Journal of Analytical Atomic Spectrometry最新文献

{"title":"Application of a local outlier detection algorithm based on high-dimensional subspaces in near-infrared spectroscopy","authors":"Jinfeng Zhang, Yuhua Qin, Hao Zhang, Weiyao Hu and Xiaoli Bai","doi":"10.1039/D4JA00366G","DOIUrl":"https://doi.org/10.1039/D4JA00366G","url":null,"abstract":"<p >Due to the high dimensionality and non-linearity of the near infrared (NIR) spectral data, measuring outliers becomes difficult. During the near-infrared spectrum collection process, outliers usually appear due to factors such as uneven distribution of samples, environmental changes, measurement instrument deviations, improper operation, <em>etc.</em> These outliers will bias the direction predicted by the model, making the model prediction results unreliable. Therefore, it is necessary to eliminate the outliers in the process of near-infrared modeling to improve the accuracy of the model. This paper proposes an outlier detection algorithm based on high-dimensional subspaces. This algorithm first introduces a new method for determining local subspaces, which combines local sparsity with adaptive neighborhood selection to determine the local subspace. At the same time, we use the concept of jump degree to adaptively determine the anomaly threshold, thereby achieving the recognition of outliers. In order to investigate the effectiveness of the algorithm, a comparison was made with commonly used PCA-Mahalanobis distance, spectral residual (SR), and leverage method in terms of projection performance, to test the accuracy of the algorithm in distinguishing outliers. In addition, to verify the accuracy in processing high-dimensional data, we compared LoOP and SOD with our method. The experimental results showed that the subspace-based outlier detection method effectively improved the performance of outlier identification and calibration for NIR analysis.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2548-2555"},"PeriodicalIF":3.1,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909599","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":"Design and analysis of a spectral imaging detection instrument based on a digital micromirror device†","authors":"Tingwen Gu, Ziheng Xu, Zihan Wang, Junjie Huang, Guang Yang and Chunsheng Li","doi":"10.1039/D5JA00160A","DOIUrl":"https://doi.org/10.1039/D5JA00160A","url":null,"abstract":"<p >We present the design of a spectral imaging inspection instrument based on a Digital Micromirror Device (DMD). The instrument utilizes an enhanced optical path that is compatible with the near-ultraviolet spectrum. The optical path design leverages the flexibility and high reliability of DMDs to enable precise control over spatial light modulation and spectral wavelength selection. Additionally, we evaluated the instrument's spectral range and spatial resolution using a mercury lamp and a resolution plate. The results indicate that the instrument operates within the 250–500 nm range, with a spatial resolution of up to 35 μm. Finally, we use the plasma generated by the Laser-Induced Breakdown Spectroscopy (LIBS) instrument as the observed sample. Instrumental observations reveal subtle spatio-temporal variations in the plasma across different spectral lines.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2573-2581"},"PeriodicalIF":3.1,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909583","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":"Quantification of cadmium, rhenium and thallium in low-content samples via isotope dilution ICP-MS combined with single-step anion exchange preconcentration","authors":"Jia-Lu Wang, Qiao-Hui Zhong, Zhao-Yang Wang, Lu Yin, Jia-Kai Guo, Zhi-Bing Wang and Jie Li","doi":"10.1039/D4JA00458B","DOIUrl":"https://doi.org/10.1039/D4JA00458B","url":null,"abstract":"<p >Cadmium (Cd), rhenium (Re) and thallium (Tl) are dispersed metals that serve as geochemical tracers for various geological and environmental processes. Both Cd and Tl exhibit high toxicity and slow metabolic clearance rates, posing risks to plants, animals, and humans. Determining their concentrations in natural samples is challenging due to their low abundance, especially in water samples where concentrations are typically in the range of ng L<small>⁻¹</small> to μg L<small>⁻¹</small>. In this study, we developed a simple, efficient and robust method for the simultaneous separation and quantification of Cd, Re and Tl from a single sample aliquot using an anion exchange resin. Concentrations were subsequently measured by isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). The validity of this method was demonstrated through repeated analysis of reference materials BHVO-2, BIR-1a and GBW07105 (GSR-3). The results are consistent with previously published values within errors, including precision and accuracy. Additionally, the standard deviations of our concentration measurements are less than 1.49% for Cd, 3.83% for Re, and 1.63% for Tl in in-house water samples. The optimized approach was applied to river samples collected from the Pearl River tributaries. These investigations demonstrate that our sample purification and ID-ICP-MS measurement methods are effective for the quantitative determination of Cd, Re, and Tl concentrations in both rock and river samples. Our study enhances understanding of the aquatic geochemistry of Cd, Re, and Tl, thereby enhancing our ability to predict trace-element dynamics in hydrosystems.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 8","pages":" 2232-2242"},"PeriodicalIF":3.1,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740076","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":"High-precision Fe isotope analysis for low contents using a Nu Sapphire instrument†","authors":"Kai Yang, Hongfu Zhang, Jinjun Zhou, Qiwen Ying, Shenghua Zhou, Yishan Cheng, Xiping Wei, Xiaoyan Gu, Qunke Xia and Jia Liu","doi":"10.1039/D5JA00225G","DOIUrl":"https://doi.org/10.1039/D5JA00225G","url":null,"abstract":"<p >Iron (Fe) isotopes serve as a powerful tracer for studying planetary evolution, magmatic processes, redox conditions, biological activities, and other key geological processes. However, the application of stable Fe isotopes in depleted-Fe samples has been significantly constrained by pervasive argon-related isobaric interferences inherent to conventional multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). This study purified rock samples with varying Fe concentrations and precisely measured Fe isotope ratios using the collision cell pathway in the low-resolution mode of the Nu Sapphire instrument. We systematically evaluated the effects of total Fe concentration in solution, Fe signal intensity mismatch between samples and standards, and HNO<small>₃</small> molarity differences on measurement precision and accuracy. For precise Fe isotope ratio measurements using sapphire, strict analytical conditions must be met: (1) matched nitric acid concentrations between samples and bracketing standards (1% deviation induces 0.2‰ Fe isotope offset); (2) consistent Fe signal intensities (5% concentration mismatch introduces 0.05‰ bias); and (3) suppression of matrix interferences to minimize isotopic fractionation. The results demonstrate that the Nu Sapphire can achieve precise measurements with as little as 1 μg of Fe, representing a tenfold improvement relative to conventional instruments. The Fe isotopic data obtained for 13 geological references show good agreement with previous studies. Therefore, the exceptional sensitivity of Nu Sapphire facilitates high-precision Fe isotope ratio measurements for iron-depleted samples, offering broad application potential.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2418-2425"},"PeriodicalIF":3.1,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909573","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":"Quantification of laser-induced aerosols by microdroplet calibration and investigation of matrix effects using LA-ICP-TOFMS†","authors":"Tobias Schöberl, Mirjam Bachmann and Detlef Günther","doi":"10.1039/D5JA00171D","DOIUrl":"10.1039/D5JA00171D","url":null,"abstract":"<p >The application of monodisperse microdroplets for non-matrix-matched quantification in LA-ICP-TOFMS was investigated for inorganic and organic matrices. Suppression behavior in droplet signals caused by addition of typical major elements of geological samples (Al, Si, Ca, Ti, and Fe) in the μg g<small>⁻¹</small> range was studied using microdroplets introduced <em>via</em> a falling tube and compared to solution nebulization. Signal suppression patterns observed for microdroplets could be attributed to neither mass load effects nor in-plasma oxide formation, nor reproduced <em>via</em> solution nebulization, suggesting a fundamentally different behavior of microdroplets in the plasma. Radial diffusion profiles were acquired to assess in-plasma behavior of droplets and laser-induced aerosol from NIST SRM 610 (glass). Diffusion profiles overlapped and showed similar full width at half maxima (FWHM) for microdroplets and the laser-induced aerosol, with minor spatial shifts in intensity maxima, likely due to not complete on-axis droplet introduction into the plasma. Quantification based on microdroplet calibration yielded relative deviations from reference values below ±20% across certified reference materials and an in-house prepared gelatine standard. Quantification of gelatine samples using NIST SRM 610 (glass) as an external standard resulted in larger deviations compared to droplet-based calibration, which yielded values in agreement with digestion data. These results demonstrate the suitability of monodisperse microdroplets for non-matrix-matched calibration in LA-ICP-TOFMS, particularly for elements non-certified or uncommonly reported in reference materials used in LA-ICP-MS.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2438-2446"},"PeriodicalIF":3.1,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12320928/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792991","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":"Analysis of high purity boron carbide by solid sampling graphite furnace atomic absorption spectrometry†","authors":"Edson I. Muller, Paola A. Mello, Thiago C. Pereira, Rodrigo C. Bolzan and Erico M. M. Flores","doi":"10.1039/D5JA00131E","DOIUrl":"https://doi.org/10.1039/D5JA00131E","url":null,"abstract":"<p >An alternative method for the determination of metallic impurities in high purity boron carbide (B<small>₄</small>C) using solid sampling graphite furnace atomic absorption spectrometry (SS-GFAAS) was proposed. The feasibility of using a Zeeman-effect background correction system operating with a variable magnetic field (VMF) was evaluated to provide a large working range for Al, Cr, Cu, Mn and Ni determination in B<small>₄</small>C samples. The following parameters were evaluated: pyrolysis and atomization temperatures, sample mass, as well as the use of alternative wavelengths for Al and Mn. As an important achievement, calibration using aqueous standard solutions was feasible and chemical modifiers were not necessary. However, it was observed that the use of graphite powder to cover the sample platform avoided the damage of the pyrolytic layer of the graphite platform. Working ranges from 0.01 to 1500 μg g<small>⁻¹</small> were obtained for the metallic impurity determination by SS-GFAAS. Sample masses up to 2.5 mg were used providing limits of detection ranging from 0.003 to 1 μg g<small>⁻¹</small>, with a RSD lower than 17%. The accuracy was evaluated using the B<small>₄</small>C certified reference material (BAM/ERM-ED 102) and by comparison of the results obtained by microwave-assisted-wet digestion and alkaline fusion with subsequent determination by inductively coupled plasma optical emission spectrometry (ICP-OES). No differences were observed between the results obtained by SS-GFAAS and those by ICP-OES after both digestion methods (<em>t</em>-test, 95% confidence level). Additionally, the results presented no significant differences with the values of the certified reference material. The proposed SS-GFAAS method allowed quality control related to determination of Al, Cr, Cu, Mn and Ni in B<small>₄</small>C with a large working range and limits of detection lower than those achieved by other methods reported in the literature.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2498-2506"},"PeriodicalIF":3.1,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909595","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":"Elemental composition analysis of electronic waste using neutron-based analytical techniques: a novel approach to assessing environmental and resource recovery potential†","authors":"Noémi Anna Buczkó, Boglárka Maróti, Katalin Gméling and László Szentmiklósi","doi":"10.1039/D5JA00233H","DOIUrl":"https://doi.org/10.1039/D5JA00233H","url":null,"abstract":"<p >Development of environmentally friendly technologies and assessing economic return for electronic waste recycling require the determination of the mass fractions of valuable, critical, and hazardous elements in e-waste. Neutron-based analytical methods have rarely been applied to this task so far, despite their merits, such as multi-element analysis of solid samples without dissolution and no need for matrix-matched calibration. In this study, instrumental neutron activation analysis, prompt-gamma neutron activation analysis and in-beam neutron activation analysis techniques were applied to determine the elemental composition of two major e-waste types, printed circuit boards and integrated circuits. With a proper analysis strategy, most metallic and non-metallic elements relevant to the circular economy were measurable, or adequate detection limits could be obtained.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2385-2396"},"PeriodicalIF":3.1,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909570","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":"Discrimination of subtypes and stages of non-Hodgkin lymphomas using serum laser-induced breakdown spectroscopy†","authors":"Xiaohui Li, Xinxin Zhang, Xue Chen, Zihao Guo and Yumeng Yuan","doi":"10.1039/D5JA00212E","DOIUrl":"https://doi.org/10.1039/D5JA00212E","url":null,"abstract":"<p >Non-Hodgkin lymphomas (NHLs) are a major group of lymphomas. Accurate diagnosis of subtypes and stages of NHLs plays an important role in clinical practice for precise treatment and prognosis evaluation of the disease. In this work, serum laser-induced breakdown spectroscopy (serum LIBS) was applied to discriminate two major subtypes of NHLs, namely, diffuse large B-cell lymphoma (DLBCL) and follicular lymphoma (FL). Serum samples from confirmed patients with DLBCLs and FLs, and healthy normal controls (NCs) were collected for LIBS measurements. For DLBCLs, both germinal center B-cell (GBC) and activated B-cell (ABC) originated subgroups were included, each subgroup containing samples at different progressive stages. The serum samples were deposited onto silicon substrates, naturally dried, and ablated with a focused Nd:YAG laser to generate laser-induced plasmas. The spectral intensities of typical elemental emissions from the plasmas were compared among DLBCLs, FLs and NCs, between the GBC- and ABC-originated DLBCL subgroups, and among different stages. The <em>k</em> nearest neighbors and support vector machine classifiers were used to discriminate the two subtypes of NHLs, to classify the originating B-cell subgroups of DLBCLs, and to stage within the GBC- and ABC-originated DLBCL subgroups. Accuracy of about 90% was achieved for discrimination of DLBCLs and FLs, about 88% for classification of the GBC- and ABC-originated DLBCLs, and about 92% and 85% for staging within the GBC- and ABC-originated DLBCL subgroups, respectively. The results show that the serum LIBS supported by chemometric methods could be a potential solution for discrimination of subtypes of NHLs, and for diagnosis and staging of DLBCLs. The serum LIBS may help to diagnose the NHLs in a minimally invasive, rapid and cost-effective way, and to provide valuable references for precise treatment and prognosis prediction of the disease.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 9","pages":" 2397-2407"},"PeriodicalIF":3.1,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909571","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":"Stable carbon isotope analysis of fluorinated organic compounds using infrared spectrometer coupled to gas chromatography†","authors":"Xinyi Du, Biao Jin, Hans H. Richnow, Lingling Zhang, Shutao Gao, Zhiqiang Yu and Ping'an Peng","doi":"10.1039/D5JA00168D","DOIUrl":"https://doi.org/10.1039/D5JA00168D","url":null,"abstract":"<p >Compound-specific isotope analysis (CSIA) is a powerful tool for tracing the sources and transformation processes of organic pollutants. With the rising concern on fluorinated organic compounds, there is a pressing need to develop reliable CSIA methods for determining their carbon isotopic compositions. This study developed a gas chromatography–isotope ratio infrared spectrometer (GC-IRIS) method for carbon CSIA of perfluorinated carboxylic acids and ethers. The <em>δ</em><small>¹³</small>C signatures determined by GC-IRIS were −26.1 ± 0.3‰ for heptafluorobutyric acid, −30.1 ± 0.3‰ for perfluoro-2-butyltetrahydrofuran, −30.2 ± 0.3‰ for trifluoroacetic acid, −41.0 ± 0.2‰ for perfluoropentanoic acid, −45.3 ± 0.2‰ for perfluorobutyl methyl ether, and −55.9 ± 0.4‰ for perfluoropropyl vinyl ether, respectively. Cross-validation using elemental analysis–isotope ratio mass spectrometry (EA-IRMS) confirmed consistency between the two methods, showing good agreement in the <em>δ</em><small>¹³</small>C values, supporting the reliability of the GC-IRIS method. The method was further applied to resolve carbon isotope fractionation during volatilization of perfluorobutyl methyl ether and perfluoro-2-butyltetrahydrofuran, both exhibiting inverse carbon isotope effects. This work reports a novel and robust GC-IRIS method for carbon CSIA of fluorinated compounds, highlighting the potential for characterizing isotopic signatures and environmental behaviors of different fluorinated organic compounds.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 8","pages":" 1940-1945"},"PeriodicalIF":3.1,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740024","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":"Fusion of elemental and molecular fingerprints for accurate classification of kimchi by country of origin†","authors":"Sandeep Kumar, Yujin Oh, Hyemin Jung, Kyung-Sik Ham, Hyun-Jin Kim, Song-Hee Han, Sang-Ho Nam and Yonghoon Lee","doi":"10.1039/D5JA00200A","DOIUrl":"https://doi.org/10.1039/D5JA00200A","url":null,"abstract":"<p >The geographical origin of commercial kimchi products is a key indicator of their quality, authenticity, and economic value. In this study, we propose a spectroscopic classification method combining laser-induced breakdown spectroscopy (LIBS) and infrared (IR) spectroscopy to differentiate kimchi samples from South Korea and China. LIBS was used to obtain elemental profiles based on the emission intensities of K, Mg, Na, Ca, C, H, and O, while IR spectroscopy captured molecular features. Principal component analysis of IR spectra in the carbohydrate absorption region (1254–1018 cm<small>⁻¹</small>) identified the third principal component (PC3) as the most discriminative. Classification models using <em>k</em>-nearest neighbors (<em>k</em>-NN) were evaluated with leave-one-out cross-validation. Two LIBS-only models—using variable sets (i) K I (766 nm), O I (777 nm), C I (248 nm), and (ii) K I, O I, Mg II (279 nm)—achieved 94.4% accuracy. The IR-only model reached 86.4%. Fusion of LIBS and IR features, with optimized weighting for the IR variable, enhanced model performance. The best result (96.8% accuracy) was achieved by combining LIBS variables K I, O I, and C I with IR PC3. We also introduce a statistical method to predict the optimal weighting factor for fusion, reducing computational complexity by minimizing the number of neighbors in <em>k</em>-NN. This LIBS-IR fusion strategy provides a robust tool for verifying kimchi origin.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 8","pages":" 2222-2231"},"PeriodicalIF":3.1,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740075","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}