Geochemical studies of geological samples require the precise determination of their major and trace element contents and, when measured, of their isotopic compositions. It is now commonly accepted ...that the accuracy and precision of geochemical analyses are best estimated by the concomitant analysis of international reference materials run as unknown samples. Although the composition of a wide selection of basalts is relatively well constrained, this is far from being the case for sedimentary materials. We present here a comprehensive set of major and trace element data as well as Nd, Hf, Sr and Pb isotopic compositions for thirteen commonly used international reference materials – eight magmatic rocks (BHVO‐2, BR, BE‐N, BR 24, AGV‐1, BIR‐1, UB‐N, RGM‐1) and five sediments (JLk‐1, JSd‐1, JSd‐2, JSd‐3, LKSD‐1). We determined the concentrations of over forty elements in the magmatic rocks together with Sr, Nd, Hf and Pb isotopic compositions. Our trace element results were both accurate (difference ≤ 3%) and precise (reproducibility at 1s ≤ 3%) and the isotopic results were very similar to other published values. In contrast, we observed a significant chemical and isotopic variability in the sedimentary materials, which we attribute to mineral heterogeneities in the powders. Despite the limitation imposed by this heterogeneity, our work presents a complete set of data determined with a precision not yet achieved in the literature for sedimentary material. We also provide the first Nd, Hf and Pb isotopic measurements for the five sediments, which are commonly used by the geochemical community. Our study of both basalt and sediment reference materials represents a comprehensive and self‐consistent set of geochemical data and can therefore be considered as a reference database for the community.
Les études géochimiques des échantillons géologiques exigent la détermination précise de leurs teneurs en éléments majeurs et traces et, lorsqu’elle est mesurée, de leurs compositions isotopiques. Il est maintenant communément admis que l’exactitude et la précision des analyses géochimiques sont les mieux estimées par l’analyse simultanée, comme échantillons inconnus, de matériaux de référence internationaux. La composition d’une large sélection de basaltes est relativement bien contrainte, ce qui est loin d’être le cas pour les matériaux sédimentaires. Nous présentons ici un jeu complet de données d’éléments majeurs et traces ainsi que les compositions isotopiques du Nd, de l’Hf, du Sr et du Pb pour treize matériaux de référence internationaux couramment utilisés – huit roches magmatiques (BHVO‐2, BR, BE‐N, BR 24, AGV‐1, BIR‐1, UB‐N, RGM‐1) et cinq sédiments (JLk‐1, JSD‐1, JSD‐2, JSD‐3, LKSD‐1). Nous avons déterminé les concentrations de plus de quarante éléments dans les roches magmatiques ainsi que leurs compositions isotopiques du Sr, du Nd, de l’Hf et du Pb. Nos résultats pour les éléments traces sont à la fois précis (différence ≤ 3%) et justes (reproducibilitéà 1s ≤ 3%) et les résultats isotopiques sont très similaires aux autres valeurs publiées. En revanche, nous avons observé une variabilité chimique et isotopique significative pour les matériaux sédimentaires, que nous attribuons à la présence d’hétérogénéités minérales au sein des poudres. Malgré les limitations imposées par ces hétérogénéités, notre travail présente un jeu complet de données déterminé avec une précision encore jamais atteinte dans la littérature pour des matériaux sédimentaires. Nous fournissons également les premières mesures isotopiques du Nd, de l’Hf et du Pb pour les cinq sédiments, qui sont couramment utilisées par la communauté géochimique. Notre étude à la fois de basaltes et de sédiments de référence représente un ensemble complet et auto‐cohérent de données géochimiques qui peut donc être considéré comme une base de données de référence pour la communauté.
Three synthetic reference glasses were prepared by directly fusing and stirring 3.8 kg of high‐purity oxide powders to provide reference materials for microanalytical work. These glasses have ...andesitic major compositions and are doped with fifty‐four trace elements in nearly identical abundance (500, 50, 5 µg g−1) using oxide powders or element solutions, and are named ARM‐1, 2 and 3, respectively. We further document that sector‐field (SF) ICP‐MS (Element 2 or Element XR) is capable of sweeping seventy‐seven isotopes (from 7Li to 238U, a total of sixty‐eight elements) in 1 s and, thus, is able to quantify up to sixty‐eight elements by laser sampling. Micro‐ and bulk analyses indicate that the glasses are homogeneous with respect to major and trace elements. This paper provides preliminary data for the ARM glasses using a variety of analytical techniques (EPMA, XRF, ICP‐OES, ICP‐MS, LA‐Q‐ICP‐MS and LA‐SF‐ICP‐MS) performed in ten laboratories. Discrepancies in the data of V, Cr, Ni and Tl exist, mainly caused by analytical limitations. Preliminary reference and information values for fifty‐six elements were calculated with uncertainties 2 relative standard error (RSE) estimated in the range of 1–20%.
Key Points
Three synthetic andesite reference glasses (ARM‐1, ARM‐2 and ARM‐3) were prepared, and characterised by a variety of analytical techniques.
The homogeneity of the ARM glasses was evaluated by multiple EPMA and LA‐ICP‐MS spot analyses on randomly selected glass splits.
Preliminary reference values of the ARM glasses are provided.
The discharge of plastic waste and subsequent formation and global distribution of microplastics (MPs) has caused great concern and highlighted the need for dedicated methods to characterise MPs in ...complex environmental matrices like seawater. Single particle inductively coupled plasma – mass spectrometry (SP ICP-MS) is an elegant method for the rapid analysis of nano- and microparticles and to characterise number concentrations, mass, and size distributions. However, the analysis of carbon (C)-based microstructures such as MPs by SP ICP-MS is at an early stage. This paper investigates various strategies to improve figures of merit to detect and characterise MPs in complex matrices, such as seawater. Ten methods operating distinct acquisition modes with various collision/reaction gases, tandem MS (ICP-MS/MS) and targeting 12C or 13C were developed and compared for the analysis of polystyrene-based MPs standards in ultra-pure water and seawater. The robust analysis of MPs in seawater was accomplished by on-line aerosol dilution enabling repeatable size calibration while minimising drift effects. However, the direct analysis of seawater decreased ion transmission and required matrix-matching for accurate size calibration. Analysis of the 12C isotope instead of 13C improved the size detection limits (sDL) to 0.62 μm in ultra-pure water and to 0.96 μm in seawater. ICP-MS/MS methods decreased ion transmission but also reduced background signal and increased selectivity, particularly in the presence of spectral interferences. In the second part of this study, it was demonstrated that the developed methods were applicable for the analysis of C in unicellular organisms and allowed calibration of physical dimensions. This is relevant for the investigation and understanding of phenotypical traits associated, for example, with climate change resilience as well as oceanic C storage. SP/SC ICP-MS was employed to target five different intact Symbiodiniaceae algae strains with diverse life-histories in seawater and polystyrene-based MPs were used to calibrate cellular C masses, which were between 51 and 83 pg. The C mass distribution across the analysed unicellular cells was used for modelling cell sizes, which were in the range of 7.6 and 10.1 μm. Determined values were in line with values obtained with complementary techniques (Coulter-counting, total organic C analysis and microscopic analysis).
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•SP/SC ICP-MS method development and application for the individual analysis of C-based microstructures in seawater.•Matrix-matching and on-line aerosol dilution for robust mass and size characterisation of microplastics.•Size detection limit for polystyrene-based microplastics is improved to 0.6 μm.•Developed methods are applied for the direct analysis of carbon in unicellular algae in seawater.•C mass distribution and cellular sizes of unicellular algae are determined via SP and SC ICP-MS.
From its early beginnings in characterizing aerosol particles to its recent applications for investigating natural waters and waste streams, single particle inductively coupled plasma-mass ...spectrometry (spICP-MS) has proven to be a powerful technique for the detection and characterization of aqueous dispersions of metal-containing nanomaterials. Combining the high-throughput of an ensemble technique with the specificity of a single particle counting technique and the elemental specificity of ICP-MS, spICP-MS is capable of rapidly providing researchers with information pertaining to size, size distribution, particle number concentration, and major elemental composition with minimal sample perturbation. Recently, advances in data acquisition, signal processing, and the implementation of alternative mass analyzers (e.g., time-of-flight) has resulted in a wider breadth of particle analyses and made significant progress toward overcoming many of the challenges in the quantitative analysis of nanoparticles. This review provides an overview of spICP-MS development from a niche technique to application for routine analysis, a discussion of the key issues for quantitative analysis, and examples of its further advancement for analysis of increasingly complex environmental and biological samples.
Graphical Abstract
Single particle ICP-MS workflow for the analysis of suspended nanoparticles
Carbon dioxide (CO2) was used as a reaction gas to investigate the gas‐phase ion‐molecule interactions using the Agilent 8900 ICP‐MS/MS. A solution containing forty‐five elements representative of ...the periodic table was used to supply the ions to react with CO2 in the collision/reaction cell (CRC). The only significant product ions formed were monoxides. The general reactivity was shown to be consistent with density functional theory (DFT)‐predicted reaction enthalpies, such that all predicted exothermic reactions produced product ions at levels of at least 1% of the unreacted ion. Most endothermic reactions observed had sufficient kinetic energy in excess of the reaction enthalpies. Our results suggest that reaction enthalpy is a reasonable predictor of reactivity with CO2 on the timescales of the interactions in non‐thermal ICP‐MS/MS systems. The ease and rapidity of data collection with the ICP‐MS/MS and DFT calculations using the NWChem suite has value given the scarcity of thermochemical data of CO2 reactions in the literature. These studies are especially useful for the identification of targeted reaction chemistries to be leveraged for analytical method development, such as for the inline separation of isobaric interferences from analytes of interest.
Key Points
Gas phase ion‐molecule reactivity was studied using CO2 and 45 elements representative of the periodic table on an Agilent 8900 ICP‐MS/MS.
Monoxides were the main product ion formed with CO2.
Comparisons between the DFT derived reaction enthalpy, the tuning dependent ion kinetic energy and the observed product ions indicate that reaction enthalpy explains product ion formation in 93% of the ions studied.
•A comprehensive evaluation on various aspects of uranium in groundwater.•Detection and determination of elemental and isotopic concentrations of uranium in water.•Currently available remediation ...technologies for the removal of uranium from water.
Uranium concentration/contamination in groundwater is currently a subject of concern all over the world due to related severe health problems to humans, as groundwater is the main drinking water source in rural and urban India and also in several parts of the world. Uranium concentration in groundwater in shallow aquifers in various states such as Punjab, Rajasthan, Karnataka Telangana, and Madhya Pradesh of India varies from 0 to 1443 ng/ml exceeding the permissible levels by WHO for drinking water (30 ng/ml), at several places. Very high concentrations ranging up to 1400 ng/ml were reported in some areas in other countries such as Canada, the USA, Mongolia, Burundi, Zambia, Nigeria, South Korea, Pakistan, Jordon, Afghanistan, China, and Myanmar. Various natural aspects which influence the uranium concentration in groundwater such as bedrock geology, water chemistry, and redox conditions, and anthropogenic sources such as mining activities (uranium, coal, and phosphate rock), nuclear activities, agricultural practices of using phosphate fertilizers, and prevalence of excessive nitrate in some areas, are described with examples. Some of the important analytical techniques for the precise and accurate determination of elemental and isotopic concentrations of uranium in water samples, such as LED fluorimetry, Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), high-resolution ICP-MS (HR-ICP-MS), and multi-collector ICP-MS (MC-ICP-MS), are described. A number of advancements have taken place in remediation technologies for the removal of uranium in drinking water using different physical, chemical, and biological methods including rainwater harvesting. Various mitigation strategies for the effective removal of uranium from water during treatment, such as bioremediation using biochars from different sources, nanoparticle technology, and adsorption by magnesium (Mg)-iron (Fe)-based hydrotalcite-like compounds (MF-HT), are described in detail.
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Cerium dioxide nanoparticles (CeO
2
NPs) are among the most broadly used engineered nanoparticles that will be increasingly released into the environment. Thus, understanding their uptake, ...transportation, and transformation in plants, especially food crops, is critical because it represents a potential pathway for human consumption. One of the primary challenges for the endeavor is the inadequacy of current analytical methodologies to characterize and quantify the nanomaterial in complex biological samples at environmentally relevant concentrations. Herein, a method was developed using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) technology to simultaneously detect the size and size distribution of particulate Ce, particle concentration, and dissolved cerium in the shoots of four plant species including cucumber, tomato, soybean, and pumpkin. An enzymatic digestion method with Macerozyme R-10 enzyme previously used for gold nanoparticle extraction from the tomato plant was adapted successfully for CeO
2
NP extraction from all four plant species. This study is the first to report and demonstrate the presence of dissolved cerium in plant seedling shoots exposed to CeO
2
NPs hydroponically. The extent of plant uptake and accumulation appears to be dependent on the plant species, requiring further systematic investigation of the mechanisms.
Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing 25Mg, 43Ca and ...87Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.
Les rapports Mg/Ca et Sr/Ca des carbonates de calcium sont importants pour de nombreuses études paléoclimatiques. Nous présentons une méthode de dilution isotopique s’appuyant sur un simple ajout (« spike ») constitué d’un mélange contenant 25Mg, 43Ca et 87Sr. Des dizaines d’échantillons par jour, aussi petit que 10 μg of carbonate, pourraient être dissous, enrichis (« spiked ») et analysés dans un ICP‐MS avec une précision de 0.8% (2 RSD). Deux types d’instruments, ICP‐MS à secteur magnétique et ICP‐MS quadripolaire, ont été comparés. La meilleure précision à long terme constatéétait de 0.4% (2 RSD), bien que cette valeur ait augmenté jusqu’à un facteur deux lorsque des échantillons caractérisés par des teneurs en Mg ou Sr très différentes ont été analysés ensemble dans une même séquence. Les moyennes à long terme pour les deux instruments sont du même ordre. Aucun effet de matrice n’a été détecté pour une gamme de concentrations de Ca comprise entre 0.2 et 2 mmol l‐1. La précision, testée par la mesure de solutions standards de synthèse, était de 0.8%, avec certaines tendances systématiques. Nous démontrons la robustesse de cette méthode de dilution isotopique pour: (1) l’obtention de résultats précis pour des ensembles d’échantillons qui présentent une large gamme de teneurs en Mg et Sr, et (2) tester des carbonates solides comme matériaux de référence candidats à des études de cohérence entre laboratoires. Les rapports Mg/Ca et Sr/Ca obtenus pour les matériaux de référence sont en bon accord avec les valeurs de la littérature.
The Flinton Group is a metasedimentary succession of the Grenville Province in SE Ontario, potentially allowing insight into the tectono‐thermal evolution of continental crust during the ...Mesoproterozoic. At its Green Bay locality, Flinton Group metapelites of the staurolite zone contain abundant, post‐kinematic garnet porphyroblasts. Whereas the larger garnet crystals are typically impinged, smaller crystals are isolated from each other, occasionally exhibiting elongated shapes with apparently trigonal morphology. Central sections of the garnet population of a representative sample reveal that garnet is composed of different compositional and microstructural domains. In the largest crystals of the population, garnet contains rectangular to rhombic domains, marked by sharp increases in the concentrations of Nb, V, Ti, and Cr. These domains are associated with irregularly shaped patches, characterized by spatially heterogenous enrichments of Ca and LREE, and depletions in the contents of P, Y, MREE, and HREE, accompanied by increased densities of comparatively coarse‐grained quartz inclusions hosting apatite. Microstructural relationships indicate that these domains correspond to portions of garnet that pseudomorphed biotite, with the enrichments of Nb, V, Ti, and Cr outlining the original biotite shapes. The compositional patterns formed by Ca, P, Y, and REE indicate that apatite participated in the grain‐fluid interactions that operated during the metasomatic replacement of biotite by garnet. The statistical analyses of the garnet number and size distributions confirm that garnet initially nucleated on biotite, controlled by the kinetics of attachment and detachment processes at the garnet/biotite interface, resulting in the typical impingement habit. In situ Lu–Hf garnet geochronology applied to garnet that did not pseudomorph biotite, and hence is enriched in HREE, points to a first metamorphic event at c. 1080
± 31 Ma. Subsequent pseudomorphism of staurolite by white mica in a Al2O3‐ and FeO‐mobile system resulted in the concomitant crystallization of a new garnet generation, forming overgrowths on the first garnet generation and nuclei in the fine‐grained matrix. Garnet that nucleated during this event grew to isolated and elongated crystals with apparently trigonal morphology, aligned in a direction c. perpendicular to the rock matrix foliation. The open‐system behaviour during this event limits the use of whole‐rock‐based geochronological and thermobarometrical applications. However, previously published in situ U–Pb ages of monazite included in the rims of the garnet crystals and in the rock matrix indicate that this event took place at c. 976
± 4 Ma, likely associated with a period of increased hydrothermal activity late in the metamorphic history of the Grenvillian Orogeny. Diffusion geospeedometry calculations indicate that garnet growth during this hydrothermal event lasted for less than 6 Myr.
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