Evaluation strategies for isotope ratio measurements of single particles by LA-MC-ICPMS.
Ontology highlight
ABSTRACT:
SUBMITTER: Kappel S
PROVIDER: S-EPMC3589628 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:The 138La-138Ce decay system (half-life 1.02 × 1011 years) is a potentially highly useful tool to unravel information about the timing of geological processes and about the interaction of geological reservoirs on earth, complementing information from the more popular 147Sm-143Nd and 176Lu-176Hf isotope systems. Previously published analytical protocols were limited to TIMS. Here we present for the first time an analytical protocol that employs MC-ICPMS, with an improved precision and sensitivity. To perform sufficiently accurate La-Ce measurements, an efficient ion-chromatographic procedure is required to separate Ce from the other rare earth elements (REE) and Ba quantitatively. This study presents an improved ion-chromatographic procedure that separates La and Ce from rock samples using a three-step column separation. After REE separation by cation exchange, Ce is separated employing an Ln Spec column and selective oxidation. In the last step, a cation clean-up chemistry is performed to remove all remaining interferences. Our MC-ICPMS measurement protocol includes all stable Ce isotopes (136Ce, 138Ce, 140Ce and 142Ce), by employing a 1010 ohm amplifier for the most abundant isotope 140Ce. An external reproducibility of ±0.25?-units (2 r.s.d) has been routinely achieved for 138Ce measurements for as little as 150-600 ng Ce, depending on the sample-skimmer cone combinations being used. Because the traditionally used JMC-304 Ce reference material is not commercially available anymore, a new reference material was prepared from AMES laboratory Ce metal (Cologne-AMES). In order to compare the new material with the previously reported isotopic composition of AMES material prepared at Mainz (Mainz-AMES), Cologne-AMES and JMC-304 were measured relative to each other in the same analytical session, demonstrating isotope heterogeneity between the two AMES and different JMC-304 batches used in the literature. To enable sufficiently precise age correction of radiogenic 138Ce and to perform isochron dating, a protocol was developed where La and Ce concentrations are determined by isotope dilution (ID), using an isotope tracer enriched in 138La and 142Ce. The new protocols were applied to determine the variations of Ce isotope compositions and La-Ce concentrations of certified geochemical reference materials (CRMs): BCR-2, BCR-1, BHVO-2, JR-1, JA-2, JB-3, JG-1, JR-1, JB-1b, AGV-1 and one in-house La Palma standard.
| S-EPMC5789583 | biostudies-literature
Project description:We report a method for the chemical purification of Pt from geological materials by ion-exchange chromatography for subsequent Pt stable isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using a 196Pt-198Pt double-spike to correct for instrumental mass bias. Double-spiking of samples was carried out prior to digestion and chemical separation to correct for any mass-dependent fractionation that may occur due to incomplete recovery of Pt. Samples were digested using a NiS fire assay method, which pre-concentrates Pt into a metallic bead that is readily dissolved in acid in preparation for anion-exchange chemistry. Pt was recovered from anion-exchange resin in concentrated HNO3 acid after elution of matrix elements, including the other platinum group elements (PGE), in dilute HCl and HNO3 acids. The separation method has been calibrated using a precious metal standard solution doped with a range of synthetic matrices and results in Pt yields of ?90% with purity of ?95%. Using this chemical separation technique, we have separated Pt from 11 international geological standard reference materials comprising of PGE ores, mantle rocks, igneous rocks and one sample from the Cretaceous-Paleogene boundary layer. Pt concentrations in these samples range from ca. 5 ng g-1 to 4 ?g g-1. This analytical method has been shown to have an external reproducibility on ?198Pt (permil difference in the 198Pt/194Pt ratio from the IRMM-010 standard) of ±0.040 (2 sd) on Pt solution standards (Creech et al., 2013, J. Anal. At. Spectrom. 28, 853-865). The reproducibility in natural samples is evaluated by processing multiple replicates of four standard reference materials, and is conservatively taken to be ca. ±0.088 (2 sd). Pt stable isotope data for the full set of reference materials have a range of ?198Pt values with offsets of up to 0.4‰ from the IRMM-010 standard, which are readily resolved with this technique. These results demonstrate the potential of the Pt isotope system as a tracer in geochemical systems.
| S-EPMC4326679 | biostudies-literature
Project description:This paper reviews the problems encountered in eleven studies of Sr isotope analysis using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) in the period 1995-2006. This technique has been shown to have great potential, but the accuracy and precision are limited by: (1) large instrumental mass discrimination, (2) laser-induced isotopic and elemental fractionations and (3) molecular interferences. The most important isobaric interferences are Kr and Rb, whereas Ca dimer/argides and doubly charged rare earth elements (REE) are limited to sample materials which contain substantial amounts of these elements. With modern laser (193 nm) and MC-ICPMS equipment, minerals with >500 ppm Sr content can be analysed with a precision of better than 100 ppm and a spatial resolution (spot size) of approximately 100 microm. The LA MC-ICPMS analysis of 87Sr/86Sr of both carbonate material and plagioclase is successful in all reported studies, although the higher 84Sr/86Sr ratios do suggest in some cases an influence of Ca dimer and/or argides. High Rb/Sr (>0.01) materials have been successfully analysed by carefully measuring the 85Rb/87Rb in standard material and by applying the standard-sample bracketing method for accurate Rb corrections. However, published LA-MC-ICPMS data on clinopyroxene, apatite and sphene records differences when compared with 87Sr/86Sr measured by thermal ionisation mass spectrometry (TIMS) and solution MC-ICPMS. This suggests that further studies are required to ensure that the most optimal correction methods are applied for all isobaric interferences.
| S-EPMC2175028 | biostudies-other
Project description:This paper critically reviews the state-of-the-art of isotope amount ratio measurements by solution-based multi-collector inductively coupled plasma mass spectrometry (MC ICP-MS) and presents guidelines for corresponding data reduction strategies and uncertainty assessments based on the example of n((87)Sr)/n((86)Sr) isotope ratios. This ratio shows variation attributable to natural radiogenic processes and mass-dependent fractionation. The applied calibration strategies can display these differences. In addition, a proper statement of uncertainty of measurement, including all relevant influence quantities, is a metrological prerequisite. A detailed instructive procedure for the calculation of combined uncertainties is presented for Sr isotope amount ratios using three different strategies of correction for instrumental isotopic fractionation (IIF): traditional internal correction, standard-sample bracketing, and a combination of both, using Zr as internal standard. Uncertainties are quantified by means of a Kragten spreadsheet approach, including the consideration of correlations between individual input parameters to the model equation. The resulting uncertainties are compared with uncertainties obtained from the partial derivatives approach and Monte Carlo propagation of distributions. We obtain relative expanded uncertainties (U rel; k?=?2) of n((87)Sr)/n((86)Sr) of <?0.03 %, when normalization values are not propagated. A comprehensive propagation, including certified values and the internal normalization ratio in nature, increases relative expanded uncertainties by about factor two and the correction for IIF becomes the major contributor.
| S-EPMC4709391 | biostudies-literature
Project description:Geochemical markers are being increasingly applied to fundamental questions in population and community ecology in marine habitats because they allow inferences on individuals dispersal, but vital effects, small sample size and instrumental limitation are still challenging particularly in deep-sea studies. Here we use shells of the deep-sea bivalve Idas modiolaeformis to assess potential effects of sample storage, mineralogy, and valve orientation on LA-ICPMS measurements. Trace element concentrations of (24)Mg, (43)Ca, (88)Sr, (137)Ba, (208)Pb, and (238)U are not affected by the two most commonly used storage methods of biologic deep-sea samples (frozen at -20°C and fixed in 95% ethanol); thus combined analysis of differently preserved specimens is possible when the number of individuals is insufficient and distinct sample fixation is needed for multiple purposes. Valve orientation had a strong impact on quantification of trace elements in the calcitic but not in the aragonitic layer of adult shells. Hence, to enable comparisons between adult shells and entirely aragonitic embryonic shells, a reference map of site-specific signatures can potentially be generated using the aragonitic layer of the adult shells. Understanding ontogenetic changes and environmental effects in trace element incorporation is critical before geochemical fingerprinting can be used as a tool for larval dispersal studies in the deep-sea.
| S-EPMC4672299 | biostudies-other
Project description:In this work, a novel standardization strategy for quantitative elemental bioimaging is evaluated. More specifically, multi-element quantification by laser ablation-inductively coupled plasma-time-of-flight mass spectrometry (LA-ICP-TOFMS) is performed by multi-point calibration using gelatin-based micro-droplet standards and validated using in-house produced reference materials. Fully automated deposition of micro-droplets by micro-spotting ensured precise standard volumes of 400 ± 5 pL resulting in droplet sizes of around 200 μm in diameter. The small dimensions of the micro-droplet standards and the use of a low-dispersion laser ablation setup reduced the analysis time required for calibration by LA-ICPMS significantly. Therefore, as a key advance, high-throughput analysis (pixel acquisition rates of more than 200 Hz) enabled to establish imaging measurement sequences with quality control- and standardization samples comparable to solution-based quantification exercises by ICP-MS. Analytical figures of merit such as limit of detection, precision, and accuracy of the calibration approach were assessed for platinum and for elements with biological key functions from the lower mass range (phosphorus, copper, and zinc). As a proof-of-concept application, the tool-set was employed to investigate the accumulation of metal-based anticancer drugs in multicellular tumor spheroid models at clinically relevant concentrations. Graphical abstract.
| S-EPMC8748332 | biostudies-literature
Project description:BackgroundFractional flow reserve is widely used for the functional evaluation of coronary artery stenosis. Some studies have similarly used the translesional pressure ratio measurements for the functional evaluation of intracranial atherosclerotic stenosis. In this paper, we aimed to investigate the relationship between pressure ratio and cerebral tissue perfusion by MR perfusion imaging and provided a non-invasive method for evaluating the functional significance of intracranial atherosclerotic stenosis.MethodsA total of 18 consecutive patients with intracranial atherosclerotic stenosis patients including 19 stenotic vessels were recruited. The pressure was measured using a pressure guidewire, the pressure ratio before and after the endovascular intervention was calculated and compared with the severity of diameter stenosis and perfusion-derived MR (the time to maximum tissure residue function (Tmax)). Moreover, the DSA-derived pressure ratio was computed using a novel computational fluid dynamics-based model, termed CFD-PR, and was compared with the actual pressure ratio to assess its diagnostic accuracy.ResultsThe pressure ratio increased after percutaneous transluminal angioplasty or stenting, while the correlation between pressure ratio and diameter stenosis was not significant. The pressure ratio was negatively correlated with Tmax (r = -0.73, P < 0.01), and a 95% confidence interval for the cutoff value of pressure ratio = 0.67 (95% confidence interval: 0.58-0.76) was suggested. There was a good correlation (mean = 0.02, Spearman's correlation coefficient r = 0.908, P < 0.001) and agreement (limits of agreement: -0.157 to 0.196, P = 0.954) between CFD-PR and the actual pressure ratio.ConclusionsThis exploratory study indicates the pressure ratio may correlate with the perfusion status. The pressure ratio can be calculated through a non-invasive method using a computational fluid dynamics-based method.
| S-EPMC9958418 | biostudies-literature
Project description:The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3-0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%).
| S-EPMC5087850 | biostudies-literature
Project description:At Norje Sunnansund, an Early Holocene settlement in southern Sweden, the world's earliest evidence of fermentation has been interpreted as a method of managing long-term and large-scale food surplus. While an advanced fishery is suggested by the number of recovered fish bones, until now it has not been possible to identify the origin of the fish, or whether and how their seasonal migration was exploited. We analysed strontium isotope ratios (87Sr/86Sr) in 16 cyprinid and 8 pike teeth, which were recovered at the site, both from within the fermentation pit and from different areas outside of it, by using laser ablation multi-collector inductively coupled plasma mass spectrometry. Our investigation indicates three different regions of origin for the fish at the site. We find that the most commonly fermented fish, cyprinids (roach), were caught in the autumn during their seasonal migration from the Baltic Sea to the sheltered stream and lake next to the site. This is in contrast to the cyprinids from other areas of the site, which were caught when migrating from nearby estuaries and the Baltic Sea coast during late spring. The pikes from the fermentation pit were caught in the autumn as by-catch to the mainly targeted roach while moving from the nearby Baltic Sea coast. Lastly, the pikes from outside the fermentation pit were likely caught as they migrated from nearby waters in sedimentary bedrock areas to the south of the site, to spawn in early spring. Combined, these data suggest an advanced fishery with the ability to combine optimal use of seasonal fish abundance at different times of the year. Our results offer insights into the practice of delayed-return consumption patterns, provide a more complete view of the storage system used, and increase our understanding of Early Holocene sedentism among northern hunter-fisher-gatherers. By applying advanced strontium isotope analyses to archaeological material integrated into an ecological setting, we present a methodology that can be used elsewhere to enhance our understanding of the otherwise elusive indications of storage practices and fish exploitation patterns among ancient foraging societies.
| S-EPMC7817046 | biostudies-literature
Project description:BackgroundAn objective measure of added sugar (AS) and sugar-sweetened beverage (SSB) intake is needed. The δ(13)C value of finger-stick blood is a novel validated biomarker of AS/SSB intake; however, nonsweetener corn products and animal protein also carry a δ(13)C value similar to AS sources, which may affect blood δ(13)C values. The δ(15)N value of blood has been proposed as a "correction factor" for animal protein intake.ObjectivesThe objectives were to 1) identify foods associated with δ(13)C and δ(15)N blood values, 2) determine the contribution of nonsweetener corn to the diet relative to AS intake, and 3) determine if the dual-isotope model (δ(13)C and δ(15)N) is a better predictor of AS/SSB intake than δ(13)C alone.MethodsA cross-sectional sample of southwest Virginian adults (n = 257; aged 42 ± 15 y; 74% overweight/obese) underwent dietary intake assessments and provided finger-stick blood samples, which were analyzed for δ(13)C and δ(15)N values by using natural abundance stable isotope mass spectrometry. Statistical analyses included ANOVAs, paired-samples t tests, and multiple linear regressions.ResultsThe mean ± SD daily AS intake was 88 ± 59 g and nonsweetener corn intake was 13 ± 13 g. The mean δ(13)C value was -19.1 ± 0.9‰, which was significantly correlated with AS and SSB intakes (r = 0.32 and 0.39, respectively; P ≤ 0.01). The δ(13)C value and nonsweetener corn intake and the δ(15)N value and animal protein intake were not correlated. AS intake was significantly greater than nonsweetener corn intake (mean difference = 76.2 ± 57.2 g; P ≤ 0.001). The δ(13)C value was predictive of AS/SSB intake (β range: 0.28-0.35; P ≤ 0.01); however, δ(15)N was not predictive and minimal increases in R(2) values were observed when the δ(15)N value was added to the model.ConclusionsThe data do not provide evidence that the dual-isotope method is superior for predicting AS/SSB intakes within a southwest Virginian population. Our results support the potential of the δ(13)C value of finger-stick blood to serve as an objective measure of AS/SSB intake. This trial was registered at clinicaltrials.gov as NCT02193009.
| S-EPMC4442118 | biostudies-literature