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Spectrochimica Acta
Pergamon Press
Spectrochimica Acta

Pergamon Press

0584-8547

Spectrochimica Acta/Journal Spectrochimica Acta
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    Tag-laser-induced breakdown spectroscopy with Si, Ti, and Fe micro-particles and analysis of leptin in a phosphate buffer solution

    Melikechi, NoureddineMarkushin, Yuriy
    7页
    查看更多>>摘要:The micro-particles composed of different chemical elements potentially can be used to yield the multi-element code for labeling of the molecules of interest. Proposed approach can recognize numerous analytes (biomarkers of diseases) of interest in parallel with minimum interfering. We report on a Laser Induced Breakdown Spectroscopy analysis of samples with known and controlled ratio of concentration of three metallic, two tags and a substrate, micro-particles, containing one of the chemical elements Ti, Si and Fe, as a function of the load of a particular element in a single or binary target sample. In addition, we report on the detection of ovarian cancer biomarker leptin in PBS buffer with 5% BSA using two metal micro-particles as Tags for LIBS with magnetic particle separation. We also show that the dual-TAG LIBS approach yields a 1.3 to 10 times enhancement in signal response obtained by the dual-over the single elemental marker approach.

    Improved elemental quantification in copper ores by laser-induced breakdown spectroscopy with judicious data processing

    Velasquez, MarizuAlvarez, JonnathanSandoval, ClaudioRamirez, Eimmy...
    9页
    查看更多>>摘要:The trading price and taxes of copper-concentrate exports depend on the chemical composition. Valuable elements such as Cu, Ag, and Mo increase the price while the presence of As reduces it. The quantification of these elements by laser induced breakdown spectroscopy (LIBS) in mineral ores with varied concentrations spanning from ppm to percentage is challenging. Several factors such as matrix effects, signal fluctuations (laser energy fluctuations, plasma instability, sample inhomogeneity), and self-absorption effects can contribute to analytical errors. Although advanced chemometric methods like artificial neural networks (ANN) can account for these limitations, tuning too many parameters may lead to overfitting of the results. Hence, to avoid overfitting, meaningful information should be fed to the model. In this work, a systematic procedure for getting meaningful LIBS spectral data i.e. "judicious data processing" is proposed. It consists of spectra normalization, feature selection and stratified data division. First, the normalization is done by using an internal standard (ISSN) considering emission lines (Al, Ca, Fe, Zn, and Si) of the main components of the matrix. Second, the feature selection is performed by identifying linearly correlated wavelengths (LCW) with the concentration of each target element. Third, stratified data division in the ANN regression is implemented. This approach, involving LIBS-ANN regression, is applied for multi-elemental quantification of valuable (Cu, Ag, Mo) and penalized (As) elements in copper ores. We compared the ANN models, considering features selection by LCW and prior knowledge spectral lines (PKSL), which are usually utilized in the literature. In terms of analytical figures, the root mean square error of predictions (RMSEP) using LCW improved for Cu (1.45% to 1.04%), Ag (8.5 mg.kg(-1) to 6.0 mg.kg(-1)), and As (0.16% to 0.06%), while it remained unchanged for Mo (0.04%). These improvements can be attributed to the decrease of spectral interferences, caused by the selection of the least affected lines and the compensation of signal fluctuations by spectral normalization.

    Ultrasound-assisted dispersive micro-solid phase extraction of Pb(II) in water samples with in situ synthesis of magnetic Fe3O4-PbS nanocomposites followed by electrothermal atomic absorption spectrometry determination

    Sanmartin, RaquelRomero, VanesaLavilla, IselaBendicho, Carlos...
    7页
    查看更多>>摘要:Herein, an ultrasound-assisted dispersive magnetic micro-solid phase extraction (DM-mu SPE) approach, along with electrothermal atomic absorption spectrometry (ETAAS) for the determination of lead at trace level in spring, well, river mineral and tap water samples was developed. The extraction step is based on the synthesis of PbS, following the sonochemical decomposition of L-cysteine used as sulphide precursor and its anchoring onto bare magnetite nanoparticles yielding the Fe3O4@PbS nanocomposite. Overall, DM-mu SPE with in situ precipitation of PbS and retention onto magnetic sorbent requires a time as short as 6 min. After trapping Pb(II) as PbS, the magnetic nanocomposite was easily separated from the aqueous matrix by applying an external magnetic field and analyzed by ETAAS following slurry sampling. Different parameters involved in both the sorbent preparation/extraction and Pb quantification were optimized. Under optimal conditions, the method showed a detection limit of 0.02 mu g L-1 Pb and a quantification limit of 0.07 mu g L-1 Pb. The repeatability, expressed as relative standard deviation was 2% (for 0.6 mu g L-1; n = 3). An experimental enrichment factor of 79 and an extraction efficiency of 99% were obtained. Finally, the method was applied for the determination of ultratrace levels of Pb (II) in spring, well, river mineral and tap water samples, showing quantitative recoveries in the range of 95-100%.

    Three-dimensional topographic and multi-elemental mapping by unilateral-shift-subtracting confocal controlled LIBS microscopy

    He, ChunjingHuang, WeihuaMao, YuqiongLi, Angze...
    9页
    查看更多>>摘要:Laser induced breakdown spectroscopy (LIBS) is a promising analytical technique based on the interaction between laser and material, which can quantitatively analyse the composition and content of material from the perspective of spectroscopy. The element distribution of non-uniform samples, such as natural ore, can be obtained by pointwise scanning without pretreatment. LIBS excitation intensity is the highest near the focus, so low imaging speed and low focusing accuracy will lead to unreliable element maps. Hence, an ultrasensitive technique called unilateral-shift-subtracting confocal controlled LIBS microscopy (UCCLIBS) was prepared to rapidly acquire high spatial resolution multi-elemental maps of the sample surface, which utilizes a laser induced breakdown spectrometer attached to a unilateral-shift-subtracting confocal microscope. A surface axial focusing ability of approximately 18 nm under 20x objective lens with the N.A. value of 0.4 is obtained, which is more than two orders of magnitude higher than that of ever traditional LIBS approaches, and the inherent anti-drift capability is successfully realized. The chemometric method of principal component analysis (PCA) is applied to the multi-element analysis of agate ore, which improved the accuracy and efficiency of sample analysis. We show the multi-layer element map of a solid-state electrolyte with a tomographic resolution of 2.3 mu m. With these excellent properties, the UCCLIBS might provide a new idea for the detection of three-dimensional elemental characterization of minerals and chemical materials.

    Accurate lithium isotopic analysis of twenty geological reference materials by multi-collector inductively coupled plasma mass spectrometry

    Miao, ZhuangLi, XiaoqiangHan, GuilinZhang, Qian...
    8页
    查看更多>>摘要:The lithium (Li) isotopes can be used to track the evolution of continental silicate weathering, which has an important role in maintaining Earth's long-term climate stability. At present, complex separation procedures and analytical mass bias restrict the accurate determination of Li isotopic compositions in various geological samples with different Li concentrations and matrix/Li ratios. Here, an optimization of dual-column chromatography achieves high Li recovery, low procedural blank, and low Na/Li ratio (< 1) after purification, allowing the acquisition of high precision Li isotope ratios by a Nu Plasma 3 multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). In order to evaluate the accuracy of new method, the 87Li values of BHVO-2, BCR-2, AGV-2, JG-2, RGM-2, SGR-1b, GSR-6, GSR-12, and seawater, are repeatedly analyzed more than 3 times each and are consistent with the published data within the uncertainty. The long-term external reproducibility of 87Li based on L-SVEC and IRMM-016 pure solutions is about +/- 0.2%0 (2SD), and is suitable for analysis of geological samples. These results suggest that new dual-column method is reproducible and reliable. We also report ten new reference materials including two USGS rocks (SDC-1: 1.8 +/- 0.4%0; W-2a: 2.9 +/- 0.3%0), four soils (GSS-3: 1.3 +/- 0.2%0; GSS-4: -5.1 +/- 0.4%0; GSS-6: -1.9 +/- 0.3%0; GSS-8: 0.4 +/- 0.3%0), and four stream sediments (GSD-6: -1.0 +/- 0.4%0; GSD-11: 1.1 +/- 0.3%0; GSD-12: 1.8 +/- 0.2%0; GSD-14: 1.6 +/- 0.4%0), all previously analyzed for K isotopes. There is significantly fractionation of Li and K isotopes during silicate weathering. Compared to the K isotopes, Li isotopes have more promising as an isotope tool for weathering due to its larger fractionation and its abiotic property.

    SuperCam calibration targets on board the perseverance rover: Fabrication and quantitative characterization

    Cousin, A.Sautter, VFabre, C.Dromart, G....
    26页
    查看更多>>摘要:Acknowledgements The authors would like to acknowledge Jeremy Guignard for his advice concerning the sample preparation for the EMPA analyses, as well as the Centre Castaing in Toulouse and the IsTep facility (UMR 7193) and ALIPP6 at Sorbonne University in Paris for their help, support and reactivity for the quantitative characterization of the samples. Authors would also like to acknowledge the SAP facility in Aude, France, for their help and professionalism concerning the machining of most of the targets, as well as Geoffroy Chevallier for the sintering of most targets in Toulouse, Florian Mercier (MATEIS, Lyon) for the SPS and Guillaume Servin (SCERAM, Lyon) for the machining done in Lyon. Also, the authors would like to thank the "Ecole des Mines ", for the natural diopside that comes from their collection. The authors would like to thank as well The Carlsberg Foundation (grantCF16-0981) for supporting the purchase of parts, tools and processes for producing targets 1 through 5. Authors would like to acknowledge Adrian Brown for his very useful inputs concerning orbital observations at Jezero crater. Authors would also like to thank all the engineering and technical team of SuperCam. The SuperCam project is supported in the US by NASA's Mars Exploration Program, and in France by CNES. Last, authors would also like to acknowledge the support of the International Space Science Institute (ISSI).

    High energy synchrotron X-ray fluorescence trace element study of a millimeter-sized asteroidal particle in preparation for the Hayabusa2 return sample analyses

    De Pauw, E.Tkalcec, B. J.Tack, P.Vekemans, B....
    10页
    查看更多>>摘要:The trace element content and distribution including rare Earth elements (REEs) measured in mm-sized asteroidal samples returned by JAXA's Hayabusa2 mission are important chemical parameters to decipher asteroid Ryugu's chronology of formation linked to early Solar System processes. In order to identify and analyze ancient Solar Nebula components, such as calcium-aluminum-rich inclusions (CAIs), by their trace element and REE content, a synchrotron beam with an incident energy of 90 keV is used to optimize the XRF signal and increase the information depth in the sample. The application of a (sub-)microscopic X-ray beam with such a high excitation energy not only allows for the detection of a wide range of heavy elements, but also to study their 3 dimensional distribution in mm-sized samples by means of X-ray fluorescence computed tomography (XRF-CT). The experiment was performed in anticipation of the initial analysis of the Hayabusa2 return samples at beamline ID15a of the European Synchrotron Radiation Facility (ESRF), Grenoble, France. The samples were analyzed with a focused beam of 0.5 x 0.5 mu m2, achieving limit of detection values as low as 0.5 ppm with an acquisition time of 1 s. Here we present results of scanning XRF(-CT) analysis of a mm-sized sample of the Murchison meteorite, a Mighei type chondrite (CM2), wherein a 9.6 x 11.5 x 8.2 mu m(3) CAI phase was detected and analyzed. The CAI grain is shown to be detectable throughout the entire sample volume (~700 mu m) during an XRF-CT scan over a full 360 & nbsp; angular range, thus proving the applicability of the method to study the microscopic distribution of high-Z elements at trace level concentration within millimeter-sized asteroidal particles.

    Post-landing major element quantification using SuperCam laser induced breakdown spectroscopy

    Anderson, Ryan B.Forni, OlivierFabre, CecileFouchet, Thierry...
    33页
    查看更多>>摘要:The SuperCam instrument on the Perseverance Mars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions and spectra are normalized to minimize signal fluctuations and effects of target distance. In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositions of diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g., silicates, sulfates, carbonates, oxides), more unusual compositions (e.g., Mn ore and sodalite), and replicates of the sintered SuperCam calibration targets (SCCTs) onboard the rover. For each major element (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), the database was subdivided into five "folds " with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining four folds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3 m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

    Preparation of sulfur-bearing reference materials for in situ sulfur isotope measurements using laser ablation multicollector inductively coupled plasma-mass spectrometry

    Chen, KaiyunBao, ZhianLiang, PengNie, Xiaojuan...
    10页
    查看更多>>摘要:In this study, a method for solidifying sulfide and sulfate nanoparticulate powder to prepare bracketing standards and samples for in situ S isotopic analysis using laser ablation multicollector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) was developed. Sulfide or sulfate powder was transformed into a stable and mechanically resistant target by mixing it with epoxy resin. Using this method, seven bracketing standards with diverse matrix minerals (pyrite, chalcopyrite, sphalerite, galena, arsenopyrite, barite, and gypsum) were synthesized in the form of resin-preserved powders (RPPs). The effects of ablation behavior, powder particle size, and homogeneity on the S isotopic ratios in these RPPs were rigorously evaluated. The precision of the delta S-34(VCDT) sulfur isotopic results obtained by LA-MC-ICP-MS was better than 0.47%0 (2SD uncertainty, n >= 20 over 4 months) for the S-bearing mineral RPPs. Finally, the in situ S isotope results of the seven RPPs measured by LA-MC-ICP-MS were consistent with the values obtained using solution nebulizer (SN)-MC-ICP-MS. The isotopic composition and homogeneity of a range of sulfide mineral RPPs (seven minerals referred to above) were characterized for use as potential reference materials. Our method provides the opportunity to prepare brack-eting standards and samples for in situ S isotope analysis for a wide range of sulfur-bearing materials and is particularly appropriate for geologic samples with complex matrices and for which high spatial resolution in situ microbeam analysis is critical. More importantly, this method provides new prospects for the preparation of homogenized reference materials from natural minerals that are urgently needed for matrix-matched calibration and quality control of LA-ICP-MS geochemical and isotope data.