Journal of Analytical Atomic Spectrometry最新文献

In various technological fields, different nanomaterials are being used to push toward ever smaller and more complex structures. Different X-ray based methods can be extremely helpful to develop, analyze and improve such materials. Combining element sensitivity with lateral in-depth resolution, grazing incidence X-ray fluorescence (GIXRF) is a perfect candidate for this task. GIXRF represents an extension of standard X-ray fluorescence analysis (XRF) and total reflection XRF, and its utility has been demonstrated in a number of synchrotron studies over the years. Especially with improvements in X-ray sources and X-ray optics, GIXRF has become accessible to laboratory setups as well. Based on the principle of reciprocity, grazing emission – or gazing exit X-ray fluorescence (GEXRF) was postulated and proven to work in a similar way as GIXRF, with different advantages and disadvantages due to the inverse geometry. However, with their comparably more complex analysis procedures GIXRF and GEXRF methodologies are not yet widespread in research and industry. Thus, this review aims to give a comprehensive overview on the physical principle, technical requirements and recent applications in research and industry of these versatile nanoscale characterization methods.

Single particle microwave plasma optical emission spectrometry (SP MWP OES) was applied for the characterization of selenium nanopowder synthesized via a microwave-assisted green protocol using citrus juice as a reducing and stabilizing agent. The technique enabled real-time, single-particle detection of elemental signals, allowing assessment of particle size distribution and surface composition. The influence of particle size on signal intensity was determined using in-house synthesized quasi-spherical SeNP standards of known sizes. Time-correlated selenium and carbon signals confirmed the presence of surface-bound carbon-containing biomolecules, while co-detection of cadmium indicated potential interactions between SeNPs and cadmium species. These findings highlight the utility of SP MWP OES for probing nanoparticle surface functionalization and compositional variability. Although current calibration focused on spherical SeNPs, further development will address more complex systems. Overall, SP MWP OES proves to be a sensitive and informative tool for the characterization of SeNPs in biologically and environmentally relevant contexts.

Spot U–Pb isotopic dating of columbite–tantalite minerals provides a useful way to directly constrain the timing of Nb–Ta mineralization and fingerprint the provenance of columbite–tantalite ore concentrates. However, application of accurate columbite–tantalite U–Pb isotopic dating using microbeam techniques, such as laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) or secondary ion mass spectrometry, relies largely on the availability of well-characterized matrix-matched reference materials. Although some columbite–tantalite reference materials have been developed for microanalysis, columbite–tantalite minerals are typically highly variable in chemical composition, which may strongly affect the accuracy and quality of spot U–Pb dating. Here, a columbite megacryst LCT02 is investigated using a combined LA-ICPMS and isotope dilution-thermal ionization mass spectrometry (ID-TIMS) approach to assess its suitability as a reference material for spot U–Pb dating. The LA-ICPMS U–Pb measurements of LCT02 in two laboratories yield reproducible U–Pb dates, which are in good agreement with the ID-TIMS date within analytical uncertainties, indicating that LCT02 has the potential to become a new reference material for spot columbite U–Pb isotopic microanalysis. The weighted mean ID-TIMS ²⁰⁷Pb/²⁰⁶Pb date of 908.6 ± 1.4 Ma (2σ) is recommended as the best estimated crystallization age for LCT02.

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In this communication, we report the first LIBS imaging of soil thin sections at 25 μm resolution over 25 cm² with a 100 Hz acquisition rate. Coupled with micromorphology, this approach enables high-throughput elemental mapping, enhancing the analysis of soil structure, composition, and anthropogenic influences through nearly 4 million laser shots.

With the rising popularity of laser-induced breakdown spectroscopy (LIBS) for studying skeletal samples, the need for a matrix-matched reference material for quantitative analysis of bone has become a priority. Previous calibration materials used for laser-based sampling include glass standards, bone powders, carbonates, and hydroxyapatite standards, all of which fail to imitate both the physical and the chemical properties of the matrix of bone samples. This study focuses on the development, characterization, and application of matrix-matched reference material for bone. These materials are composed of a compact collagen scaffold that is embedded with elementally-enriched hydroxyapatite crystals. Physical characterization of the composites indicates a hydroxyapatite crystallinity and pore size that corresponds to bone. Molecular characterization confirms the presence of hydroxyapatite and collagen throughout the material, while elemental analysis reveals a profile nearly identical to that of bone. Calibration curves for strontium and barium were developed for portable LIBS (pLIBS) analysis, finding limits of detection and quantification values of 123 μg g⁻¹ and 140 μg g⁻¹ for strontium, and 29 μg g⁻¹ and 37 μg g⁻¹ for barium. Validation was performed on bone fragments for which pLIBS signal was used to determine the concentration of strontium and barium.

As one of the primary climate archives on earth, carbonates in different geological settings (e.g. corals, foraminifera, mollusks, and speleothems) can record multiple facets of the climate system with their elemental and isotopic compositions. In situ geochemical measurements of carbonates at high spatial resolution have the potential to generate climate records at annual, seasonal or even higher temporal resolution, yet such measurements are often costly and associated with relatively high analytical uncertainties. The accuracy of in situ measurements of trace element contents in carbonates can be additionally complicated by the availability of homogeneous and matrix-matched calibration standards. Here we propose a calibration method based on laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for trace element contents in natural carbonate samples, measured in element-to-calcium (El/Ca) ratios, with a series of commercially available nanoparticulate carbonate standards of various origins and compositions. Through a series of tests, we demonstrate that these nanoparticulate carbonate standards have sufficient homogeneity to serve as matrix-matched reference materials. With El/Ca calibration lines obtained from the standards, our method is able to generate more accurate and reproducible measurements of a dozen El/Ca ratios in carbonates at 15 μm or better resolution. Accurate high-resolution characterization of trace element contents in carbonates can not only improve our understanding of the evolution of earth's environmental history, but also shed light on the formation mechanisms of carbonate minerals of different origins.

An aqueous operation mode for graphite furnace molecular absorption spectrometry (GF-MAS) was established for the determination of total fluorine by combination with mineralization techniques. Pyrohydrolytic combustion was identified as the most effective sample preparation method, offering quantitative fluorine recovery after conversion into fluoride with a sample dilution factor of down to 100. Benchmarked against direct GF-MAS analysis, species discrimination, which can bias the results for up to two orders of magnitude, was eliminated. The procedure was evaluated using consumer product extracts spiked with different perfluorinated compounds. Detection limits of 40 μg per kg fluorine were obtained for the combined approach, offering a promising addition to combustion ion chromatography both in terms of sensitivity and sample throughput.

Laser-induced breakdown spectroscopy (LIBS) offers significant advantages in the rapid, sensitive, and environmentally friendly detection of toxic elements in water. However, its sensitivity for liquid samples remains a critical limitation, hindering broader practical applications. This work introduces a novel method combining femtosecond laser selective irradiation and chemical modification to construct a hybrid superhydrophobic and hydrophilic surface structure on an aluminum substrate, effectively forming a hydrophobic–hydrophilic enclosure structure. This structure facilitates the stable accumulation and uniform deposition of droplets within the hydrophilic area, significantly suppressing the “coffee ring” effect and enhancing both the concentration efficiency and detection sensitivity. Compared to traditional LIBS, the proposed method achieves limits of detection for Cr, Pb, and As at the ppb level (<3 μg L⁻¹), with determination coefficients (R²) exceeding 0.98. Furthermore, by incorporating the Partial Least Squares Regression (PLSR) model, this method further enhances the accuracy and reliability of the quantitative analysis, maintaining low root mean square errors (RMSEs) in both the training and test datasets. Overall, this innovative method holds considerable potential for water quality monitoring and trace element analysis, offering a novel strategy for high-sensitivity, simultaneous multi-element detection.

Sulfur (S), selenium (Se) and tellurium (Te), characterized by their chalcophile, siderophile and volatile properties, are increasingly critical in geoscience and planetary research. However, efficient and high-precision quantification of S–Se–Te in rocks remains analytically challenging due to severe spectral interferences, ultralow abundances, and potential volatile losses. In this study, a novel isotope dilution-inductively coupled plasma tandem mass spectrometry (ID-ICP-MS/MS) method was developed. Potential elemental volatile losses were addressed by isotope dilution, while the spectral interferences of S–Se–Te were suppressed online with N₂O or O₂ as reaction gases, eliminating the need for complicated chemical purification or hydride generation typically required by conventional methods. Interference-free measurements were performed by systematic investigation of reaction gas flow rate and ion kinetic energy (controlled by the octopole bias voltage). S and Se were mass-shifted to their oxide species for analysis, resulting in a substantial reduction of both background signals and interference signals compared to the single-quadrupole mode. Te was measured in “on-mass” mode, and the background equivalent concentrations from geological matrices for both Se and Te reached ppt levels. Isotope ratio precision and accuracy were enhanced through further optimization of integration times and mass bias correction strategies. Outstanding method detection limits of <0.29 ng mL⁻¹ for S, <0.0017 ng mL⁻¹ for Se, and <0.0033 ng mL⁻¹ for Te were achieved. Both N₂O and O₂ modes demonstrated good agreement with conventional ID-ICP-MS results across geological reference materials. This method simplifies sample preparation, enables high-precision and high-throughput analysis, and has great application potential for geochemical studies.