Spectrochimica Acta Part B: Atomic Spectroscopy最新文献

英文中文

Novel insights on the matrix effect of acid solutions in nitrogen microwave-induced plasma optical emission spectrometry: Analytes signal enhancement in formic acid

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-11 DOI: 10.1016/j.sab.2025.107152

Christiane Duyck , Edmilson Arruda dos Santos , João Victor Soares de Araújo , Thiago Silva Santos , Ricardo Jorgensen Cassella , Rafaella Regina Alves Peixoto

This study evaluated the matrix effect of acid solutions on the nitrogen microwave-induced plasma optical emission spectrometry (N₂-MIP-OES) sensitivity of 24 elements. A model solution of 0.2 % nitric acid was used to compare the element's emission line sensitivity in nitric (1.0 %, and 5.0 %, v v⁻¹), sulfuric (0.2 % and 1 %), hydrochloric, formic, and acetic acid solutions (0.2 %, 1.0 %, and 5.0 %, v v⁻¹). The relative sensitivity was estimated by the linear regression slope (LRS) of signal intensities obtained at eight concentration levels (blank + standards). Principal component analysis (PCA) was applied to the LRS data to distinguish matrix effects. Signal enhancement was noted for a group of elements (Al, As, B, Ba, Cd, Co, Cu, Fe, Mn, Pb, Sr, and Zn) in formic acid solutions (0.2 % and 1 %) and varied from +50 % (Cd, Zn) to +80 % (B, Ba, Pb, Sr) of the corresponding sensitivity in HNO₃ 0.2 %. In contrast, signal suppression occurred for K (−15 %), Ca (−20 %), and Mg (−40 %) and in diluted hydrochloric solutions (0.2 % and 1 %). The ratio values of Mg(II)/Mg(I) and (N₂⁺/OH) used in robustness metrics increased in these solutions, indicating higher robustness. An increase in CO⁺ species formation in the plasma was also observed. Refractory oxide-forming elements (Ce, Cr, La, Mo, Ni, Se, and V) were less impacted by acid matrix effects. This study aimed to contribute to the increasing interest in multi-elemental determination by MIP-OES.

{"title":"Novel insights on the matrix effect of acid solutions in nitrogen microwave-induced plasma optical emission spectrometry: Analytes signal enhancement in formic acid","authors":"Christiane Duyck , Edmilson Arruda dos Santos , João Victor Soares de Araújo , Thiago Silva Santos , Ricardo Jorgensen Cassella , Rafaella Regina Alves Peixoto","doi":"10.1016/j.sab.2025.107152","DOIUrl":"10.1016/j.sab.2025.107152","url":null,"abstract":"<div><div>This study evaluated the matrix effect of acid solutions on the nitrogen microwave-induced plasma optical emission spectrometry (N<sub>2</sub>-MIP-OES) sensitivity of 24 elements. A model solution of 0.2 % nitric acid was used to compare the element's emission line sensitivity in nitric (1.0 %, and 5.0 %, v v<sup>−1</sup>), sulfuric (0.2 % and 1 %), hydrochloric, formic, and acetic acid solutions (0.2 %, 1.0 %, and 5.0 %, v v<sup>−1</sup>). The relative sensitivity was estimated by the linear regression slope (LRS) of signal intensities obtained at eight concentration levels (blank + standards). Principal component analysis (PCA) was applied to the LRS data to distinguish matrix effects. Signal enhancement was noted for a group of elements (Al, As, B, Ba, Cd, Co, Cu, Fe, Mn, Pb, Sr, and Zn) in formic acid solutions (0.2 % and 1 %) and varied from +50 % (Cd, Zn) to +80 % (B, Ba, Pb, Sr) of the corresponding sensitivity in HNO<sub>3</sub> 0.2 %. In contrast, signal suppression occurred for K (−15 %), Ca (−20 %), and Mg (−40 %) and in diluted hydrochloric solutions (0.2 % and 1 %). The ratio values of Mg(II)/Mg(I) and (N<sub>2</sub><sup>+</sup>/OH) used in robustness metrics increased in these solutions, indicating higher robustness. An increase in CO<sup>+</sup> species formation in the plasma was also observed. Refractory oxide-forming elements (Ce, Cr, La, Mo, Ni, Se, and V) were less impacted by acid matrix effects. This study aimed to contribute to the increasing interest in multi-elemental determination by MIP-OES.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107152"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403560","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}

引用次数: 0

Outside Front Cover - Journal name, Cover image, Volume issue details, ISSN, Cover Date, Elsevier Logo and Society Logo if required

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-11 DOI: 10.1016/S0584-8547(25)00028-X

引用次数: 0

Acoustic signal in overcoming the matrix effect in LIBS: Toward reliable applicability

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-07 DOI: 10.1016/j.sab.2025.107140

Markéta Bosáková , Karel Novotný , Javier Moros , Javier Laserna

The versatility of laser-induced breakdown spectroscopy (LIBS) resulting from its advantageous analytical characteristics is, unfortunately, still limited by challenges inherent to the fundamental principles of the method – the processes of laser ablation and laser-induced plasma generation. Unwanted effects (generally known as matrix effects) significantly decrease the analytical performance of LIBS, complicating quantification and impairing reproducibility.

This study investigates acoustic signals accompanying plasmas (LIPAc) to overcome these limitations and enhance LIBS performance. The influence of instrumental (microphone types), operational (laser wavelength and fluence) and sample parameters on acoustic responses were evaluated. The results indicate that laser fluence strongly influences acoustic wave oscillation. When laser fluence substantially exceeds the breakdown thresholds of the different components in the matter, acoustic responses may become identical across various materials. On the other hand, proportionality in differences of acoustic signal is maintained for different microphones and laser wavelength settings.

Promising solutions for eliminating matrix effects on various surfaces were identified, but the suitability and efficiency may be highly dependent on the emission line used. This is demonstrated using the signals of atomic Cu(I) 324.74 nm and ionic Cu(II) 329.04 nm lines measured from an aluminum sample with a partially coppered and partially roughened surface.

Acoustic maps of a galena ore sample demonstrate the applications of LIPAc in spatially resolved LIBS imaging and elemental mapping. These maps can help eliminate the discrepancy between the intensities of the calcium atomic line of Ca(I) at 422.67 nm measured from the galena mineral and calcium carbonate.

{"title":"Acoustic signal in overcoming the matrix effect in LIBS: Toward reliable applicability","authors":"Markéta Bosáková , Karel Novotný , Javier Moros , Javier Laserna","doi":"10.1016/j.sab.2025.107140","DOIUrl":"10.1016/j.sab.2025.107140","url":null,"abstract":"<div><div>The versatility of laser-induced breakdown spectroscopy (LIBS) resulting from its advantageous analytical characteristics is, unfortunately, still limited by challenges inherent to the fundamental principles of the method – the processes of laser ablation and laser-induced plasma generation. Unwanted effects (generally known as matrix effects) significantly decrease the analytical performance of LIBS, complicating quantification and impairing reproducibility.</div><div>This study investigates acoustic signals accompanying plasmas (LIPAc) to overcome these limitations and enhance LIBS performance. The influence of instrumental (microphone types), operational (laser wavelength and fluence) and sample parameters on acoustic responses were evaluated. The results indicate that laser fluence strongly influences acoustic wave oscillation. When laser fluence substantially exceeds the breakdown thresholds of the different components in the matter, acoustic responses may become identical across various materials. On the other hand, proportionality in differences of acoustic signal is maintained for different microphones and laser wavelength settings.</div><div>Promising solutions for eliminating matrix effects on various surfaces were identified, but the suitability and efficiency may be highly dependent on the emission line used. This is demonstrated using the signals of atomic Cu(I) 324.74 nm and ionic Cu(II) 329.04 nm lines measured from an aluminum sample with a partially coppered and partially roughened surface.</div><div>Acoustic maps of a galena ore sample demonstrate the applications of LIPAc in spatially resolved LIBS imaging and elemental mapping. These maps can help eliminate the discrepancy between the intensities of the calcium atomic line of Ca(I) at 422.67 nm measured from the galena mineral and calcium carbonate.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107140"},"PeriodicalIF":3.2,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387074","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}

引用次数: 0

Characterization of electron density and ionization of a uranium laser produced plasma using laser absorption spectroscopy

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-06 DOI: 10.1016/j.sab.2025.107142

Ryland G. Wala , Mathew P. Polek , Sivanandan S. Harilal , R. Jason Jones , Mark C. Phillips

High-resolution tunable laser spectroscopy is used to measure time-resolved absorption spectra for ten neutral uranium transitions and six singly-ionized transitions in a laser produced plasma. Spectral lineshapes are analyzed to determine temporal variations in ion and neutral total column densities, excitation temperatures, kinetic temperatures, and collisional broadening effects as the plasma cools. Comparison of ion to neutral column densities shows a ratio greater than 10 at times

<

15 μs after plasma onset, with the ratio not reaching unity until 50 μs. Spectral lineshapes are analyzed to separate Stark and van der Waals contributions to collisional broadening, from which electron densities are determined and found to decrease from

\sim

10¹⁵–10¹³ cm⁻³ over times from 4–25 μs. Using absorption spectroscopy to determine charge properties and electron density over these time scales and at low magnitudes provides valuable insight into plasma properties not obtainable using conventional emission spectroscopy. Comparisons between ion and neutral densities, excitation temperatures, kinetic temperatures, and electron densities could indicate potential deviations from local thermodynamic equilibrium and Saha ionization predictions.

{"title":"Characterization of electron density and ionization of a uranium laser produced plasma using laser absorption spectroscopy","authors":"Ryland G. Wala , Mathew P. Polek , Sivanandan S. Harilal , R. Jason Jones , Mark C. Phillips","doi":"10.1016/j.sab.2025.107142","DOIUrl":"10.1016/j.sab.2025.107142","url":null,"abstract":"<div><div>High-resolution tunable laser spectroscopy is used to measure time-resolved absorption spectra for ten neutral uranium transitions and six singly-ionized transitions in a laser produced plasma. Spectral lineshapes are analyzed to determine temporal variations in ion and neutral total column densities, excitation temperatures, kinetic temperatures, and collisional broadening effects as the plasma cools. Comparison of ion to neutral column densities shows a ratio greater than 10 at times <span><math><mo><</mo></math></span>15 μs after plasma onset, with the ratio not reaching unity until 50 μs. Spectral lineshapes are analyzed to separate Stark and van der Waals contributions to collisional broadening, from which electron densities are determined and found to decrease from <span><math><mo>∼</mo></math></span>10<sup>15</sup>–10<sup>13</sup> cm<sup>−3</sup> over times from 4–25 μs. Using absorption spectroscopy to determine charge properties and electron density over these time scales and at low magnitudes provides valuable insight into plasma properties not obtainable using conventional emission spectroscopy. Comparisons between ion and neutral densities, excitation temperatures, kinetic temperatures, and electron densities could indicate potential deviations from local thermodynamic equilibrium and Saha ionization predictions.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"227 ","pages":"Article 107142"},"PeriodicalIF":3.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487617","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}

引用次数: 0

Duplication of periodic micro-structure on the surface of a nickel substrate and its application in surface-enhanced laser-induced breakdown spectroscopy

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-06 DOI: 10.1016/j.sab.2025.107139

Zenghui Wang, Yufeng Li, Yuqi Chen, Runhua Li

In order to improve the analytical performance of surface-enhanced laser-induced breakdown spectroscopy (SENLIBS) on the elemental analysis of liquid samples, a 20 μm cylindric rod periodic micro-structure with 20 μm rod diameter, 15 μm rod height and 40 μm periodic length was successfully duplicated on the surface of a nickel substrate using electroplating method. The presence of periodic micro-structure on nickel surface changes the interaction of the laser and substrate; thus, plasma with higher temperature and higher electron density can be generated. The atomic emissions of both analytes and substrates' elements can be significantly enhanced in SENLIBS analysis if compared with that of using a flat substrate without any micro-structures. Mn, Pb, and Cr in aqueous solution samples were quantitatively analyzed by SENLIBS using these surface micro-structured nickel substrates. The detection limit of Mn, Pb, and Cr reached to 107.9 ng/mL, 76.0 ng/mL and 70.5 ng/mL under current experimental condition, respectively. In comparison with that obtained in similar analysis using flat nickel substrates, 4.2–5.1 folds improvement factors on the analytical sensitivity were achieved. This approach demonstrates a cost-effective and convenient method for the substrate preparation and provides a more sensitive elemental analysis of liquid samples by SENLIBS.

{"title":"Duplication of periodic micro-structure on the surface of a nickel substrate and its application in surface-enhanced laser-induced breakdown spectroscopy","authors":"Zenghui Wang, Yufeng Li, Yuqi Chen, Runhua Li","doi":"10.1016/j.sab.2025.107139","DOIUrl":"10.1016/j.sab.2025.107139","url":null,"abstract":"<div><div>In order to improve the analytical performance of surface-enhanced laser-induced breakdown spectroscopy (SENLIBS) on the elemental analysis of liquid samples, a 20 μm cylindric rod periodic micro-structure with 20 μm rod diameter, 15 μm rod height and 40 μm periodic length was successfully duplicated on the surface of a nickel substrate using electroplating method. The presence of periodic micro-structure on nickel surface changes the interaction of the laser and substrate; thus, plasma with higher temperature and higher electron density can be generated. The atomic emissions of both analytes and substrates' elements can be significantly enhanced in SENLIBS analysis if compared with that of using a flat substrate without any micro-structures. Mn, Pb, and Cr in aqueous solution samples were quantitatively analyzed by SENLIBS using these surface micro-structured nickel substrates. The detection limit of Mn, Pb, and Cr reached to 107.9 ng/mL, 76.0 ng/mL and 70.5 ng/mL under current experimental condition, respectively. In comparison with that obtained in similar analysis using flat nickel substrates, 4.2–5.1 folds improvement factors on the analytical sensitivity were achieved. This approach demonstrates a cost-effective and convenient method for the substrate preparation and provides a more sensitive elemental analysis of liquid samples by SENLIBS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107139"},"PeriodicalIF":3.2,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143348992","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}

引用次数: 0

Corrigendum to “Quantitative analysis of coal quality by mutual information-particle swarm optimization (MI-PSO) hybrid variable selection method coupled with spectral fusion strategy of laser-induced breakdown spectroscopy (LIBS) and fourier transform infrared spectroscopy (FTIR)” [Spectrochimica Acta Part B: Atomic Spectroscopy 178 (2021) 106112]

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-05 DOI: 10.1016/j.sab.2025.107135

Ting He , Jing Liang , Hongsheng Tang , Tianlong Zhang , Chunhua Yan , Hua Li

引用次数: 0

Application of total-reflection X-ray fluorescence (TXRF) to study authigenic carbonates in planktonic foraminifera

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-04 DOI: 10.1016/j.sab.2025.107141

Artem S. Maltsev , Galina V. Pashkova , Alena N. Zhilicheva , Alexandra V. Romanova

In this study we present results showing the elemental composition of diagenetic coatings on foraminiferal tests by total-reflection X-ray fluorescence (TXRF) within N. pachyderma diagenetic shells from the Holocene sediments in the Okhotsk Sea. The method includes direct deposition of individual foraminifera of micro-size on the quartz carrier and digestion by 2 N nitric acid on it. The investigation of the specimen prepared shows its suitability for TXRF analysis based on its thickness and the distribution of particles within. The quantification of elements is based on the standardless method, but the elements with atomic number Z < 13 were not determined since the measurement is made in air. Since the total composition of the sample was not calculated, the element concentrations were accepted only as relative. Precision values did not exceed 10 % for all elements. 14 types of foraminifera shells (129 samples in total) were analyzed by the TXRF method and the following elements were determined: Cl, K, Ca, Mn, Fe, Zn, Sr. Application of principal component analysis showed the difference among samples with a respect to diagenetic alternation degree. The results of diagenetic studies were confirmed by literature data.

{"title":"Application of total-reflection X-ray fluorescence (TXRF) to study authigenic carbonates in planktonic foraminifera","authors":"Artem S. Maltsev , Galina V. Pashkova , Alena N. Zhilicheva , Alexandra V. Romanova","doi":"10.1016/j.sab.2025.107141","DOIUrl":"10.1016/j.sab.2025.107141","url":null,"abstract":"<div><div>In this study we present results showing the elemental composition of diagenetic coatings on foraminiferal tests by total-reflection X-ray fluorescence (TXRF) within <em>N. pachyderma</em> diagenetic shells from the Holocene sediments in the Okhotsk Sea. The method includes direct deposition of individual foraminifera of micro-size on the quartz carrier and digestion by 2 N nitric acid on it. The investigation of the specimen prepared shows its suitability for TXRF analysis based on its thickness and the distribution of particles within. The quantification of elements is based on the standardless method, but the elements with atomic number Z < 13 were not determined since the measurement is made in air. Since the total composition of the sample was not calculated, the element concentrations were accepted only as relative. Precision values did not exceed 10 % for all elements. 14 types of foraminifera shells (129 samples in total) were analyzed by the TXRF method and the following elements were determined: Cl, K, Ca, Mn, Fe, Zn, Sr. Application of principal component analysis showed the difference among samples with a respect to diagenetic alternation degree. The results of diagenetic studies were confirmed by literature data.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"226 ","pages":"Article 107141"},"PeriodicalIF":3.2,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377705","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}

引用次数: 0

High-precision Rb-Sr isotope analysis with Neoma MS/MS: Enhancing in situ geochronology by laser ablation

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-01 DOI: 10.1016/j.sab.2025.107117

Chao Huang , Hao Wang , Liewen Xie , Lei Xu , Shitou Wu , Yueheng Yang , Jinhui Yang

The development of multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) with tandem mass spectrometry (MS/MS) technology has brought significant advancements for in situ Rubidium‑strontium (Rb-Sr) geochronology, coupled with a laser ablation system (LA). This study investigates the potential of high-precision in situ Rb-Sr dating by the Neoma MS/MS instrument, using both solution and LA analysis, with a focus on optimizing instrumental parameters and the evaluating reference materials. We systematically assess the removal of Ar⁺, the influence of Focus Lens 2 voltage on Sr isotope analytical accuracy, and the effectiveness of reaction mode in eliminating isobaric interferences. Results of LA analyses demonstrate the capability of Neoma MS/MS to achieve high-precision in situ Rb-Sr isotope ratio measurements, with external precisions better than 1.9 % and 0.036 % relative standard deviation (RSD) for ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr ratios in standard glasses, respectively. The homogeneity of the Mica-Mg reference material is further assessed, with an inter-session RSD of 0.17 % for its Rb-Sr isochron age, demonstrating good age homogeneity across nine analytical sessions. Similarly, the natural ZMT04 muscovite yielded an inter-session RSD of 0.69 % for its Rb-Sr isochron age, and its Rb-Sr isochron age of 1778.8 ± 4.9 Ma (2 s, n = 180) is consistent with the reported Ar-Ar age (1772.2 ± 2.7 Ma, 2 s) within the uncertainty, confirming its suitability as a monitor reference material for Rb-Sr dating. These findings highlight the potential of the Neoma MS/MS in enhancing the precision of in situ Rb-Sr dating, for micro-scale investigations and revealing intricate age zonation patterns within individual minerals.

{"title":"High-precision Rb-Sr isotope analysis with Neoma MS/MS: Enhancing in situ geochronology by laser ablation","authors":"Chao Huang , Hao Wang , Liewen Xie , Lei Xu , Shitou Wu , Yueheng Yang , Jinhui Yang","doi":"10.1016/j.sab.2025.107117","DOIUrl":"10.1016/j.sab.2025.107117","url":null,"abstract":"<div><div>The development of multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) with tandem mass spectrometry (MS/MS) technology has brought significant advancements for <em>in situ</em> Rubidium‑strontium (Rb-Sr) geochronology, coupled with a laser ablation system (LA). This study investigates the potential of high-precision <em>in situ</em> Rb-Sr dating by the Neoma MS/MS instrument, using both solution and LA analysis, with a focus on optimizing instrumental parameters and the evaluating reference materials. We systematically assess the removal of Ar<sup>+</sup>, the influence of Focus Lens 2 voltage on Sr isotope analytical accuracy, and the effectiveness of reaction mode in eliminating isobaric interferences. Results of LA analyses demonstrate the capability of Neoma MS/MS to achieve high-precision <em>in situ</em> Rb-Sr isotope ratio measurements, with external precisions better than 1.9 % and 0.036 % relative standard deviation (RSD) for <sup>87</sup>Rb/<sup>86</sup>Sr and <sup>87</sup>Sr/<sup>86</sup>Sr ratios in standard glasses, respectively. The homogeneity of the Mica-Mg reference material is further assessed, with an inter-session RSD of 0.17 % for its Rb-Sr isochron age, demonstrating good age homogeneity across nine analytical sessions. Similarly, the natural ZMT04 muscovite yielded an inter-session RSD of 0.69 % for its Rb-Sr isochron age, and its Rb-Sr isochron age of 1778.8 ± 4.9 Ma (2 s, <em>n</em> = 180) is consistent with the reported Ar-Ar age (1772.2 ± 2.7 Ma, 2 s) within the uncertainty, confirming its suitability as a monitor reference material for Rb-Sr dating. These findings highlight the potential of the Neoma MS/MS in enhancing the precision of <em>in situ</em> Rb-Sr dating, for micro-scale investigations and revealing intricate age zonation patterns within individual minerals.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107117"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103866","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}

引用次数: 0

Multimodal elemental analysis: A unique tool for the provenance of radiolarite artefacts

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-01 DOI: 10.1016/j.sab.2024.107111

Filip Gregar , Martin Moník , Petr Hamrozi , Jitka Součková , Zdeňka Nerudová , Tomáš Pluháček

Tracing the provenance of lithic artefacts to reconstruct the movements, territories, and social relations of Palaeolithic hunter-gatherers is an important part of modern archaeometry. To estimate the provenance of radiolarites, a type of fine-grained silica rocks, we have developed and validated a multimodal statistical approach consisting of visual examination and elemental analysis. The determination of main and trace elements with portable X-ray fluorescence (pXRF) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allowed us to separate Central European radiolarites into one of three groups of close geographical proximity or, using LA-ICP-MS and multimodal approach, into six groups, ranging from the Northern Calcareous Alps to the eastern edge of the Pieniny Klippen Belt. It emerged that the ten analysed radiolarite artefacts collected at the Nová Dědina I Aurignacian site originated from the Slovak-Polish region, thus confirming the hypothesis that Moravian (Czech Republic) Upper Palaeolithic hunter-gatherers periodically moved towards the mountainous Pieniny Klippen Belt area.

{"title":"Multimodal elemental analysis: A unique tool for the provenance of radiolarite artefacts","authors":"Filip Gregar , Martin Moník , Petr Hamrozi , Jitka Součková , Zdeňka Nerudová , Tomáš Pluháček","doi":"10.1016/j.sab.2024.107111","DOIUrl":"10.1016/j.sab.2024.107111","url":null,"abstract":"<div><div>Tracing the provenance of lithic artefacts to reconstruct the movements, territories, and social relations of Palaeolithic hunter-gatherers is an important part of modern archaeometry. To estimate the provenance of radiolarites, a type of fine-grained silica rocks, we have developed and validated a multimodal statistical approach consisting of visual examination and elemental analysis. The determination of main and trace elements with portable X-ray fluorescence (pXRF) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allowed us to separate Central European radiolarites into one of three groups of close geographical proximity or, using LA-ICP-MS and multimodal approach, into six groups, ranging from the Northern Calcareous Alps to the eastern edge of the Pieniny Klippen Belt. It emerged that the ten analysed radiolarite artefacts collected at the Nová Dědina I Aurignacian site originated from the Slovak-Polish region, thus confirming the hypothesis that Moravian (Czech Republic) Upper Palaeolithic hunter-gatherers periodically moved towards the mountainous Pieniny Klippen Belt area.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"224 ","pages":"Article 107111"},"PeriodicalIF":3.2,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094320","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}

引用次数: 0

Dielectric silica NPs for nanoparticle-enhanced laser-induced breakdown spectroscopy: Improving the cobalt element spectral intensity

IF 3.2 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2025-02-01 DOI: 10.1016/j.sab.2024.107086

Zexuan Wang, Pengji Ding, Shengxian Han, Shan Xue, Zuoming Zhu, Zuoye Liu, Bitao Hu, Shaohua Sun

We investigated the enhancement of cobalt spectral using nanoparticle-enhanced laser-induced breakdown spectroscopy (NELIBS) through the utilisation of silica nanoparticles (NPs) with excellent sphericity. The exceptional sphericity of the silica NPs guaranteed stable and consistent experimental results. The spectral intensity of Co as a function of the concentration and the size of silica NPs was explored. Numerical simulations reveal that the abnormal trend of the Co spectral against NPs size is mainly attributed to the local electric field enhancement effect and the adsorption capacity of the silica NPs. Moreover, the silica NPs exhibited excellent dispersion in a mixed solution of ethanol and ultrapure water, resulting in a reduced drying time of approximately one minute. This facilitated the efficient and practical application of silica NPs in NELIBS.

引用次数: 0

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全部 ACS Publications Elsevier ieeexplore Springer The Royal Society of Chemistry Wiley

期刊

Spectrochimica Acta Part B: Atomic Spectroscopy

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