Germanium is a technologically critical element with increasing environmental concerns. However, data on its potential toxic effects on the environment are limited because of the challenges associated with analyzing Ge. Determining sub-nanogram to nanogram per liter levels of Ge in natural water using ICP-MS/MS remains challenging because of low concentrations and spectral interferences. This study presents a reliable method for direct Ge determination in natural waters using ICP-MS/MS. Ge was measured at a mass-to-charge ratio (m/z) = 88 instead of 72 using N2O as the reaction gas. The reaction of 72Ge+ with N2O forms 72Ge16O+ (m/z = 88), adding 16 amu and avoiding on-mass interference at m/z = 72. Signal intensity of 72Ge16O+ improved 2.5-fold upon adding 3 % methanol, with minimal changes in background signal at m/z 88. A 13.4 % suppression of the Ge-related signal due to the matrix (100 mg L−1 NaCl and 50 mg L−1 Ca) was corrected using 103Rh as the internal standard. Under the optimized conditions, the limit of quantification was 0.10 ng L−1, with reproducibility <2 %. Results for Ge in the river-certified reference materials SLRS-5 and SLRS-6 matched reported values, confirming the reliability of the proposed method for detecting ultra-trace levels of Ge in natural waters.
{"title":"Determining germanium in natural waters by ICP-MS/MS using N2O as reaction gas and methanol as signal enhancer","authors":"Jiang-yi Zhang , Wen-jing Liu , Guang-liang Wu , Zhi-fang Xu","doi":"10.1016/j.sab.2025.107354","DOIUrl":"10.1016/j.sab.2025.107354","url":null,"abstract":"<div><div>Germanium is a technologically critical element with increasing environmental concerns. However, data on its potential toxic effects on the environment are limited because of the challenges associated with analyzing Ge. Determining sub-nanogram to nanogram per liter levels of Ge in natural water using ICP-MS/MS remains challenging because of low concentrations and spectral interferences. This study presents a reliable method for direct Ge determination in natural waters using ICP-MS/MS. Ge was measured at a mass-to-charge ratio (<em>m</em>/<em>z</em>) = 88 instead of 72 using N<sub>2</sub>O as the reaction gas. The reaction of <sup>72</sup>Ge<sup>+</sup> with N<sub>2</sub>O forms <sup>72</sup>Ge<sup>16</sup>O<sup>+</sup> (<em>m</em>/<em>z</em> = 88), adding 16 amu and avoiding on-mass interference at m/z = 72. Signal intensity of <sup>72</sup>Ge<sup>16</sup>O<sup>+</sup> improved 2.5-fold upon adding 3 % methanol, with minimal changes in background signal at <em>m</em>/<em>z</em> 88. A 13.4 % suppression of the Ge-related signal due to the matrix (100 mg L<sup>−1</sup> NaCl and 50 mg L<sup>−1</sup> Ca) was corrected using <sup>103</sup>Rh as the internal standard. Under the optimized conditions, the limit of quantification was 0.10 ng L<sup>−1</sup>, with reproducibility <2 %. Results for Ge in the river-certified reference materials SLRS-5 and SLRS-6 matched reported values, confirming the reliability of the proposed method for detecting ultra-trace levels of Ge in natural waters.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107354"},"PeriodicalIF":3.8,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326251","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}
Pub Date : 2025-10-09DOI: 10.1016/j.sab.2025.107353
Pavlína Modlitbová , Dominik Kočenda , Daniel Holub , Mark Starin , Janja Novak , Ula Putar , Gabriela Kalčíková , Lukas Brunnbauer , Andreas Limbeck , Pavel Pořízka , Jozef Kaiser
This study investigates the potential of Laser-Induced Breakdown Spectroscopy (LIBS) combined with Principal Component Analysis (PCA) for the differentiation and characterization of microplastics (MPs) in various stages of environmental aging. Three commonly encountered polymer types, polystyrene, polyethylene, and polyvinyl chloride, in the form of fragments were subjected to controlled aging under abiotic and biotic conditions for one and six weeks in the absence and presence of selected heavy metal ions (cadmium, chromium, and lead) to simulate environmentally relevant contamination. The LIBS-PCA approach effectively distinguishes between pristine and aged MPs and among different polymer types and aging scenarios. Biotic aging led to pronounced elemental changes which were further supported by parallel chlorophyll a measurements assessing the biofilm development. These findings highlight the applicability of LIBS-PCA as a rapid and informative tool for monitoring microplastic transformation in complex environmental settings.
{"title":"Laser-Induced Breakdown Spectroscopy for direct analysis of pristine and environmentally aged microplastics: A PCA-based approach","authors":"Pavlína Modlitbová , Dominik Kočenda , Daniel Holub , Mark Starin , Janja Novak , Ula Putar , Gabriela Kalčíková , Lukas Brunnbauer , Andreas Limbeck , Pavel Pořízka , Jozef Kaiser","doi":"10.1016/j.sab.2025.107353","DOIUrl":"10.1016/j.sab.2025.107353","url":null,"abstract":"<div><div>This study investigates the potential of Laser-Induced Breakdown Spectroscopy (LIBS) combined with Principal Component Analysis (PCA) for the differentiation and characterization of microplastics (MPs) in various stages of environmental aging. Three commonly encountered polymer types, polystyrene, polyethylene, and polyvinyl chloride, in the form of fragments were subjected to controlled aging under abiotic and biotic conditions for one and six weeks in the absence and presence of selected heavy metal ions (cadmium, chromium, and lead) to simulate environmentally relevant contamination. The LIBS-PCA approach effectively distinguishes between pristine and aged MPs and among different polymer types and aging scenarios. Biotic aging led to pronounced elemental changes which were further supported by parallel chlorophyll <em>a</em> measurements assessing the biofilm development. These findings highlight the applicability of LIBS-PCA as a rapid and informative tool for monitoring microplastic transformation in complex environmental settings.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107353"},"PeriodicalIF":3.8,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145327117","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}
Pub Date : 2025-10-08DOI: 10.1016/j.sab.2025.107355
Zihan Yang , Shumao Bi , Yang Pu , Chun Lou , Yindi Zhang
In-situ detection of gaseous alkali metal sodium (Na) release during combustion is crucial for optimizing fuel utilization and improving operational efficiency. Combustion inherently produces emission spectra, which contain characteristic information about Na release within the flame. However, gas-phase Na in flue gas doesn't have a spontaneous emission spectrum. Laser-induced breakdown spectroscopy (LIBS) can effectively excite and detect the spectral signature of gaseous Na in flue gas. In this study, flame emission spectroscopy (FES) and LIBS were employed simultaneously to analyze Na release dynamics in flame and flue gas during the combustion of high-alkali coal. The synchronous detection of sodium release in both regions indicated a rapid migration of gas-phase Na from the flame to the flue gas. Gas-phase Na concentration in the flue gas was lower in the flue gas than in the flame, suggesting that not all sodium released in the flame migrates to the flue gas pathway. The addition of Kaolin significantly suppressed the release of Na in flame and flue gas, as well as Na migration from flame to flue gas. Furthermore, 40–50 % of Na released from the flame migrated to the flue gas under different blending conditions. This study presents a novel approach for online detection of alkali metal release during coal combustion and provides new insights for predicting slagging and fouling in coal-fired utility plants.
{"title":"Simultaneous analysis alkali metal elements using LIBS and flame emission spectroscopy: Na release during coal combustion","authors":"Zihan Yang , Shumao Bi , Yang Pu , Chun Lou , Yindi Zhang","doi":"10.1016/j.sab.2025.107355","DOIUrl":"10.1016/j.sab.2025.107355","url":null,"abstract":"<div><div>In-situ detection of gaseous alkali metal sodium (Na) release during combustion is crucial for optimizing fuel utilization and improving operational efficiency. Combustion inherently produces emission spectra, which contain characteristic information about Na release within the flame. However, gas-phase Na in flue gas doesn't have a spontaneous emission spectrum. Laser-induced breakdown spectroscopy (LIBS) can effectively excite and detect the spectral signature of gaseous Na in flue gas. In this study, flame emission spectroscopy (FES) and LIBS were employed simultaneously to analyze Na release dynamics in flame and flue gas during the combustion of high-alkali coal. The synchronous detection of sodium release in both regions indicated a rapid migration of gas-phase Na from the flame to the flue gas. Gas-phase Na concentration in the flue gas was lower in the flue gas than in the flame, suggesting that not all sodium released in the flame migrates to the flue gas pathway. The addition of Kaolin significantly suppressed the release of Na in flame and flue gas, as well as Na migration from flame to flue gas. Furthermore, 40–50 % of Na released from the flame migrated to the flue gas under different blending conditions. This study presents a novel approach for online detection of alkali metal release during coal combustion and provides new insights for predicting slagging and fouling in coal-fired utility plants.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107355"},"PeriodicalIF":3.8,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326247","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}
Pub Date : 2025-10-08DOI: 10.1016/j.sab.2025.107356
L. García-Gómez , J.K. Soriano , J.M. Vadillo , Y. Ikeda
The detection of molecular emissions in laser-induced breakdown spectroscopy (LIBS) remains a subject of active research, driven by the need to improve both signal-to-noise ratios and spectral definition. Various enhancement strategies have been proposed, including double-pulse configurations and hybrid systems combining LIBS with complementary techniques like Raman spectroscopy or laser-induced fluorescence. While effective, these methods often introduce considerable experimental complexity. In this context, the present study explores microwave re-excitation (MW-LIBS) as a more accessible alternative capable of modifying plasma dynamics without additional optical alignment. The introduction of microwave energy increases collisional activity within the plasma, extending its duration to the millisecond range and amplifying emission signals. Molecular species were monitored under this regime, focusing on canonical emitters such as CN and CaO, as well as less commonly reported systems like SnO, which has not been previously described in LIBS literature. The most significant enhancements were observed under conditions approaching the plasma ablation threshold. Moreover, MW-LIBS enabled the observation of molecular emissions in the red and near-infrared regions, which are generally limited in conventional LIBS due to detector inefficiencies and reduced plasma radiative output. These findings provide new insights into the mechanisms of molecular formation in sustained plasmas and demonstrate the potential of MW-LIBS for enhancing molecular diagnostics.
{"title":"Improved detection capabilities of molecular emission in microwave-enhanced laser-induced plasma","authors":"L. García-Gómez , J.K. Soriano , J.M. Vadillo , Y. Ikeda","doi":"10.1016/j.sab.2025.107356","DOIUrl":"10.1016/j.sab.2025.107356","url":null,"abstract":"<div><div>The detection of molecular emissions in laser-induced breakdown spectroscopy (LIBS) remains a subject of active research, driven by the need to improve both signal-to-noise ratios and spectral definition. Various enhancement strategies have been proposed, including double-pulse configurations and hybrid systems combining LIBS with complementary techniques like Raman spectroscopy or laser-induced fluorescence. While effective, these methods often introduce considerable experimental complexity. In this context, the present study explores microwave re-excitation (MW-LIBS) as a more accessible alternative capable of modifying plasma dynamics without additional optical alignment. The introduction of microwave energy increases collisional activity within the plasma, extending its duration to the millisecond range and amplifying emission signals. Molecular species were monitored under this regime, focusing on canonical emitters such as CN and CaO, as well as less commonly reported systems like SnO, which has not been previously described in LIBS literature. The most significant enhancements were observed under conditions approaching the plasma ablation threshold. Moreover, MW-LIBS enabled the observation of molecular emissions in the red and near-infrared regions, which are generally limited in conventional LIBS due to detector inefficiencies and reduced plasma radiative output. These findings provide new insights into the mechanisms of molecular formation in sustained plasmas and demonstrate the potential of MW-LIBS for enhancing molecular diagnostics.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107356"},"PeriodicalIF":3.8,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145271003","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}
Pub Date : 2025-09-30DOI: 10.1016/j.sab.2025.107347
Andrii Tupys , Jakub Nożykowski , Barbara Wagner , Marcin Strawski , Andrzej Gawor , Myroslava Petrovska , Ewa Bulska
Fluorine is vital to the environment and biological systems. However, given the limited analytical capabilities of the instrumental techniques currently available, there is a need for the development of novel methodological approaches for its determination. It has recently been demonstrated that there is significant potential in applying high resolution continuum source molecular absorption spectrometry (HR-CS-MAS). In this approach, optimal analytical parameters for fluorine determination can be achieved by monitoring molecular absorption of monofluorides formed in the presence of a mixture of modifiers, in which monofluoride forming elements and stabilizing substances are essential. One potential alternative to the “modifier cocktail” is the use of tantalum foil inserted into the atomizer to cover the graphite surface. However, given the limited thermomechanical strength of the tantalum foil, this study examined the possibility of applying tantalum(V) ethoxide solution to direct the modification of the graphite surface. The objective of this study was to develop a simplified protocol with enhanced analytical parameters for fluorine determination. The morphology and chemical composition of the graphite surface were investigated using surface techniques (TOF-SIMS and LA-ICP-MS). The analytical performance of the proposed approach for fluorine determination was evaluated and compared with previously reported methods. The optimized time-temperature programme was used to determine the fluorine content in groundwater, and the protocol, which had been elaborated, was applied to analyze fluorine in PFAS.
{"title":"Tantalum-modified graphite furnace as a novel approach for total fluorine determination and indirect PFAS analysis by HR-CS-MAS","authors":"Andrii Tupys , Jakub Nożykowski , Barbara Wagner , Marcin Strawski , Andrzej Gawor , Myroslava Petrovska , Ewa Bulska","doi":"10.1016/j.sab.2025.107347","DOIUrl":"10.1016/j.sab.2025.107347","url":null,"abstract":"<div><div>Fluorine is vital to the environment and biological systems. However, given the limited analytical capabilities of the instrumental techniques currently available, there is a need for the development of novel methodological approaches for its determination. It has recently been demonstrated that there is significant potential in applying high resolution continuum source molecular absorption spectrometry (HR-CS-MAS). In this approach, optimal analytical parameters for fluorine determination can be achieved by monitoring molecular absorption of monofluorides formed in the presence of a mixture of modifiers, in which monofluoride forming elements and stabilizing substances are essential. One potential alternative to the “modifier cocktail” is the use of tantalum foil inserted into the atomizer to cover the graphite surface. However, given the limited thermomechanical strength of the tantalum foil, this study examined the possibility of applying tantalum(V) ethoxide solution to direct the modification of the graphite surface. The objective of this study was to develop a simplified protocol with enhanced analytical parameters for fluorine determination. The morphology and chemical composition of the graphite surface were investigated using surface techniques (TOF-SIMS and LA-ICP-MS). The analytical performance of the proposed approach for fluorine determination was evaluated and compared with previously reported methods. The optimized time-temperature programme was used to determine the fluorine content in groundwater, and the protocol, which had been elaborated, was applied to analyze fluorine in PFAS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107347"},"PeriodicalIF":3.8,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227393","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}
Pub Date : 2025-09-27DOI: 10.1016/j.sab.2025.107342
Pratyush Ranjan Sen Sarma, Maria Teresa Belmonte, Sara Llorente, Santiago Mar
Accurate atomic data for lanthanides, particularly neodymium (Nd), are essential for astrophysical applications, including modelling kilonova opacity and determining stellar abundances. However, reliable experimental data for these ions remain scarce due to the spectral complexity of the lanthanides. In this study, we present a comprehensive characterisation of a high-resolution spectroscopic setup optimised for measuring transition probabilities of Nd lines. The system consists of a 1.5 m Czerny-Turner spectrometer coupled to a high-sensitivity CMOS detector, achieving a resolving power of up to 150,000. A modified hollow cathode lamp, originally developed at Imperial College London, was used to generate a stable neodymium plasma using argon as a carrier gas. We include an in-depth characterisation of our high-resolution setup, including spectral calibration, resolution assessment, instrument response function, and CMOS noise analysis. The validity of the partial local thermodynamic equilibrium (pLTE) assumption in the hollow cathode lamp was tested by measuring transition probabilities for 15 Nd II lines in the spectral range 378–521 nm. The derived transition probabilities show agreement within 30% of the reference values. This validation paves the way for accurate measurements of currently unreported Nd III transition probabilities, providing critical data for future astrophysical modelling efforts.
{"title":"Characterisation of a high-resolution spectroscopic setup for experimental determination of transition probabilities of neodymium","authors":"Pratyush Ranjan Sen Sarma, Maria Teresa Belmonte, Sara Llorente, Santiago Mar","doi":"10.1016/j.sab.2025.107342","DOIUrl":"10.1016/j.sab.2025.107342","url":null,"abstract":"<div><div>Accurate atomic data for lanthanides, particularly neodymium (Nd), are essential for astrophysical applications, including modelling kilonova opacity and determining stellar abundances. However, reliable experimental data for these ions remain scarce due to the spectral complexity of the lanthanides. In this study, we present a comprehensive characterisation of a high-resolution spectroscopic setup optimised for measuring transition probabilities of Nd lines. The system consists of a 1.5 m Czerny-Turner spectrometer coupled to a high-sensitivity CMOS detector, achieving a resolving power of up to 150,000. A modified hollow cathode lamp, originally developed at Imperial College London, was used to generate a stable neodymium plasma using argon as a carrier gas. We include an in-depth characterisation of our high-resolution setup, including spectral calibration, resolution assessment, instrument response function, and CMOS noise analysis. The validity of the partial local thermodynamic equilibrium (pLTE) assumption in the hollow cathode lamp was tested by measuring transition probabilities for 15 Nd II lines in the spectral range 378–521 nm. The derived transition probabilities show agreement within 30% of the reference values. This validation paves the way for accurate measurements of currently unreported Nd III transition probabilities, providing critical data for future astrophysical modelling efforts.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"235 ","pages":"Article 107342"},"PeriodicalIF":3.8,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145364505","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}
Pub Date : 2025-09-26DOI: 10.1016/j.sab.2025.107345
Yijun Zhang , Yiwei Chen , Yuhang Zhang , Yan Deng , Jiahan Wang
To address the critical national demand for securing titanium, zirconium, and hafnium resources, an enhanced alkali fusion–ICP-MS analytical method was developed using a lithium metaborate–lithium tetraborate composite flux. This method effectively overcomes the technical challenges posed by the high-salt matrix and refractory minerals commonly found in marine placer deposits from the Hainan coastal region. It enables high-throughput quantification of ten major and trace elements, including Ti, Zr, and Hf, in coastal placer deposits. Validation using certified reference materials across five concentration levels demonstrated excellent accuracy and precision, with relative errors (RE) ≤ 5.5 % and relative standard deviations (RSD) ≤ 5.1 %. The method provides a reliable solution for multi-element batch analysis of complex matrices and offers significant practical value in the assessment and development of marine mineral resources. When applied to the analysis of placer samples from the eastern coastal waters of Hainan Island, the results revealed strong positive correlations among Ti, Zr, and Hf (correlation coefficient r ≥ 0.94), as well as co-enrichment of Mn and V with the major ore-forming elements (r = 0.77–0.85). These findings offer preliminary insights into the metallogenic mechanisms of the region.
{"title":"Determination of ten major and trace elements in coastal placer deposits using composite flux alkali fusion-ICP-MS and analysis of their elemental associations","authors":"Yijun Zhang , Yiwei Chen , Yuhang Zhang , Yan Deng , Jiahan Wang","doi":"10.1016/j.sab.2025.107345","DOIUrl":"10.1016/j.sab.2025.107345","url":null,"abstract":"<div><div>To address the critical national demand for securing titanium, zirconium, and hafnium resources, an enhanced alkali fusion–ICP-MS analytical method was developed using a lithium metaborate–lithium tetraborate composite flux. This method effectively overcomes the technical challenges posed by the high-salt matrix and refractory minerals commonly found in marine placer deposits from the Hainan coastal region. It enables high-throughput quantification of ten major and trace elements, including Ti, Zr, and Hf, in coastal placer deposits. Validation using certified reference materials across five concentration levels demonstrated excellent accuracy and precision, with relative errors (RE) ≤ 5.5 % and relative standard deviations (RSD) ≤ 5.1 %. The method provides a reliable solution for multi-element batch analysis of complex matrices and offers significant practical value in the assessment and development of marine mineral resources. When applied to the analysis of placer samples from the eastern coastal waters of Hainan Island, the results revealed strong positive correlations among Ti, Zr, and Hf (correlation coefficient <em>r</em> ≥ 0.94), as well as co-enrichment of Mn and V with the major ore-forming elements (<em>r</em> = 0.77–0.85). These findings offer preliminary insights into the metallogenic mechanisms of the region.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107345"},"PeriodicalIF":3.8,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227392","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}
Pub Date : 2025-09-26DOI: 10.1016/j.sab.2025.107346
Manisankar Palai , S. Maji , S. Sriram , Suranjan Bera , K. Sundararajan
In the present work, a simple and novel method has been developed to determine the isotopic composition of boron (10B/11B) in boron carbide (B4C) by using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Peak intensities of BI atomic line and BII ionic line at 208.96 nm and 345.13 nm, respectively, are used to obtain calibration curves. The intensities of peak maxima of both lines are found to execute excellent linearity (R2 > 0.995) with isotopic composition over the range 20–95 % of 10B. Further, it has been shown that calibration curves obtained from the first derivative of peak maxima are more sensitive compared to the one obtained using peak maxima. Peak shift at 345.13 nm is nearly four times more sensitive than that of 208.96 nm and so calibration plot obtained at 345.13 nm is used for analytical purpose. This method is successfully applied for estimation of isotopic composition in four synthetic mixtures and one boric acid sample. The results are compared with the values obtained by Thermal Ionization Mass Spectrometer (TIMS) and found to have a good agreement between the two techniques. The present ICP-OES method for the determination of boron isotopic composition employed here is proved to be indigenous, economical, rapid and precise.
{"title":"Determination of boron isotopic composition in boron carbide using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES)","authors":"Manisankar Palai , S. Maji , S. Sriram , Suranjan Bera , K. Sundararajan","doi":"10.1016/j.sab.2025.107346","DOIUrl":"10.1016/j.sab.2025.107346","url":null,"abstract":"<div><div>In the present work, a simple and novel method has been developed to determine the isotopic composition of boron (<sup>10</sup>B/<sup>11</sup>B) in boron carbide (B<sub>4</sub>C) by using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Peak intensities of BI atomic line and BII ionic line at 208.96 nm and 345.13 nm, respectively, are used to obtain calibration curves. The intensities of peak maxima of both lines are found to execute excellent linearity (R<sup>2</sup> > 0.995) with isotopic composition over the range 20–95 % of <sup>10</sup>B. Further, it has been shown that calibration curves obtained from the first derivative of peak maxima are more sensitive compared to the one obtained using peak maxima. Peak shift at 345.13 nm is nearly four times more sensitive than that of 208.96 nm and so calibration plot obtained at 345.13 nm is used for analytical purpose. This method is successfully applied for estimation of isotopic composition in four synthetic mixtures and one boric acid sample. The results are compared with the values obtained by Thermal Ionization Mass Spectrometer (TIMS) and found to have a good agreement between the two techniques. The present ICP-OES method for the determination of boron isotopic composition employed here is proved to be indigenous, economical, rapid and precise.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107346"},"PeriodicalIF":3.8,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227388","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}
Pub Date : 2025-09-25DOI: 10.1016/j.sab.2025.107338
C. Collet , A. Cousin , O. Beyssac , P. Beck , O. Forni , S. Clegg , J. Comellas , E. Clavé , A. Fau , S. Pont , F. Poulet , R.K. Martinez , H. Austrheim , S. Maurice , R.C. Wiens
The NASA Perseverance rover is exploring Jezero crater on Mars since February 2021. Orbital data from Nili Fossae and Jezero crater show a wide diversity of mineralogical signatures including primary mineral like olivine as well as diverse secondary minerals like clays and serpentines and one of the strongest spectral signatures of carbonate on Mars from orbit. This olivine and carbonate-bearing unit is regionally extensive. Most of the studies interpreted the relationship between olivine and carbonate-bearing units as a result of weathering processes involving fluid–rock interactions such as serpentinization and carbonation. Since February 2021, Perseverance has confirmed this large diversity of primary and secondary minerals. The detection of serpentine is of particular interest in order to better constrain the past environment at Jezero crater. Among the science payload, SuperCam is combining three spectral techniques (Laser-Induced Breakdown Spectroscopy - LIBS, Raman, and Visible and near InfraRed - VISIR) that give access to the elemental composition of the targets but also to their mineral and molecular structure. Here, we use terrestrial ultramafic rocks with various degrees of alteration that were well characterized from previous studies, and we analyze them with SuperCam replicate laboratory setups to investigate the sensitivity of SuperCam to detect olivine and secondary phases, in particular serpentines. Distinguishing serpentine from olivine by LIBS is challenging since they have similar chemistry. On the other hand, Raman spectroscopy is able to detect all the phases present in the analyzed samples, when their content is high enough. Finally, the VISIR technique detected the secondary phases while it did not observe easily the olivine. We found that the synergy between these three techniques is of particular importance to differentiate such specific phases, which occur as intricate mixtures down to the sub-micrometer scale in natural targets.
{"title":"Variably weathered ultramafic rocks: Investigation of their mineralogy with SuperCam-like techniques","authors":"C. Collet , A. Cousin , O. Beyssac , P. Beck , O. Forni , S. Clegg , J. Comellas , E. Clavé , A. Fau , S. Pont , F. Poulet , R.K. Martinez , H. Austrheim , S. Maurice , R.C. Wiens","doi":"10.1016/j.sab.2025.107338","DOIUrl":"10.1016/j.sab.2025.107338","url":null,"abstract":"<div><div>The NASA Perseverance rover is exploring Jezero crater on Mars since February 2021. Orbital data from Nili Fossae and Jezero crater show a wide diversity of mineralogical signatures including primary mineral like olivine as well as diverse secondary minerals like clays and serpentines and one of the strongest spectral signatures of carbonate on Mars from orbit. This olivine and carbonate-bearing unit is regionally extensive. Most of the studies interpreted the relationship between olivine and carbonate-bearing units as a result of weathering processes involving fluid–rock interactions such as serpentinization and carbonation. Since February 2021, Perseverance has confirmed this large diversity of primary and secondary minerals. The detection of serpentine is of particular interest in order to better constrain the past environment at Jezero crater. Among the science payload, SuperCam is combining three spectral techniques (Laser-Induced Breakdown Spectroscopy - LIBS, Raman, and Visible and near InfraRed - VISIR) that give access to the elemental composition of the targets but also to their mineral and molecular structure. Here, we use terrestrial ultramafic rocks with various degrees of alteration that were well characterized from previous studies, and we analyze them with SuperCam replicate laboratory setups to investigate the sensitivity of SuperCam to detect olivine and secondary phases, in particular serpentines. Distinguishing serpentine from olivine by LIBS is challenging since they have similar chemistry. On the other hand, Raman spectroscopy is able to detect all the phases present in the analyzed samples, when their content is high enough. Finally, the VISIR technique detected the secondary phases while it did not observe easily the olivine. We found that the synergy between these three techniques is of particular importance to differentiate such specific phases, which occur as intricate mixtures down to the sub-micrometer scale in natural targets.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107338"},"PeriodicalIF":3.8,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227389","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}
Pub Date : 2025-09-24DOI: 10.1016/j.sab.2025.107344
Thalyta Fonseca Silva Oliveira , Lisiane O. Diehl , Eliana T.F. Larruscain , Cezar A. Bizzi , Fabio A. Duarte , Paola A. Mello
Lignocellulosic biomass presents a high potential for biofuel production. Knowledge of its chemical composition is essential to understand the contamination in the final products, and to select appropriate conversion technology. Hence, this study aimed to optimize an alternative analytical protocol for elemental determination in sugarcane straw (SS), sugarcane bagasse (SB), pine wood residue (PWR) and eucalyptus wood residue (EWR). Metals and sulfur were determined by inductively coupled plasma optical emission spectrometry and microwave-induced plasma optical emission spectrometry and optimization of a powerful and greener sample preparation protocol was investigated. The combination of nitric acid (0.5 mL), hydrogen peroxide (0.20 mL), hydrofluoric acid (0.06 mL) and boric acid (0.6 mL) for sample digestion resulted in accurate results (79 to 116%). The developed protocol reduced the reagent volume by up to sixteen times compared to the EN ISO 16967 standard method while maintaining accuracy within the confidence limit (ANOVA, p < 0.05). A certified reference material of sugarcane leaves (CRM Agro C1005a) was analyzed under optimized conditions to evaluate the accuracy of the proposed method. Limits of quantification ranged from 1.00 μg g−1 (Cu) to 1096 μg g−1 (Si) by MIP-OES. Regarding the elemental content, Ba, Cu, and Sr were typically found at lower levels in all samples, at <1 μg g−1 (Cu) whereas Al, Ca, K, and Si reached 0.1 to 0.4% in SS and SB; Ca and K were the main contaminants in PWR and EWR (0.09 to 0.1%).
{"title":"Assessment of metals and sulfur content in lignocellulosic biomass: developing a simple method for characterizing ash composition by optical emission spectrometry","authors":"Thalyta Fonseca Silva Oliveira , Lisiane O. Diehl , Eliana T.F. Larruscain , Cezar A. Bizzi , Fabio A. Duarte , Paola A. Mello","doi":"10.1016/j.sab.2025.107344","DOIUrl":"10.1016/j.sab.2025.107344","url":null,"abstract":"<div><div>Lignocellulosic biomass presents a high potential for biofuel production. Knowledge of its chemical composition is essential to understand the contamination in the final products, and to select appropriate conversion technology. Hence, this study aimed to optimize an alternative analytical protocol for elemental determination in sugarcane straw (SS), sugarcane bagasse (SB), pine wood residue (PWR) and eucalyptus wood residue (EWR). Metals and sulfur were determined by inductively coupled plasma optical emission spectrometry and microwave-induced plasma optical emission spectrometry and optimization of a powerful and greener sample preparation protocol was investigated. The combination of nitric acid (0.5 mL), hydrogen peroxide (0.20 mL), hydrofluoric acid (0.06 mL) and boric acid (0.6 mL) for sample digestion resulted in accurate results (79 to 116%). The developed protocol reduced the reagent volume by up to sixteen times compared to the EN ISO 16967 standard method while maintaining accuracy within the confidence limit (ANOVA, <em>p</em> < 0.05). A certified reference material of sugarcane leaves (CRM Agro C1005a) was analyzed under optimized conditions to evaluate the accuracy of the proposed method. Limits of quantification ranged from 1.00 μg g<sup>−1</sup> (Cu) to 1096 μg g<sup>−1</sup> (Si) by MIP-OES. Regarding the elemental content, Ba, Cu, and Sr were typically found at lower levels in all samples, at <1 μg g<sup>−1</sup> (Cu) whereas Al, Ca, K, and Si reached 0.1 to 0.4% in SS and SB; Ca and K were the main contaminants in PWR and EWR (0.09 to 0.1%).</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"234 ","pages":"Article 107344"},"PeriodicalIF":3.8,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227390","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}
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