinite (below detection limit). LA-ICP-MS mapping demonstrated that a certain proportion of Ga could be associated with organic matter, concentrating on vitrinite. Notably, the concentration of Ga in clastic kaolinite and colloidal boehmite was found to be substantially higher compared to the whole-rock coal and erosional-sourced mudstone samples, indicative of their dominant host minerals for Ga. Conversely, the concentration of Ga in K-bearing or Na-bearing kaolinite which had experienced transformation from primary kaolinite is much lower than that in clastic kaolinite, while the concentration of Ga in fine-grained boehmite, which had altered from kaolinite, surpassed that of its corresponding kaolinite layer. These findings suggest that gallium could have undergone migration during the evolution or alteration of clay minerals.

Mineralogy and Geochemical Characteristics of Scheelite Deposit at Xuebaoding in Pingwu, Sichuan Province, China

Featuring subtle lithological alterations in the host rocks and containing colossal gemstone crystals, the scheelite deposit at Xuebaoding in the Pingwu region of Sichuan Province exhibits characteristics typical of a vein-like hydrothermal-type deposit. The scheelite from the Xuebaoding region is renowned for its high saturation of color, perfect crystal shape, and pure color. In this study, its crystal structure and mineralogical, geochemical, and in situ Sr-Nd isotope characteristics are all systematically characterized. Our objective is to determine the source of ore-forming materials, the timing of the mineralization, and the chemical composition of scheelite, including major elements, trace elements, and rare earths elements (REE). The scheelite samples were analyzed with a variety of methods such as polarizing microscopy, X-ray powder diffraction (XRD), X-ray fluorescence spectrometry (XRF), electron probing, and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In addition, conventional gemological tests were performed using instruments including gemstone microscopes, GI-UVB ultraviolet fluorescent lamps, grating spectroscopy, etc. The results demonstrate that scheelite exhibits a high refractive index, excellent crystallinity, and a granular structure. Clear color bands and ring structures are observed within the minerals, accompanied by interference colors of light blue, blue, and yellow. Additionally, the mineral components are relatively concentrated, with muscovite and illite serving as accessory minerals. Furthermore, the chemical composition of scheelite reveals a WO3/CaO mass ratio that approaches or exceeds the ideal value. Moreover, it exhibits a wide range of variations in total rare earth element (∑REE) content, which is characterized by an enrichment of light rare earths (LREE), significant negative Eu anomalies, and insignificant Ce anomalies. In addition, the metallogenic formation of scheelite can be estimated to have occurred during the Toarcian stage in the Lower Jurassic Epoch period, approximately 183 Ma. The study further revealed that A-type granite serves as the genesis type of scheelite, with most of the ore-forming materials originating from the upper crust and a few derived from younger crustal sources.

Ore genesis of the Tieshajie Cu deposit: Implications for Cu mineralization in the Qin-Hang Metallogenic Belt, South China

The Tieshajie Cu deposit, located in the northeastern part of the Qin-Hang Metallogenic Belt (QHMB), South China, has long been regarded as a representative Meso-Neoproterozoic volcanogenic massive sulfide (VMS) deposit. Here we present a hydrothermal titanite U-Pb age, Re-Os and in-situ S-Cu isotope data for chalcopyrite to constrain the timing and ore genesis of the Tieshajie deposit. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb dating of titanite from the disseminated Cu ore yielded a weighted mean 206Pb/238U age of 160.1 ± 4.4 Ma. Chalcopyrite from different ore types has low 187Os/188Os (0.85–3.60) and 187Re/188Os (46.1–614.0) ratios, combined with initial 187Os/188Os (0.74–2.00), excluding a mantle source. A Re-Os isochron age (188 ± 30 Ma) for five chalcopyrite samples is consistent with the titanite U-Pb age within errors. Moreover, the variations in Cu isotope compositions (δ65Cu: −1.13 to +0.12 ‰) and δ34S values (+3.8 to +7.7 ‰) of chalcopyrite are inconsistent with those reported from the ancient VMS deposits in previous studies. Therefore, our results are indicative of a Late Jurassic magmatic-hydrothermal origin instead of a VMS origin for the Tieshajie deposit. In combination with previous studies, we propose that the Tieshajie Cu deposit belongs to the distal part of the Mid-Late Jurassic (170–150 Ma) porphyry-skarn Cu mineralization event in the QHMB, likely triggered by the subduction of the Paleo-Pacific plate during the Late Mesozoic. This study also has new insights into the genesis of Cu mineralization in the QHMB and further provides implications for future exploration.

Migration and exchange of rare earth elements between phosphate and iron manganese phase: A case study from fish tooth-bearing nodules

Deep-sea sediments that are widely distributed in the Pacific Ocean could be an important future resource for rare earth element (REE) and yttrium (REY) due to their high concentrations of REY. Bioapatite fossils as well as Fe-Mn (oxyhydr) oxides (e.g., micronodules) are recognized as significant carriers of REY in deep-sea sediments. Notably, bioapatite fossils, account for more than 60% of the total REY content in bulk sediments, underscoring their significance as primary host for REY. However, the mechanisms of REY enrichments, variations in Ce anomalies, and REY substitution in bioapatite fossils remain under explained. In this study, we performed detailed in situ geochemical, isotope geochemical and chemical imaging analyses on fish tooth-bearing nodules.Our results indicate that fish teeth are mainly composed of Ca, P, F and Na, which accounting for over 95 % of the total composition of these teeth. On the one hand, the concentrations of Ca, P and F exhibit strong positive correlations with each other: their contents increase from the inside to the outside of the dentine shell. On the other hand, Na concentration display a different trend that the highest concentration is found in the center part of shark teeth. Despite the theoretical nearly absence of seawater as potential transport media, REYs migrated from the ferromanganese oxides phase to phosphate phase, and their contents decreased from inside layers to outside layers of dentine. During the long-term substitution processes in geological time, a portion of Ce3+ would be oxidized into immobile Ce4+ under oxic conditions, resulting in less incorporation of Ce3+ into the outer layers of dentine compared to other REY3+. As a consequence, stronger negative Ce anomalies were observed in the inside layers than in outside layers of dentine. The laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) mapping together with the in-situ geochemistry results indicate the negligible participation of Si in REY substitution, whereas Na exhibits a pronounced preference for substituting Ca2+ with REY3+. Therefore, we propose the following substitution scheme for incorporating REY into the crystal lattice of fish teeth: REY3+ + Na+↔ 2Ca2+. Our study clarified the fraction of REY during their migration from the Fe-Mn phase to the phosphate phase, and also contributes to a deeper understanding of the REY enrichment mechanism in pelagic sediments.

U-Pb geochronology and petrography of Neoproterozoic to early Cambrian volcanic rocks in basement crustal terranes beneath the deep-water Gulf of Mexico

Abstract Though the Gulf of Mexico has been studied for more than a century, the lithology, age, and origin of the basement crustal terranes remain poorly understood. New U-Pb zircon ages of a volcanic sample in the DeSoto Canyon 535 #1 Raptor well were obtained by in situ laser-ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) and resulted in a crystallization age of 509 ± 23 Ma, indicating the crustal terrane beneath the northeastern Gulf of Mexico is likely of peri-Gondwanan affinity. This basement may be associated with the felsic volcanism related to Neoproterozoic to Cambrian subduction along the supercontinent’s western margin. This subduction-related volcanism likely represents the last pulses of magmatic activity before the west coast of Gondwana transitioned into a passive margin ca. 500 Ma. The data presented here for the DeSoto Canyon 535 #1 Raptor trachyte represent the oldest radiometrically dated evidence of volcanism in the present-day deep-water Gulf of Mexico.

Imaging of Light-Enhanced Extracellular Vesicle-Mediated Delivery of Oxaliplatin to Colorectal Cancer Cells via Laser Ablation, Inductively Coupled Plasma Mass Spectrometry.

Extracellular vesicles (EVs) are lipid bilayer structures released by all cells that mediate cell-to-cell communication via the transfer of bioactive cargo. Because of the natural origin of EVs, their efficient uptake by recipient cells, capacity to stabilize and transport biomolecules and their potential for cell/tissue targeting and preferential uptake by cancer cells, they have enormous potential for bioengineering into improved and targeted drug delivery systems. In this work, we investigated the use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a tool to measure the loading of platinum-based chemotherapeutic agents. The EV loading of oxaliplatin via co-incubation was demonstrated, and LA-ICP-MS imaging showed greater efficiency of delivery to colorectal cancer cells compared to free oxaliplatin, leading to enhanced cytotoxic effect. Further, the impact of EV co-loading with a porphyrin (C5SHU, known as 'C5') photosensitizer on oxaliplatin delivery was assessed. Fluorescence analysis using nano-flow cytometry showed dose-dependent EV loading as well as a trend towards the loading of larger particles. Exposure of OXA-C5-EV-treated colorectal cancer cells to light indicated that delivery was enhanced by both light exposure and porphyrins, with a synergistic effect on cell viability observed between oxaliplatin, EVs and light exposure after the delivery of the co-loaded EVs. In summary, this work demonstrates the utility of LA-ICP-MS and mass spectrometry imaging in assessing the loading efficiency and cellular delivery of platinum-based therapeutics, which would also be suitable for agents containing other elements, confirms that EVs are more efficient at delivery compared to free drugs, and describes the use of light exposure in optimizing delivery and therapeutic effects of EV-mediated drug delivery both in combination and independently of porphyrin-based photosensitizers.

Multi-phase quantitative compositional mapping by LA-ICP-MS: Analytical approach and data reduction protocol implemented in XMapTools

Mapping of trace element signatures is an expanding tool in geoscience and material sciences, which allows the study of solid materials, and processes that may not be captured by major elements. Developments in laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICP-MS) capabilities in the last decade now provide the necessary spatial resolution for in situ element mapping. The acquisition of two-dimensional, fully quantitative and geologically meaningful data with LA-ICP-MS is still a challenging task, and a particular obstacle is the calibration of inhomogeneous phases, such as chemically zoned minerals. This work presents a novel approach to data reduction and image generation for multi-element mapping employing LA-ICP- quadrupole MS (LA-ICP-QMS), implemented in the free and open-source software XMapTools. Three geological applications are presented to illustrate the benefits of the procedures. Garnet from an eclogitic sample (Lato Hills, Togo) and plagioclase, K-feldspar, biotite from a migmatite sample (El Oro Complex, Ecuador) were mapped multiple times at different spatial resolutions to test the calibration quality and chemical detection capabilities. Rutile in a metapelite sample (Val Malenco, Italian Alps) was mapped, and Zr-in-rutile thermometry shows a temperature range of 510 to 550 °C within a single grain. The accuracy of the LA-ICP-MS method was verified by comparison with zoned major and minor element maps (garnet, plagioclase) and Ti-in-biotite geothermometry maps obtained by electron probe microanalysis (EPMA). A spatial resolution of up to 5 μm is achieved with LA-ICP-QMS, which is similar to the resolution reported for LA-ICP time-of-flight mass spectrometry (LA-ICP-TOFMS), albeit at significantly lower acquisition speed. Maps with lower spatial resolution offer better chemical detection power as demonstrated by lower per-pixel limit of detection (LOD) map calculation. Moreover, such maps are also recorded faster. The pixel allocation strategy and the instrumental conditions also have a direct impact on map quality. We recommend that maps are interpolated to square pixels, where a pixel consists of multiple sweeps to gain an improved detection power. Benchmarks using an emulated LA-ICP-MS mapping show that the spot size, together with scan direction, can lead to a shift in composition depending on the feature size of chemical patterns. This is verified by mapping a thin 10 μm annulus in garnet visible in REE and such compositional shifts can have a significant impact on e.g., diffusion modelling. The new software solution provides a multi-standard and variable composition calibration of LA-ICP-MS maps with single pixel LOD filtering at 95% confidence, allowing the user to quantify inhomogeneous materials of major and trace elements simultaneously with improved accuracy.

Trace Element Composition of Placer Gold Across the Okanagan Fault, Kelowna, British Columbia, Canada

For 100 years, placer gold has been important to the settlement, economic development, and, recently, recreational geology of the Kelowna, British Columbia, area. It is best-known to occur in modern-day, Mission Creek and Lambly Creek sedimentary rocks, as well as a paleoplacer occurrence in Miocene sediments of the historical Winfield mine. The Mission Creek and Winfield localities are east of the west-dipping, low-angle, normal Okanagan Fault, which has been active since the Eocene. Lambly Creek is west of the fault. Late Paleozoic to Eocene igneous and metasedimentary rocks occur in the Lambly Creek catchment but Eocene gneiss units, unroofed by the fault, occur on the Okanagan Valley’s east side. This study tests the hypothesis that native placer gold compositions vary across the Okanagan Fault reflecting different sources and histories for the gold. A modest number of Au and Ag analyses (23 analyses) in usefully representative placer gold samples were determined on a scanning electron microscope with an energy dispersive spectrometer (SEM-EDS). Spots analyzed for Au and Ag were also analyzed for 19 trace elements using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Mercury was semi-quantitatively determined in ‘unknown’ gold grains by first estimating its concentration (~3.69 ppm) in the AuRM2 external standard. Proportions of Au:Ag:Cu in grain cores indicate all the gold came from mesothermal/hypogene or possibly Au porphyry bedrock deposits though primary signatures may have been obscured by metamorphism or weathering. Winfield and Mission Creek grains tend to have higher siderophile Fe, Ni, Pd and Pt and chalcophile elements As, Se, Te, Hg, Pb and Bi but lower Cu and Sb concentrations than Lambly Creek gold. Mercury is distinctly higher in Winfield and Mission Creek gold than in Lambly Creek gold from the west side of the valley; the element appears particularly useful for ‘fingerprinting’ gold. Lambly Creek gold compositions indicate derivation from two orogenic/hypogene sources from greenstone and plutonic/hydrothermal rocks present in the catchment area. Modern day Mission Creek and Miocene paleoplacer Winfield grains have a similar hypogene trace element signature but there are no known local bedrock gold sources. The Mission Creek and Winfield gold grain cores are surrounded by < 10 µm, Au-rich, Ag- and trace element-poor, rims. Lambly Creek grains lack such rims. The Au-rich rims on modern day Mission Creek and Miocene Winfield gold may reflect prolonged near-surface exposure with surficial electrochemical dissolution of hypogene trace elements or the biological precipitation of gold. Low Ag and red colouration on the surface of grains support the biological precipitation hypothesis. The shared trace element signature, together with the Au-rich rims indicate that modern day placer gold in Mission Creek was multiply reworked from Miocene paleoplacers similar to the Winfield occurrence as a result of uplift and erosion of rocks on the east side of Okanagan Fault.

Mapping Phosphorus Availability in Soil at a Large Scale and High Resolution Using Novel Diffusive Gradients in Thin Films Designed for X-ray Fluorescence Microscopy.

A novel binding layer (BL) as part of the diffusive gradients in thin films (DGT) technique was developed for the two-dimensional visualization and quantification of labile phosphorus (P) in soils. This BL was designed for P detection by synchrotron-based X-ray fluorescence microscopy (XFM). It differs from the conventional DGT BL as the hydrogel is eliminated to overcome the issue that the fluorescent X-rays of P are detected mainly from shallow sample depths. Instead, the novel design is based on a polyimide film (Kapton) onto which finely powdered titanium dioxide-based P binding agent (Metsorb) was applied, resulting in superficial P binding only. The BL was successfully used for quantitative visualization of P diffusion from three conventional P fertilizers applied to two soils. On a selection of samples, XFM analysis was confirmed by quantitative laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The XFM method detected significant differences in labile P concentrations and P diffusion zone radii with the P fertilizer incubation, which were explained by soil and fertilizer properties. This development paves the way for fast XFM analysis of P on large DGT BLs to investigate in situ diffusion of labile P from fertilizers and to visualize large-scale P cycling processes at high spatial resolution.

Microchemistry of Single Hair Strands Below and Above the Scalp: Impacts of External Contamination on Cuticle and Cortex Layers.

External contamination of hair is the most significant challenge to it becoming an accepted matrix for monitoring endogenous metal exposure and nutritional deficiency. Here we use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to quantify elemental concentrations in hair strands below and above the scalp in the cuticle and cortex layers to determine the extent of external contamination in a reference population. Evidence of hair strand contamination occurred for barium, calcium, iron, magnesium, and strontium in both the outer cuticle and the inner cortex layers, with increasing concentrations from root to tip. Aluminum, boron, copper, lead, and manganese showed significant contamination in the cuticle layer only, suggesting some protection of the inner cortex. Phosphorus and potassium decreased outside the scalp suggesting loss by washing, while chromium, mercury, selenium, sodium, titanium, and zinc showed no evidence of loss or external contamination above the scalp. The results clearly show that for most elements, hair chemistry above the scalp is unreliable for use in interpretation of endogenous exposures or deficiencies, and that the below-scalp portion provides a more accurate monitoring tool. This is the first paper to provide a reference range of elemental hair chemistry that is not impacted by the external environment.

Zircon and cassiterite U-Pb geochronology and petrochemical characteristics of early Tertiary tin mineralization at Mayo Darlé, Cameroon Volcanic Line

Tin mineralization at Mayo-Darlé in the Cameroon Volcanic Line is associated with highly evolved anorogenic ferroan granite magmatism with a pervasive hydrothermal overprint. Mineralization occurs as cassiterite-quartz-muscovite stockwork and disseminated in quartz-mica and quartz-topaz greisen in low-Ca alkali feldspar granite with a composition near the 1 kbar haplogranitic thermal minimum. The trace element composition of zircon indicates elevated temperature (880 ± 55 °C) and very low oxidation state below the quartz-fayalite-magnetite buffer. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) identifies a partly disturbed U-Pb system for igneous zircon (U and Th contents >1000 ppm) but defines Tera-Wasserburg concordia ages and common-lead-corrected weighted 206Pb/238U ages of about 54 Ma, similar to a previous 87Rb/86Sr vs 87Sr/86Sr regression with a date of 56.1 ± 1.7 Ma (MSWD = 58; n = 9) and an initial 87Sr/86Sr ratio of 0.7085 ± 0.0035 (2 s). Hydrothermal cassiterite gives a pooled LA-ICPMS Tera-Wasserburg concordia age of 56.7 ± 0.6 Ma on two samples (each about 20 points, MSWD = 0.54 and 1.3). These new age data define a period of early Cenozoic intraplate calc-alkalic felsic magmatism as a precursor to abundant Oligocene to Recent alkali basalt volcanism along the Cameroon Volcanic Line. Geochemical and Sr–Nd–Hf isotopic data suggest that the granitic rocks from Mayo Darlé were largely derived by partial melting of Mesoproterozoic basement and modified by strong differentiation, all likely powered by heat (and possibly fluids) from the mantle. The Tertiary age of the rare-metal magmatism sets this system apart from the widespread Late Neoproterozoic to Early Paleozoic rare-metal pegmatites and granites in the Pan-African collisional belts of Africa, and also from the anorogenic Mesozoic ring complexes in Central Nigeria.