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There are many processes that affect the measured concentration of elements determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Depending on the element of interest, a range of corrections are required to account for sensitivity drift and downhole effects, as well as other sources of inaccuracy. Here, we present a new method of calibrating LA-ICP-MS measurements taking into consideration time-dependent sensitivity changes to produce a three-dimensional calibration surface through time. These 3D calibration surfaces result in up to 20% improvements in our example dataset for some elements. To ensure calibration surfaces that are created using multiple reference materials are not degraded by matrix effects a median yield correction factor is determined relative to a primary reference material. We also introduce sensitivity modelling for elements without accepted values or where interferences may affect calibration. In addition to the correction of drift, we further demonstrate a correction for downhole fractionation effects can improve the precision of spot analyses by up to 20% in our example dataset. A flexible solution to the sum normalisation approach is briefly introduced for calibration of multi-phase samples using different calibration parameters, along with a residual correction based on compositional affinity to a reference material. Combined, these new methodologies can improve the accuracy and precision of concentration determinations by LA-ICP-MS in a wide variety of applications. [ABSTRACT FROM AUTHOR]

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis of μ-droplets is becoming an attractive alternative for detecting and quantifying elements in biological samples. With minimal sample preparation required and detection limits comparable to solution nebulisation ICP-MS, μ-droplets have substantial advantages over traditional elemental detection, particularly for low volumes, such as aliquots taken from samples required for multiple independent biochemical assays, or fluids and tissues where elements of interest exist at native concentrations not suited to the necessary dilution steps required for solution nebulisation ICP-MS. However, the characteristics of μ-droplet residue deposition are heavily dependent on the matrix, and potential effects on signal suppression or enhancement have not been fully characterised. We present a validated and flexible high-throughput method for quantification of elements in μ-droplets using LA-ICP-MS imaging and matrix-matched external calibrants. Imaging the entire μ-droplet area removes analytical uncertainty arising from the often-heterogenous distribution when compared to radial or bisecting line scans that capture only a small portion of the droplet residue. We examined the effects of common matrices found in a standard biochemistry workflow, including native protein and salt contents, as well as reagents used in typical preparation steps for concurrent biochemical assays, such as total protein quantification and enzyme activity assays. We found that matrix composition results in systemic, concentration-dependent signal enhancement and suppression for carbon, whereas high sodium content has a specific space-charge-like suppression effect on high masses. We confirmed the accuracy of our method using both a certified serum standard (Seronorm™ L1) and independent measurements of analysed samples by solution nebulisation ICP-MS, then tested the specificity and reproducibility by examining spinal cord tissue homogenates from SOD1-G93A transgenic mice with a known molecular phenotype of increased copper- and zinc-binding superoxide dismutase-1 expression and altered copper-to-zinc stoichiometry. The method presented is rapid and transferable to multiple other biological matrices and allows high-throughput analysis of low-volume samples with sensitivity comparable to standard solution nebulisation ICP-MS protocols.ᅟ [ABSTRACT FROM AUTHOR]

The double-spike approach for correction of instrumental mass bias in mass spectrometry data is well established. However, there is very little consistency within the scientific community in terms of double-spike data reduction. Double-spike solutions require computer calculation, using either geometric or algebraic approaches, and are often performed using spreadsheet calculations that vary from group to group and between isotope systems. Here, we present IsoSpike, a generalised computer procedure for the processing of double-spike mass spectrometry data, built as an add-on for the Iolite data-reduction package (). Use of this software permits visualisation of mass spectrometry data in a time window, and rigorous treatment and screening of data. Additionally, IsoSpike uses an integration-by-integration approach where the double-spike calculations are performed on every integration within an analysis, providing straightforward quantification of uncertainties on double-spike-corrected isotope ratios. The advantages of this approach over traditional methods are discussed here. Platinum stable isotope data are presented as an example data set, although the procedure is applicable to any double-spike system. IsoSpike is freely available from . [ABSTRACT FROM AUTHOR]

Here, we present an approach to laser ablation ICP- MS mapping of multi-phase assemblages that permits the use of different internal standard elements, concentration values and reference materials for each mineral. In this way, we obtain not only broad pictures of elemental distributions within samples but can also extract high accuracy concentration data for any user-selected region. This is accomplished by assigning regions of an image to corresponding mineral phases on a pixel-by-pixel basis. In this way, accurate trace element concentrations can be determined for each mineral phase, despite potential variations in their ablation characteristics. We present an example where elemental maps are constructed from ablation of a gabbroic sample that includes the phases apatite, amphibole and plagioclase. This work represents an important first step towards development of a method to produce highly accurate LA- ICP- MS elemental maps of multi-phase samples. [ABSTRACT FROM AUTHOR]

We present a novel approach to creating compositional images using a module created for use with the freely distributed software package Iolite. The module creates images by synchronising the state of the laser (e.g., whether the laser is firing or not) and the position on the sample, which are recorded in laser log files, with concurrently collected mass spectrometer data. When these two data sources are synchronised, mass spectrometer data which are recorded temporally can then be displayed versus ablation position (i.e., spatially). Each mass spectrometer reading is then plotted as a circular spot representing the size of the area ablated. This approach has many advantages. CellSpace takes advantage of Iolite's ability to manipulate data from various mass spectrometers and to reduce data of different types. Laser ablation data can be plotted over other images, such as those produced by scanning electron microscopes, where the image has been transformed into cell coordinates using third party software. This allows the analyst to visualise laser ablation data in context and to correlate sample data from multiple sources and/or techniques. The code also has the advantage of averaging data spatially, rather than just temporally, and faithfully presents the data as a corresponding laser spot, rather than a simple rectangular pixel. Here we provide an example of a fish otolith, where trace element concentrations and Sr-isotopic compositions are overlain on microscope images, providing information on migration patterns that are applicable to population studies and fisheries conservation. [ABSTRACT FROM AUTHOR]

Abstract: It is widely acknowledged that olivine-hosted melt inclusions retain compositional information unavailable from the study of bulk-rock samples alone. Whether or not the compositions of melt inclusions are truly representative of geologically significant melt bodies has, however, been called into question; isotopic data are critical to resolving this debate but the rare existing data are contradictory. Previous studies of Pb isotope ratios suggest that large compositional variations are preserved by melt inclusions whereas Sr isotope data apparently do not. A new and extensive laser ablation Pb-isotope database is presented here and displays a degree of isotopic heterogeneity in key samples from Mangaia and the Pitcairn seamounts significantly less than previously reported. More than 95% of the inclusions analysed, including results for the low abundance Pb-isotope, 204Pb, which has previously proven difficult to measure, are within error of bulk-rock analyses from these locations. Trace element measurements on two inclusions of different isotopic character from the Pitcairn Seamounts are closely similar to each other, and do not easily support models in which melt inclusions from this locality represent mixing between the Pitcairn mantle plume and the local MORB magmas or lithosphere. Instead, a second component, likely derived from within the plume, is required to explain the isotope and trace element variations observed. In terms of isotopic compositions then, melt inclusions may in most cases be representative of geochemical conditions prevailing within the magmatic plumbing system. The range of isotopic compositions found in a single sample likely includes the composition of the transporting melt (groundmass of the rock) and compositions previously trapped in crystals in the magmatic plumbing system. [Copyright &y& Elsevier]

The copper compound CuII(atsm) has progressed to phase 2/3 testing for treatment of the neurodegenerative disease amyotrophic lateral sclerosis (ALS). CuII(atsm) is neuroprotective in mutant SOD1 mouse models of ALS where its activity is ascribed in part to improving availability of essential copper. However, SOD1 mutations cause only ~ 2% of ALS cases and therapeutic relevance of copper availability in sporadic ALS is unresolved. Herein we assessed spinal cord tissue from human cases of sporadic ALS for copper-related changes. We found that when compared to control cases the natural distribution of spinal cord copper was disrupted in sporadic ALS. A standout feature was decreased copper levels in the ventral grey matter, the primary anatomical site of neuronal loss in ALS. Altered expression of genes involved in copper handling indicated disrupted copper availability, and this was evident in decreased copper-dependent ferroxidase activity despite increased abundance of the ferroxidases ceruloplasmin and hephaestin. Mice expressing mutant SOD1 recapitulate salient features of ALS and the unsatiated requirement for copper in these mice is a biochemical target for CuII(atsm). Our results from human spinal cord indicate a therapeutic mechanism of action for CuII(atsm) involving copper availability may also be pertinent to sporadic cases of ALS. [ABSTRACT FROM AUTHOR]

Background: Ferroptosis is a form of regulated cell death characterised by lipid peroxidation as the terminal endpoint and a requirement for iron. Although it protects against cancer and infection, ferroptosis is also implicated in causing neuronal death in degenerative diseases of the central nervous system (CNS). The precise role for ferroptosis in causing neuronal death is yet to be fully resolved. Methods: To elucidate the role of ferroptosis in neuronal death we utilised co-culture and conditioned medium transfer experiments involving microglia, astrocytes and neurones. We ratified clinical significance of our cell culture findings via assessment of human CNS tissue from cases of the fatal, paralysing neurodegenerative condition of amyotrophic lateral sclerosis (ALS). We utilised the SOD1G37R mouse model of ALS and a CNS-permeant ferroptosis inhibitor to verify pharmacological significance in vivo. Results: We found that sublethal ferroptotic stress selectively affecting microglia triggers an inflammatory cascade that results in non-cell autonomous neuronal death. Central to this cascade is the conversion of astrocytes to a neurotoxic state. We show that spinal cord tissue from human cases of ALS exhibits a signature of ferroptosis that encompasses atomic, molecular and biochemical features. Further, we show the molecular correlation between ferroptosis and neurotoxic astrocytes evident in human ALS-affected spinal cord is recapitulated in the SOD1G37R mouse model where treatment with a CNS-permeant ferroptosis inhibitor, CuII(atsm), ameliorated these markers and was neuroprotective. Conclusions: By showing that microglia responding to sublethal ferroptotic stress culminates in non-cell autonomous neuronal death, our results implicate microglial ferroptotic stress as a rectifiable cause of neuronal death in neurodegenerative disease. As ferroptosis is currently primarily regarded as an intrinsic cell death phenomenon, these results introduce an entirely new pathophysiological role for ferroptosis in disease. [ABSTRACT FROM AUTHOR]

A step-change in the utility of elemental imaging in the biological sciences can be achieved by the integration of quantitative elemental distributions with structural information, allowing novel insights into how tissue development is associated with a dynamic chemical environment. To demonstrate this potential, here we construct a 3D correlative map of biometal distribution and skeletal growth for the first time in a complex organism – in a mouse embryo at developmental stage E14. We achieved this by registering laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data to micro-computerized tomography (μCT) imagery using endogenous fiducial markers. LA-ICP-MS compositional maps of Rb were used as fiducial markers of dense regions in the micro-CT dataset (e.g. skeletal structure). Results of image registration showed high spatial correlation between both datasets which improved with increasing contrast of the micro-CT images. When coupled with recent advances in analytical instrumentation promoting rapid LA-ICP-MS scanning, this technique promises an enhanced understanding of development in complex biological systems without the need for chemical pre-treatment. [ABSTRACT FROM AUTHOR]

Laser ablation tandem mass spectrometry is a burgeoning field for in situ Rb‐Sr geochronology. Here, we determined simultaneous isotope ratios of 87Sr/86Sr and 87Rb/86Sr in metamorphic biotite from western Maine, using an ESL™ imageGEO™193 excimer laser ablation system coupled to a Thermo Scientific™ Neoma™ MC‐ICP‐MS/MS. Measurements were made on Faraday cups with Rb+ at mass 87; Sr isotopes were reacted with SF6 gas and measured as SrF+ at masses 103–107. Twenty‐two laser spots in biotite from a single sample yield a "traditional" Rb‐Sr isochron date of 289 ± 6 Ma. Time‐resolved signals reveal significant zoning in 87Sr/86Sr and 87Rb/86Sr within single spot analyses, which were used to construct single spot isochrons. Individual laser spots contain multiple isochronous subpopulations; some spots contain up to three distinct Rb‐Sr isochrons that are decoupled from variations in Rb/Sr. Thirty‐five isochron dates were determined using this "sub‐spot" approach, with 87Sr/86Sr intercepts that systematically vary with Rb‐Sr date; two‐point isochrons were calculated for individual integrations (n = 780) based on these variable intercepts. Both methods yield age peaks at 303, 270 and 240 Ma. These data suggest that the Rb‐Sr system has the potential to record multiple heating, cooling or fluid‐alteration events spanning ~ 100 My within small domains in single biotite crystals. [ABSTRACT FROM AUTHOR]

Laser ablation multi‐collector mass spectrometry (LA‐MC‐ICP‐MS) has emerged as the technique of choice for in situ measurements of Sr isotopes in geological minerals. However, the method poses analytical challenges and there is no widely adopted standardised approach to collecting these data or correcting the numerous potential isobaric inferences. Here, we outline practical analytical procedures and data reduction strategies to help establish a consistent framework for collecting and correcting Sr isotope measurements in geological materials by LA‐MC‐ICP‐MS. We characterise a new set of plagioclase reference materials, which are available for distribution to the community, and present a new data reduction scheme for the Iolite software package to correct isobaric interferences for different materials and analytical conditions. Our tests show that a combination of Kr‐baseline subtraction, Rb‐peak‐stripping using βRb derived from a bracketing glass reference material, and a CaCa or CaAr correction for plagioclase and CaCa or CaAr + REE2+ correction for rock glasses, yields the most accurate and precise 87Sr/86Sr measurements for these materials. Using the analytical and correction procedures outlined herein, spot analyses using a beam diameter of 100 μm or rastering with a 50–65 μm diameter beam can readily achieve < 100 ppm 2SE repeatability ("internal") precision for 87Sr/86Sr measurements for materials with < 1000 μg g‐1 Sr. [ABSTRACT FROM AUTHOR]

[Display omitted] • Established an analytical approach for high-throughput characterization of geological samples to identify, presence, form, size, and isotopic characterization of inclusions. • LIBS screening followed by LA-ICP-MS analysis resulted in a time savings of ∼ 95 % or more equating to days of saved analytical time. • A new particle/inclusion tool within the iolite 4 software was used to more accurately determine the isotopic distribution of inclusions. • The methods developed here are amenable to various nuclear and geological related applications. The work presented herein employs two laser-based analytical techniques (laser-induced breakdown spectroscopy (LIBS) and laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS)) to spatially determine the elemental and isotopic composition of uranium bearing minerals. Uniquely, this work leverages the high-speed applicability of LIBS to "screen" the sample(s) for their elemental constituents. After determining the location of the uranium inclusions (via LIBS), high-resolution LA-ICP-MS was employed to further characterize the inclusions. The high-resolution (sub-µm) capabilities of LA-ICP-MS were able to extract important information from the uranium minerals including discerning its chemical form (e.g., finchite from carnotite, Sr- and K-bearing uranyl vanadates, respectively) as well as their 235U/238U isotopic composition. This approach, LIBS followed by LA-ICP-MS, significantly reduces the analysis time (∼95 %) in comparison to employing a LA-ICP-MS only approach. Furthermore, this work presented a novel approach to analyzing inclusions via a particle/inclusion analysis tool which is commercially available within the iolite 4 software. This tool allowed for a more accurate characterization of the isotopic distribution of the inclusions, as well as allowing for rapid sizing of the inclusions. This analytical approach could readily be applied to other sample types in which the target species (e.g., µm-sized inclusions) are embedded in complex matrices (e.g., cm-sized samples). [ABSTRACT FROM AUTHOR]

The trace-element geochemistry of speleothems is becoming increasingly used for reconstructing palaeoclimate, with a particular emphasis on elements whose concentrations vary according to hydrological conditions at the cave site (e.g. Mg, Sr, Ba and U). An important step in interpreting trace-element abundances is understanding the underlying processes of their incorporation. This includes quantifying the fractionation between the solution and speleothem carbonate via partition coefficients (where the partitioning (D) of element X (D X) is the molar ratio [X/Ca] in the calcite divided by the molar ratio [X/Ca] in the parent water) and evaluating the degree of spatial variability across time-constant speleothem layers. Previous studies of how these elements are incorporated into speleothems have focused primarily on stalagmites and their source waters in natural cave settings, or have used synthetic solutions under cave-analogue laboratory conditions to produce similar dripstones. However, dripstones are not the only speleothem types capable of yielding useful palaeoclimate information. In this study, we investigate the incorporation of Mg, Sr, Ba and U into a subaqueous calcite speleothem (CD3) growing in a natural cave pool in Italy. Pool-water measurements extending back 15 years reveal a remarkably stable geochemical environment owing to the deep cave setting, enabling the calculation of precise solution [X/Ca]. We determine the trace element variability of 'modern' subaqueous calcite from a drill core taken through CD3 to derive D Mg , D Sr , D Ba and D U then compare these with published cave, cave-analogue and seawater-analogue studies. The D Mg for CD3 is anomalously high (0.042 ± 0.002) compared to previous estimates at similar temperatures (∼8 °C). The D Sr (0.100 ± 0.007) is similar to previously reported values, but data from this study as well as those from Tremaine and Froelich (2013) and Day and Henderson (2013) suggest that [Na/Sr] might play an important role in Sr incorporation through the potential for Na to outcompete Sr for calcite non-lattice sites. D Ba in CD3 (0.086 ± 0.008) is similar to values derived by Day and Henderson (2013) under cave-analogue conditions, whilst D U (0.013 ± 0.002) is almost an order of magnitude lower, possibly due to the unusually slow speleothem growth rates (<1 μm a−1), which could expose the crystal surfaces to leaching of uranyl carbonate. Finally, laser-ablation ICP-MS analysis of the upper 7 μm of CD3, regarded as 'modern' for the purposes of this study, reveals considerable heterogeneity, particularly for Sr, Ba and U, which is potentially indicative of compositional zoning. This reinforces the need to conduct 2D mapping and/or multiple laser passes to capture the range of time-equivalent elemental variations prior to palaeoclimate interpretation. [ABSTRACT FROM AUTHOR]