Journal of Analytical Atomic Spectrometry最新文献

{"title":"A performance compensation method for miniaturized LIBS instruments in precise rock classification","authors":"Yuting Fu, Jing Chen, Biye Liu, Beibei Hu, Xueying Jin, Guang Yang and Huihui Sun","doi":"10.1039/D4JA00453A","DOIUrl":"https://doi.org/10.1039/D4JA00453A","url":null,"abstract":"<p >Rocks, as one of the most ubiquitous substances on Earth, bear the historical records of Earth's evolution and traces of geological processes. Rock identification can reveal the geological environment and resource distribution, which are important for geological research. Laser-induced breakdown spectroscopy (LIBS), a real-time, micro-destructive, and multi-element simultaneous analysis technique, has played an important role in rock identification and geological research. However, traditional laboratory-based LIBS instruments are bulky and unsuitable for field site geological exploration. While handheld LIBS instruments offer compactness and convenience, they suffer from reduced laser energy and spectrometer performance, potentially compromising analytical accuracy. There is an urgent demand for a miniaturized LIBS instrument that retains the high analytical capabilities of laboratory-based LIBS while incorporating the portability of handheld LIBS. This study proposes a compensation method for the performance loss of miniaturized LIBS instruments due to their reduced size. We designed six experimental setups of different sizes to compare rock spectra and classification accuracy in detail, aiming to validate the performance loss of a miniaturized LIBS instrument. In our experiments, the miniaturized LIBS instrument, equipped with an MPL-H-1064 laser and an AvaSpec Mini2048 spectrometer, was employed to classify 16 types of rocks using the SVM model, achieving an initial classification accuracy of 77.08%. To compensate for the performance loss inherent in miniaturized LIBS instruments, a range of preprocessing methods and principal component analysis (PCA) were employed to enhance spectral quality and elevate the accuracy of rock classification to 96.25%. Additionally, the Optuna framework was used to automatically search for the optimal hyperparameters of the SVM model, subsequently increasing the accuracy of rock classification to 99.58%. The results demonstrate that this method effectively mitigates the performance loss of miniaturized LIBS instruments and achieves precise rock classification.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 715-726"},"PeriodicalIF":3.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In situ calcium isotope analysis of Sr-rich carbonates using laser ablation multi-collector inductively coupled plasma mass spectrometry","authors":"Jiao Jiang, Wei Chen, Jue Lu, Yonghong Liu, Ming Li, Jian Sun, Kuidong Zhao, Shaoyong Jiang and Yongsheng Liu","doi":"10.1039/D4JA00289J","DOIUrl":"https://doi.org/10.1039/D4JA00289J","url":null,"abstract":"<p >The <em>in situ</em> Ca isotopic composition of carbonates serves as a fundamental tool for tracing geological and biological processes. However, doubly charged Sr ions pose significant interference challenges in Ca isotope measurement using laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). This study reports a method established for high-precision Ca isotope microanalysis in Sr-rich carbonates. Instrumental parameters including gas flow, torch position and laser settings were optimized to minimize the yield of doubly charged Sr ions. The two key factors involved in the correction strategy for Sr<small>²⁺</small> interference are the true <small>⁸⁷</small>Sr/<small>⁸⁶</small>Sr ratio and the mass fractionation coefficient of Sr<small>²⁺</small>. The accuracy required for the true Sr isotope ratios of carbonates for interference correction depends on the Sr/Ca ratio, <em>e.g.</em>, a variation in <small>⁸⁷</small>Sr/<small>⁸⁶</small>Sr of 0.005 (SD) can lead to a deviation in <em>δ</em><small>⁴⁴</small>/<small>⁴²</small>Ca<small>_915a</small> of approximately 0.1‰ for samples with <small>⁸⁷</small>Sr<small>²⁺</small>/<small>⁴⁴</small>Ca<small>⁺</small> of 10<small>⁻³</small>. The fractionation coefficients for Sr<small>²⁺</small> and Sr<small>⁺</small> were found to differ, and adopting <em>f</em><small>⁺</small><small>_Sr</small> in the correction results in a deviation of <em>δ</em><small>^44/42</small>Ca<small>_915a</small> up to 0.42‰ for calcite with a Sr/Ca ratio of 0.057. Utilizing the iteratively calculated Ca<small>⁺</small> fractionation coefficient improved the accuracy and precision of Ca isotope microanalysis. The resulting <em>in situ</em> Ca isotopic compositions of dolomite and calcite with Sr/Ca ratios up to 0.057 were consistent with those obtained <em>via</em> SN-MC-ICP-MS, with precisions of <em>δ</em><small>⁴⁴</small>/<small>⁴²</small>Ca<small>_915a</small> and <em>δ</em><small>⁴³</small>/<small>⁴²</small>Ca<small>_915a</small> in the ranges of 0.10–0.19‰ and 0.09–0.12‰ (2SD). The method was further validated through microanalysis of calcite from the Miaoya carbonatite-associated REE-Nb deposit, revealing distinct isotopic signatures indicative of magmatic-hydrothermal evolution.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 4","pages":" 975-988"},"PeriodicalIF":3.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Real-time elemental analysis of liquids for process monitoring using laser-induced breakdown spectroscopy with a liquid wheel sampling approach†‡","authors":"H. B. Andrews, Z. B. Kitzhaber, B. T. Manard, M. Z. Martin and L. R. Sadergaski","doi":"10.1039/D4JA00393D","DOIUrl":"https://doi.org/10.1039/D4JA00393D","url":null,"abstract":"<p >This article presents an engineered sampling system that used a rotating wheel to form a thin liquid layer, permitting the use of laser-induced breakdown spectroscopy (LIBS) for <em>in situ</em>, real-time elemental impurity quantification during liquid processing. The sampling approach was demonstrated on eight elements from across the periodic table (Na, Al, K, Ca, Ti, Sr, Mo, and Yb). Univariate and multivariate calibrations were presented for each element. The average value for percent root mean square errors of cross-validation for the multivariate models was 3.64%, highlighting the method's strong prediction accuracy. Additionally, the limits of detection for each analyte were estimated from their univariate models: Na = 0.0532, Al = 18.5, K = 0.105, Ca = 0.273, Ti = 67.7, Sr = 0.640, Mo = 22.4, and Yb = 22.9 μg mL<small>⁻¹</small>. Finally, a test in which multivariate models were used to monitor a liquid system for 80 min was performed to investigate the real-time monitoring capabilities of this liquid LIBS sampling approach. Rigorous measurements were performed to effectively predict the absence and concentrations of multiple analytes as they were spiked and diluted. This demonstration showed the feasibility of using LIBS for real-time liquid quantification models with estimated precision ≤ 8.1%. Finally, the limitations of this approach and potential future improvements are discussed.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 689-699"},"PeriodicalIF":3.1,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d4ja00393d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553598","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accuracy enhancement of laser-induced breakdown spectroscopy using a combination of a confinement ring and quadrupole discharge arc","authors":"Kaiqiang Yu, Yeping Ren, Xiaodong Liu, Xiaoning Yang, Haohan Sun, An Li, Yumei Wu, Caihao Ding, Xianshuang Wang and Ruibin Liu","doi":"10.1039/D4JA00413B","DOIUrl":"https://doi.org/10.1039/D4JA00413B","url":null,"abstract":"<p >The critical issue in laser-induced breakdown spectroscopy (LIBS) research is the uncertainty of the spectral signal and insufficient quantitative analysis accuracy. Spectral enhancement methods, such as discharge assistance and plasma spatial confinement, have been investigated as effective ways to increase analytical accuracy of LIBS. On this basis, this work develops a novel spectroscopic enhancement system that integrates a coaxial optical path, quadrupole discharge arc and confinement ring. A quadrupole discharge arc is utilized to generate a more uniform electric field around the sample to improve the stability of the discharge. Combined with a confinement ring, spectral signal stability and intensity can be further improved. Moreover, discharge arc parameters and dimensions of the confinement ring have been optimized to achieve better signal enhancement, resulting in an 11.96 times increase in signal intensity, a 29.14% reduction in relative standard deviation (RSD), and an improvement in the signal-to-noise ratio (SNR) from 52.1 to 205.6. Based on the enhanced spectrum, the accuracy and robustness of the quantitative analysis model for ash, volatile matter, and calorific value in coal samples are greatly improved, with the root mean square error (RMSE) for the test set decreasing from 1.45%, 0.489%, and 0.468 MJ kg<small>⁻¹</small> to 1.09%, 0.361%, and 0.345 MJ kg<small>⁻¹</small>, respectively, and for the robustness test set decreasing from 1.36%, 0.395%, and 0.441 MJ kg<small>⁻¹</small> to 0.921%, 0.312%, and 0.353 MJ kg<small>⁻¹</small>. Our work proposes a promising coupled enhancement method to improve the detection accuracy of LIBS, characterized by a straightforward, cost-effective setup with potential for industrial application.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 901-909"},"PeriodicalIF":3.1,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Additive manufacturing in space research: hybrid mass analyser for laser ablation ionisation mass spectrometry.","authors":"Andreas Riedo, Peter Keresztes Schmidt, Nikita J Boeren, Salome Gruchola, Luca N Knecht, Marek Tulej, Peter Wurz","doi":"10.1039/d4ja00392f","DOIUrl":"10.1039/d4ja00392f","url":null,"abstract":"<p><p>Additive manufacturing has found its way into many industrial and academic areas. In this contribution, we present an additively manufactured reflectron, integrated in a space-prototype mass analyser used in laser ablation ionisation mass spectrometry. Fused deposition modelling technology was applied to produce the reflectron's ion optical system. For the insulating parts, polylactic acid filament was used as printing material, while the conductive ion optical parts were printed using polylactic acid impregnated with carbon. Measurements were conducted on a stainless steel sample (AISI 316 L, 1.4435) and NIST SRM 661 sample to validate the performance of the reflectron. We found that this system performed nominally in terms of mass resolution and detection sensitivity. This demonstrates the suitability of 3D printing for rapid prototyping in laboratory environments. The latter is of considerable importance for future space exploration missions, as the methodology allows testing of new designs time efficiently and at reduced costs.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11795248/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of a new olivine reference material by a novel method for in situ iron and magnesium isotope analyses using laser ablation MC-ICP-MS†","authors":"Xianli Zeng, Ming Li, Wen Zhang, Hongyun Jin, Yongsheng Liu, Zhaochu Hu, Tao Luo, Shengjun Yang, Zhenyan Liu and Jingyuan Wang","doi":"10.1039/D4JA00422A","DOIUrl":"https://doi.org/10.1039/D4JA00422A","url":null,"abstract":"<p >Olivine is an important rock-forming mineral, and its stable Fe and Mg isotopes provide important indications for identifying important geological processes. <em>In situ</em> Fe and Mg isotopic analyses using laser ablation multiple-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) have proven to be a powerful strategy for examining isotopic variations in olivine growth zoning. However, the advancement of this technology has been limited by the lack of matrix-matched reference materials. In this study, we developed an efficient protocol for preparing olivine reference materials by combining ultrafine powder preparation and solid-phase sintering techniques, specifically designed for Fe–Mg isotope analyses. The synthesized olivine sample, CUG-OL-Ar, retained the initial chemical properties and showed good laser ablation behavior and a stable signal profile. The ANOVA assessment demonstrated the excellent homogeneity of Fe and Mg isotope compositions in CUG-OL-Ar in different batches. The solution-MC-ICP-MS methods were used to determine the Fe and Mg isotope ratios in CUG-OL-Ar, while the uncertainties of Fe and Mg isotope ratios were calculated based on the ISO GUIDE. The assigned values of <em>δ</em><small>⁵⁶</small>Fe<small>_IRMM-014</small> and <em>δ</em><small>²⁵</small>Mg<small>_SC</small> isotopes in CUG-OL-Ar were 0.00 ± 0.06‰ (2SD, <em>n</em> = 350) and 0.00 ± 0.05‰ (2SD, <em>n</em> = 350), respectively. The good results obtained through measuring Fe and Mg isotopes in different types of reference materials using LA-MC-ICP-MS with CUG-OL-Ar as the external standard proved the practicability and reliability of CUG-OL-Ar.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 888-900"},"PeriodicalIF":3.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Challenges in measuring nanoparticles and microparticles by single particle ICP-QMS and ICP-TOFMS: size-dependent transport efficiency and limited linear dynamic range†","authors":"Madeleine Lomax-Vogt, Lucas M. Carter, Jonas Wielinski, Stanislav Kutuzov, Gregory V. Lowry, Ryan Sullivan, Paolo Gabrielli and John W. Olesik","doi":"10.1039/D4JA00425F","DOIUrl":"10.1039/D4JA00425F","url":null,"abstract":"<p >While spICP-MS has been used mainly to measure nanoparticles, it can also be used to measure microparticles. The transport efficiency of nanoparticles is typically independent of their size. However, the transport efficiency of microparticles can be particle size (mass) dependent as well as being dependent on the sample uptake rate and sample introduction system used. To measure both nanoparticles and microparticles a very large linear dynamic range (where signal intensity is linearly proportional to the measured analyte(s) mass within a very short measurement time (∼300 to 500 µs, the width of signals produced by an individual particle)) is needed. Deviations from linearity could occur due to incomplete particle vaporization or from signals that are beyond the instrument's ion detection system linear dynamic range. To characterize and determine the cause of nonlinearity we measured sets of nearly monodisperse engineered SiO<small>₂</small> particles with diameters from 500 to 5000 nm and Au particles with diameters from 60 to 1500 nm. We found that by reducing the sensitivity (up to a factor of 269×) the upper end of the linear dynamic range, in particle size that produced signal intensities that were linearly proportional to the particle (analyte) mass, could be greatly extended. Not surprisingly, reducing the sensitivity increased the minimum size detectable particle. The results are consistent with SiO<small>₂</small> particles as large as 5000 nm being completely vaporized in the ICP.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 848-859"},"PeriodicalIF":3.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11809140/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An isotope dilution approach for validating the output of mercury gas generators for mercury pollution monitoring†","authors":"Sophie Page, Philip J. H. Dunn, Panayot Petrov, Sreekanth Vijayakumaran Nair, Igor Živković, Milena Horvat, Warren T. Corns and Heidi Goenaga-Infante","doi":"10.1039/D4JA00373J","DOIUrl":"https://doi.org/10.1039/D4JA00373J","url":null,"abstract":"<p >Mercury (Hg) gas generators produce a continuous flow of Hg vapour and are used to calibrate detectors used in the field for Hg pollution monitoring. Typically, Hg gas generators are certified using empirical equations such as Dumarey or Huber which lead to results that can differ considerably and lack traceability. This work presents, for the first time, a novel online gas phase isotope dilution (IDMS) method for the accurate quantification of the output of Hg gas generators achieving SI traceability <em>via</em> NIST SRM 3133 certified reference material. To achieve this, a <small>¹⁹⁹</small>Hg isotopically enriched standard was vapourised using a cold vapour generator and mixed with the gaseous output of a Hg gas generator. The <small>²⁰²</small>Hg/<small>¹⁹⁹</small>Hg ratio of the gaseous blend was then measured by ICP-MS, and the generator output calculated using a single IDMS equation adapted for gas mixtures. The efficiency of the <small>¹⁹⁹</small>Hg vapour generation is a key contributing parameter to the measurement uncertainty and was therefore quantified using a <small>¹⁹⁷</small>Hg radiotracer and found to be greater than 99.5%. The feasibility of this method for validating the output of Hg gas generators was demonstrated by quantifying the output of one elemental Hg at an Hg flow of approximately 32 ng L<small>⁻¹</small> and one oxidised Hg gas generator at an Hg flow of approximately 4 ng L<small>⁻¹</small>. In both cases, a relative expanded uncertainty (<em>k</em> = 2) of less than 9% was obtained. This method represents an important step towards improving the traceability, and therefore comparability of measurements for gaseous Hg which are essential for global environmental monitoring and reduction of atmospheric Hg pollution.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 785-794"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d4ja00373j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"No significant crystal orientation effect during sulfur isotope analysis of marcasite using SIMS†","authors":"Rucao Li, Jinyu Yan, Jianwei Yu, Xiao-Lei Wang, Tao Yang, Shengping Qian, Chengming Wang and Haiyang Xian","doi":"10.1039/D4JA00367E","DOIUrl":"https://doi.org/10.1039/D4JA00367E","url":null,"abstract":"&lt;p &gt;The sulfur isotopic composition of marcasite (FeS&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;, orthorhombic), a dimorph of pyrite (FeS&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;, isometric), can be used to trace ore-forming fluid source(s) and ocean acidification events in deep time. However, matrix-matched standards for marcasite are scarce, and in practice, a pyrite standard is commonly used to calibrate the sulfur isotope ratio of marcasite during laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) and secondary ion mass spectrometry (SIMS) analyses. Recently, it has been suggested that it is feasible to calibrate the sulfur isotope ratio of marcasite with a pyrite standard during SIMS analysis, but the crystal orientation effect during sulfur isotope analysis of marcasite using SIMS remains unexplored. We investigated this topic by analyzing a natural marcasite sample (NJUMc-1). We analyzed NJUMc-1 using LA-MC-ICP-MS and SIMS. The analysis spots for LA-MC-ICP-MS and SIMS were very close to each other, and both spots were located in domains with the same brightness in backscattered electron images (BSE). The results derived from these two methods lie around a 1 : 1 line in a &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;LA-MC-ICP-MS&lt;/sub&gt;&lt;/small&gt;&lt;em&gt;vs. δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;SIMS&lt;/sub&gt;&lt;/small&gt; binary diagram, indicating that SIMS data are comparable to LA-MC-ICP-MS data. However, there are some grains in which &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;LA-MC-ICP-MS&lt;/sub&gt;&lt;/small&gt; deviates from &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;SIMS&lt;/sub&gt;&lt;/small&gt; (“&lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;LA-MC-ICP-MS_NJU&lt;/sub&gt;&lt;/small&gt; − &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;SIMS&lt;/sub&gt;&lt;/small&gt;” &gt;+2‰ or &lt;−2‰). This discrepancy possibly indicates a crystal orientation effect during SIMS analysis. To confirm whether there is a crystal orientation effect during SIMS analysis, we conducted a second round of LA-MC-ICP-MS analysis in Beijing and selected two sets of NJUMc-1 marcasite grains and conducted electron backscatter diffraction (EBSD) analysis. For the first set of NJUMc-1 grains, characterized by variable “&lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;LA-MC-ICP-MS_Beijing&lt;/sub&gt;&lt;/small&gt; − &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;SIMS&lt;/sub&gt;&lt;/small&gt;” values, there is no correlation between crystal orientation and “&lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;LA-MC-ICP-MS_beijing&lt;/sub&gt;&lt;/small&gt; − &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;SIMS&lt;/sub&gt;&lt;/small&gt;” values. For the second set of NJUMc-1 grains, characterized by “&lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;LA-MC-ICP-MS_Beijing&lt;/sub&gt;&lt;/small&gt; − &lt;em&gt;δ&lt;/em&gt;&lt;small&gt;&lt;sup&gt;34&lt;/sup&gt;&lt;/small&gt;S&lt;small&gt;&lt;sub&gt;SIMS&lt;/sub&gt;&lt;/small&gt;” values around 0‰, highly variable crystal orientations are observed. These findings suggest that if a crystal orientation effect exists during SIMS analysis, it should b","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 775-784"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Data augmentation using GANN in the quantitative LIBS analysis of scarce samples: a case study on polymetallic nodules from 5000 m ocean depth","authors":"Jie Ren, Suming Jiang, Chen Sun, Zhenggang Li, Yanhui Dong, Ling Chen, Xibin Han, Jin Yu and Wendong Wu","doi":"10.1039/D4JA00412D","DOIUrl":"https://doi.org/10.1039/D4JA00412D","url":null,"abstract":"<p >As the world transitions towards renewable energy, the demand for critical resources such as nickel (Ni), cobalt (Co), and lithium (Li) in energy storage systems is ever more pronounced. The abundance of these elements in deep-sea polymetallic nodules provide an alternative to the land-based resources. However, the scarcity of deep-sea nodule samples poses a challenge in obtaining sufficient Laser-Induced Breakdown Spectroscopy (LIBS) data to train machine learning models for quantitative analysis. In this work, a Generative Adversarial Neural Network (GANN) with physical loss constraints was designed to augment the spectral database. Unsupervised classification techniques, including Principal Component Analysis (PCA) and Density-Based Spatial Clustering of Applications with Noise (DBSCAN), were employed to assess the similarity between experimental and generated spectra. Four machine learning models—Backpropagation Neural Networks (BPNN), Support Vector Machines (SVM), Extreme Gradient Boosting (XGBoost), and Convolutional Neural Networks (CNN)—were selected to represent a broad spectrum in current machine learning methods. Both experimental and expanded spectral datasets were used to train these models in quantitative elemental analysis. The model prediction performance was validated by comparing the results with those of inductively coupled plasma mass spectrometry (ICP-MS). The results demonstrated that augmenting the spectral database with GANN generated spectra improves the accuracy of machine learning models in the quantitative analysis of Ni, Co, and Li in deep-sea polymetallic nodules, providing a valuable approach for LIBS-based analysis of scarce samples.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 3","pages":" 825-835"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143553630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}