This paper is devoted to the development of a new approach towards elemental analysis in spent nuclear fuel (SNF) technological solutions. The approach is based on the registration of X-ray fluorescence (XRF) induced by the radioactivity of the SNF samples and consequent chemometric processing of the acquired XRF spectra. Here we extend this approach towards a challenging case of lanthanide quantification – due to the similar electronic structures of these elements their XRF lines are strongly overlapped. Multiple sources of radiation severely deteriorate the quality of the spectra. Nevertheless, multivariate regression models allows attaining technologically sufficient accuracy of quantification for La, Ce and Nd in 0.1–4.8 g/L concentration range with RMSE around 0.3–0.5 g/L depending on the element.
{"title":"Intrinsic radioactivity in spent nuclear fuel – The way to X-ray fluorescence measurement: Lanthanide quantification case study","authors":"Vitaly Panchuk , Yuri Petrov , Elizaveta Lisovskaya , Valentin Semenov , Dmitry Kirsanov","doi":"10.1016/j.sab.2024.107087","DOIUrl":"10.1016/j.sab.2024.107087","url":null,"abstract":"<div><div>This paper is devoted to the development of a new approach towards elemental analysis in spent nuclear fuel (SNF) technological solutions. The approach is based on the registration of X-ray fluorescence (XRF) induced by the radioactivity of the SNF samples and consequent chemometric processing of the acquired XRF spectra. Here we extend this approach towards a challenging case of lanthanide quantification – due to the similar electronic structures of these elements their XRF lines are strongly overlapped. Multiple sources of radiation severely deteriorate the quality of the spectra. Nevertheless, multivariate regression models allows attaining technologically sufficient accuracy of quantification for La, Ce and Nd in 0.1–4.8 g/L concentration range with RMSE around 0.3–0.5 g/L depending on the element.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107087"},"PeriodicalIF":3.2,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747132","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 : 2024-11-22DOI: 10.1016/j.sab.2024.107083
Shubho Mohajan , Foroogh Mehravaran , Sakila Ansari , Liam Droog , Nicholas F. Beier , Fatima Keserwan , Yingchao Huang , Abdul Bais , Robert Fedosejevs , Mohamed Gamal El-Din , Amina E. Hussein
The impact of sample preparation on bitumen content measurement using LIBS was investigated by collecting spectra from wet and dry tailings. A multivariate data analysis model was developed using optimal wavelength selection for bitumen content classification and prediction in tailings. Wet tailings can be classified into three classes (low, medium, and high bitumen) with 12.1 % error, while dry tailings have a classification error of 6.1 %. Quantitative analysis showed a bitumen content prediction error of 4.7 % for wet tailings and 8.9 % for dry tailings. Wet tailings showed a 1.8–2.5 times improvement in the limit of detection range compared to dry tailings. Plasma density and crater size measurements revealed that plasma density fluctuation was 2.7 times lower in wet tailings due to consistent crater formation from laser-tailings interaction. The lower plasma density fluctuation indicates a stable mass ablation for wet samples, which is attributed as the primary reason for significant LIBS performance improvement on wet tailings.
{"title":"Impact of sample preparation on bitumen content measurement using laser-induced breakdown spectroscopy","authors":"Shubho Mohajan , Foroogh Mehravaran , Sakila Ansari , Liam Droog , Nicholas F. Beier , Fatima Keserwan , Yingchao Huang , Abdul Bais , Robert Fedosejevs , Mohamed Gamal El-Din , Amina E. Hussein","doi":"10.1016/j.sab.2024.107083","DOIUrl":"10.1016/j.sab.2024.107083","url":null,"abstract":"<div><div>The impact of sample preparation on bitumen content measurement using LIBS was investigated by collecting spectra from wet and dry tailings. A multivariate data analysis model was developed using optimal wavelength selection for bitumen content classification and prediction in tailings. Wet tailings can be classified into three classes (low, medium, and high bitumen) with 12.1 % error, while dry tailings have a classification error of 6.1 %. Quantitative analysis showed a bitumen content prediction error of 4.7 % for wet tailings and 8.9 % for dry tailings. Wet tailings showed a 1.8–2.5 times improvement in the limit of detection range compared to dry tailings. Plasma density and crater size measurements revealed that plasma density fluctuation was 2.7 times lower in wet tailings due to consistent crater formation from laser-tailings interaction. The lower plasma density fluctuation indicates a stable mass ablation for wet samples, which is attributed as the primary reason for significant LIBS performance improvement on wet tailings.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107083"},"PeriodicalIF":3.2,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747128","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}
Pub Date : 2024-11-22DOI: 10.1016/j.sab.2024.107085
Diana Capela , Tomás Lopes , Filipa Dias , Miguel F.S. Ferreira , Joana Teixeira , Alexandre Lima , Pedro A.S. Jorge , Nuno A. Silva , Diana Guimarães
Mineral identification is a challenging task in geological sciences, which often implies multiple analyses of the physical and chemical properties of the samples for an accurate result. This task is particularly critical for the mining industry, where proper and fast mineral identification may translate into major efficiency and performance gains, such as in the case of the lithium mining industry. In this study, a mineral identification algorithm optimized for analyzing lithium-bearing samples using Laser-induced breakdown spectroscopy (LIBS) imaging, is put to the test with a set of representative samples. The algorithm incorporates advanced spectral processing techniques—baseline removal, Gaussian filtering, and data normalization—alongside unsupervised clustering to generate interpretable classification maps and auxiliary charts. These enhancements facilitate rapid and precise labelling of mineral compositions, significantly improving the interpretability and interactivity of the user interface. Extensive testing on diverse mineral samples with varying complexities confirmed the algorithm's robustness and broad applicability. Challenges related to sample granulometry and LIBS resolution were identified, suggesting future directions for optimizing system resolution to enhance classification accuracy in complex mineral matrices. The integration of this advanced algorithm with LIBS technology holds the potential to accelerate the mineral evaluation, paving the way for more efficient and sustainable mineral exploration.
{"title":"Advancing automated mineral identification through LIBS imaging for lithium-bearing mineral species","authors":"Diana Capela , Tomás Lopes , Filipa Dias , Miguel F.S. Ferreira , Joana Teixeira , Alexandre Lima , Pedro A.S. Jorge , Nuno A. Silva , Diana Guimarães","doi":"10.1016/j.sab.2024.107085","DOIUrl":"10.1016/j.sab.2024.107085","url":null,"abstract":"<div><div>Mineral identification is a challenging task in geological sciences, which often implies multiple analyses of the physical and chemical properties of the samples for an accurate result. This task is particularly critical for the mining industry, where proper and fast mineral identification may translate into major efficiency and performance gains, such as in the case of the lithium mining industry. In this study, a mineral identification algorithm optimized for analyzing lithium-bearing samples using Laser-induced breakdown spectroscopy (LIBS) imaging, is put to the test with a set of representative samples. The algorithm incorporates advanced spectral processing techniques—baseline removal, Gaussian filtering, and data normalization—alongside unsupervised clustering to generate interpretable classification maps and auxiliary charts. These enhancements facilitate rapid and precise labelling of mineral compositions, significantly improving the interpretability and interactivity of the user interface. Extensive testing on diverse mineral samples with varying complexities confirmed the algorithm's robustness and broad applicability. Challenges related to sample granulometry and LIBS resolution were identified, suggesting future directions for optimizing system resolution to enhance classification accuracy in complex mineral matrices. The integration of this advanced algorithm with LIBS technology holds the potential to accelerate the mineral evaluation, paving the way for more efficient and sustainable mineral exploration.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107085"},"PeriodicalIF":3.2,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747131","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 : 2024-11-21DOI: 10.1016/j.sab.2024.107080
L. Kusýn , A.P. Jovanović , D. Loffhagen , M.M. Becker , T. Hoder
A theoretical analysis of excited argon state densities responsible for optical emission spectra of atmospheric pressure argon plasma is presented for its use in plasma diagnostics. Nanosecond pulsed barrier discharges are simulated using spatially one- and two-dimensional fluid-Poisson models using the reaction kinetics model presented by Stankov et al. [1], which considers all ten argon 2p states (Paschen notation) separately. The very first (single) discharge and repetitive discharges with frequencies from 5 kHz to 100 kHz are considered. A semi-automated procedure is utilized to find appropriate 2p states for electric field determination using an intensity ratio method, which is based on a time-dependent collisional-radiative model. The fluid simulations in combination with the semi-automated procedure are used to quantify the sensitivity of selected 2p-state ratios to given preionization of the gas. A highly sensitive time-correlated single photon counting experiment shows clearly that the selected ratio is sensitive to the electric field variation in the streamer head, yet additional calibration is needed for absolute values determination. Different approaches for effective lifetime determination are tested and applied also to measured data. The influence of radial and axial 2p state density integration on the intensity ratio method is discussed. The above mentioned models and procedures result in a flexible theory-based methodology applicable for development of new diagnostic techniques.
{"title":"Theoretical analysis of argon 2p states' density ratios for nanosecond plasma optical emission spectroscopy","authors":"L. Kusýn , A.P. Jovanović , D. Loffhagen , M.M. Becker , T. Hoder","doi":"10.1016/j.sab.2024.107080","DOIUrl":"10.1016/j.sab.2024.107080","url":null,"abstract":"<div><div>A theoretical analysis of excited argon state densities responsible for optical emission spectra of atmospheric pressure argon plasma is presented for its use in plasma diagnostics. Nanosecond pulsed barrier discharges are simulated using spatially one- and two-dimensional fluid-Poisson models using the reaction kinetics model presented by Stankov et al. [<span><span>1</span></span>], which considers all ten argon 2p states (Paschen notation) separately. The very first (single) discharge and repetitive discharges with frequencies from 5 kHz to 100 kHz are considered. A semi-automated procedure is utilized to find appropriate 2p states for electric field determination using an intensity ratio method, which is based on a time-dependent collisional-radiative model. The fluid simulations in combination with the semi-automated procedure are used to quantify the sensitivity of selected 2p-state ratios to given preionization of the gas. A highly sensitive time-correlated single photon counting experiment shows clearly that the selected ratio is sensitive to the electric field variation in the streamer head, yet additional calibration is needed for absolute values determination. Different approaches for effective lifetime determination are tested and applied also to measured data. The influence of radial and axial 2p state density integration on the intensity ratio method is discussed. The above mentioned models and procedures result in a flexible theory-based methodology applicable for development of new diagnostic techniques.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107080"},"PeriodicalIF":3.2,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747127","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 : 2024-11-20DOI: 10.1016/j.sab.2024.107084
Oleg V. Komin, Oleg V. Pelipasov
The effect of Ar content in the range of 0–100 % was studied separately in the outer, intermediate and nebulizer gas flow on the excitation temperature and electron density, the intensity of element lines and the molecular background in a N2 microwave induced plasma. The addition of Ar to the nebulizer flow leads to an increase in the intensities of both atomic and ionic lines with total excitation energies (Esum) 3–13 eV to 1.7 times, depending on the selected line. Addition to the outer or intermediate flow shifts the atomic-ionic equilibrium towards the formation of ions. As a result, the intensity of ionic lines (Esum = 10–13 eV) increases up to 1.2 times, the decrease in the intensity of atomic lines (Esum = 3–6 eV) reaches up to 20 %. The excitation temperature and electron density in the plasma did not change significantly regardless of which flow the argon was fed into. The intensity of the molecular components of the plasma background (OH, NH, NO) changes significantly when Ar is introduced into the nebulizer flow. The OH intensity increases to 1.8 times, and NH intensity increases to 1.5 times at 100 % Ar relative to pure N2 plasma. Supplying 100 % Ar simultaneously into the intermediate and nebulizer gas flow and N2 into the outer flow allows one to reduce the limits of detection by up to 3.3 times, depending on the selected spectral line of the element.
{"title":"Effect of Ar on parameters of nitrogen microwave-induced plasma optical emission spectrometry","authors":"Oleg V. Komin, Oleg V. Pelipasov","doi":"10.1016/j.sab.2024.107084","DOIUrl":"10.1016/j.sab.2024.107084","url":null,"abstract":"<div><div>The effect of Ar content in the range of 0–100 % was studied separately in the outer, intermediate and nebulizer gas flow on the excitation temperature and electron density, the intensity of element lines and the molecular background in a N<sub>2</sub> microwave induced plasma. The addition of Ar to the nebulizer flow leads to an increase in the intensities of both atomic and ionic lines with total excitation energies (E<sub>sum</sub>) 3–13 eV to 1.7 times, depending on the selected line. Addition to the outer or intermediate flow shifts the atomic-ionic equilibrium towards the formation of ions. As a result, the intensity of ionic lines (E<sub>sum</sub> = 10–13 eV) increases up to 1.2 times, the decrease in the intensity of atomic lines (E<sub>sum</sub> = 3–6 eV) reaches up to 20 %. The excitation temperature and electron density in the plasma did not change significantly regardless of which flow the argon was fed into. The intensity of the molecular components of the plasma background (OH, NH, NO) changes significantly when Ar is introduced into the nebulizer flow. The OH intensity increases to 1.8 times, and NH intensity increases to 1.5 times at 100 % Ar relative to pure N<sub>2</sub> plasma. Supplying 100 % Ar simultaneously into the intermediate and nebulizer gas flow and N<sub>2</sub> into the outer flow allows one to reduce the limits of detection by up to 3.3 times, depending on the selected spectral line of the element.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107084"},"PeriodicalIF":3.2,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747126","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 : 2024-11-20DOI: 10.1016/j.sab.2024.107081
Nusrat Karim , Mathew P. Polek , Andrew M. Casella , David J. Senor , Sivanandan S. Harilal , Elizabeth J. Kautz
Laser Induced Breakdown Spectroscopy (LIBS) offers a promising rapid detection method for 6,7Li isotopic analysis. The Li I 670.8 nm provides the largest isotopic shift in the UV-VIS spectral region (15.8 pm). However, Li 670.8 nm transition is a resonance doublet and possesses very high transition probability, making it susceptible to self-absorption and self-reversal, which can affect line width, shape, and overall analytical capabilities. Environmental factors, such as the pressure and type of ambient gas, significantly influence the physical conditions of plasma and its hydrodynamics, thereby impacting the self-reversal phenomenon. In this study, we investigate plasmas generated via nanosecond laser ablation of a LiAlO2 target with natural isotopic abundance in an inert gas (Ar) environment at pressures ranging from 0.1 to 100 Torr. Complementary fast-gated Li monochromatic imaging and spatially-integrated optical emission spectroscopy were used to explore the relationship between Li atomic distribution and emission gradients in laser-produced plasmas and self-reversal in Li I spectral features. Results highlight that self-reversal is prominent at later times in plasma evolution (greater than 5 μs) for Ar pressure levels between 1 and 100 Torr, due to a significant buildup of Li ground level population at the plume-background gas interface. Conversely, at lower pressures (0.1 Torr or less), rapid plasma expansion without a strong plume-background interface results in the absence of self-reversal in the Li I spectral profiles.
{"title":"Unraveling Li I 670.8 nm self-reversal and atomic distribution inhomogeneity in laser ablation plumes under varying argon pressures","authors":"Nusrat Karim , Mathew P. Polek , Andrew M. Casella , David J. Senor , Sivanandan S. Harilal , Elizabeth J. Kautz","doi":"10.1016/j.sab.2024.107081","DOIUrl":"10.1016/j.sab.2024.107081","url":null,"abstract":"<div><div>Laser Induced Breakdown Spectroscopy (LIBS) offers a promising rapid detection method for <sup>6,7</sup>Li isotopic analysis. The Li I 670.8 nm provides the largest isotopic shift in the UV-VIS spectral region (<span><math><mo>≈</mo></math></span>15.8 pm). However, Li 670.8 nm transition is a resonance doublet and possesses very high transition probability, making it susceptible to self-absorption and self-reversal, which can affect line width, shape, and overall analytical capabilities. Environmental factors, such as the pressure and type of ambient gas, significantly influence the physical conditions of plasma and its hydrodynamics, thereby impacting the self-reversal phenomenon. In this study, we investigate plasmas generated via nanosecond laser ablation of a LiAlO<sub>2</sub> target with natural isotopic abundance in an inert gas (Ar) environment at pressures ranging from 0.1 to 100 Torr. Complementary fast-gated Li monochromatic imaging and spatially-integrated optical emission spectroscopy were used to explore the relationship between Li atomic distribution and emission gradients in laser-produced plasmas and self-reversal in Li I spectral features. Results highlight that self-reversal is prominent at later times in plasma evolution (greater than 5 μs) for Ar pressure levels between 1 and 100 Torr, due to a significant buildup of Li ground level population at the plume-background gas interface. Conversely, at lower pressures (0.1 Torr or less), rapid plasma expansion without a strong plume-background interface results in the absence of self-reversal in the Li I spectral profiles.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107081"},"PeriodicalIF":3.2,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747129","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 : 2024-11-19DOI: 10.1016/j.sab.2024.107077
Wei Wang, Lei Feng, Ruiyang Xi, Wenliang Wang, Jiang Xu, Yalong Wang, Siqi Guo, Pengfei Zhang, Manchao Zhang, Yunhe Zhang, Fan Yu, Yufeng Wang, Yongyang Su, Sui Fang, Xianglong Yuang, Zhiming Li
Americium isotopes are crucial in various nuclear-related fields such as nuclear fuel cycle, nuclear forensics and nuclear safeguards. This study introduces enhanced methodologies for precise determination of 242Am/241Am and 243Am/241Am in trace americium by employing Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) and Total Evaporation-Thermal Ionization Mass Spectrometry (TE-TIMS). We established a standard-sample bracketing (SSB) method with uranium-certified reference material (U CRM) to correct the mass fractionation and ion counter gain yield among different isotopes in MC-ICP-MS. The new methods were successfully applied to an aliquot of an 241Am progeny sample, an 241Am activity standard solution and an in-house Am isotopic working standard, achieving detection limits of 10−7 for 242Am and 243Am. Analysis requires an aliquot containing about 1 ng of 241Am for MC-ICP-MS with a desolvation device for sample introduction and about 5 ng for TE-TIMS to determine 242Am/241Am ratios close to 10−5 and 243Am/241Am ratios close to 10−4, with observed relative standard deviations of 0.2 %. Comparative analysis of 242Am/241Am and 243Am/241Am using classical TE-TIMS and the newly developed MC-ICP-MS confirms their consistency within uncertainties, validating the precision of MC-ICP-MS in americium isotope ratio determination. These findings indicate that the 241Am activity standard sample was directly sourced from irradiated material rather than from a 241Pu solution, highlighting the methodology's applicability to nuclear forensics and nuclear fuel cycles.
{"title":"Determination of Am full isotope compositions (241Am, 242Am, 243Am) at trace level by multiple-collector - ICP-MS with a desolvation device for sample introduction","authors":"Wei Wang, Lei Feng, Ruiyang Xi, Wenliang Wang, Jiang Xu, Yalong Wang, Siqi Guo, Pengfei Zhang, Manchao Zhang, Yunhe Zhang, Fan Yu, Yufeng Wang, Yongyang Su, Sui Fang, Xianglong Yuang, Zhiming Li","doi":"10.1016/j.sab.2024.107077","DOIUrl":"10.1016/j.sab.2024.107077","url":null,"abstract":"<div><div>Americium isotopes are crucial in various nuclear-related fields such as nuclear fuel cycle, nuclear forensics and nuclear safeguards. This study introduces enhanced methodologies for precise determination of <sup>242</sup>Am/<sup>241</sup>Am and <sup>243</sup>Am/<sup>241</sup>Am in trace americium by employing Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) and Total Evaporation-Thermal Ionization Mass Spectrometry (TE-TIMS). We established a standard-sample bracketing (SSB) method with uranium-certified reference material (U CRM) to correct the mass fractionation and ion counter gain yield among different isotopes in MC-ICP-MS. The new methods were successfully applied to an aliquot of an <sup>241</sup>Am progeny sample, an <sup>241</sup>Am activity standard solution and an in-house Am isotopic working standard, achieving detection limits of 10<sup>−7</sup> for <sup>242</sup>Am and <sup>243</sup>Am. Analysis requires an aliquot containing about 1 ng of <sup>241</sup>Am for MC-ICP-MS with a desolvation device for sample introduction and about 5 ng for TE-TIMS to determine <sup>242</sup>Am/<sup>241</sup>Am ratios close to 10<sup>−5</sup> and <sup>243</sup>Am/<sup>241</sup>Am ratios close to 10<sup>−4</sup>, with observed relative standard deviations of 0.2 %. Comparative analysis of <sup>242</sup>Am/<sup>241</sup>Am and <sup>243</sup>Am/<sup>241</sup>Am using classical TE-TIMS and the newly developed MC-ICP-MS confirms their consistency within uncertainties, validating the precision of MC-ICP-MS in americium isotope ratio determination. These findings indicate that the <sup>241</sup>Am activity standard sample was directly sourced from irradiated material rather than from a <sup>241</sup>Pu solution, highlighting the methodology's applicability to nuclear forensics and nuclear fuel cycles.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107077"},"PeriodicalIF":3.2,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747130","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 : 2024-11-19DOI: 10.1016/j.sab.2024.107079
A.V. Rylov, A.S. Zakuskin, T.A. Labutin
Reconstructing spatial distribution of emissivity is important for study of heterogeneous plasma sources. However, often used Radon and Abel transforms tend to amplify noise in the data. The small size and short lifetime of laser-induced plasma result in short exposures for signal acquisition, and, consequently limited number of points along the source available for measurements and noisy signals. We compared 14 Abel transform algorithms and various noise processing methods, focusing on both limited data points and high noise levels. All algorithms were presented in matrix form to ensure fair comparison, and we proposed a metric based on the largest singular value of matrix operator for error assessment. An error analysis is performed to show the contribution of approximation and noise errors to the overall reconstruction error. Our results indicate that at higher noise levels, the choice of noise reduction method is more critical than the inversion algorithm itself, with regularization proving to be the most effective for noise control. Given the minimal impact of algorithm choice on the final result, simple and easy-to-implement methods like “Onion Peeling” are recommended to be combined with regularization. Furthermore, transforms with regularization were the most stable for reconstructing complex profiles. Summarizing the results for all considered cases, “Hankel-Fourier” and “Cubic Spline” are the most accurate for noiseless data with limited number of spatial points, while for cases with a large amount of data, “Polynomial”, “Piessens-Verbaeten”, and “Minerbo-Levy” are better, especially for noisy data.
{"title":"Abel transform of laser-induced plasma image: Overcoming challenges of noisy and insufficient data for reliable reconstruction","authors":"A.V. Rylov, A.S. Zakuskin, T.A. Labutin","doi":"10.1016/j.sab.2024.107079","DOIUrl":"10.1016/j.sab.2024.107079","url":null,"abstract":"<div><div>Reconstructing spatial distribution of emissivity is important for study of heterogeneous plasma sources. However, often used Radon and Abel transforms tend to amplify noise in the data. The small size and short lifetime of laser-induced plasma result in short exposures for signal acquisition, and, consequently limited number of points along the source available for measurements and noisy signals. We compared 14 Abel transform algorithms and various noise processing methods, focusing on both limited data points and high noise levels. All algorithms were presented in matrix form to ensure fair comparison, and we proposed a metric based on the largest singular value of matrix operator for error assessment. An error analysis is performed to show the contribution of approximation and noise errors to the overall reconstruction error. Our results indicate that at higher noise levels, the choice of noise reduction method is more critical than the inversion algorithm itself, with regularization proving to be the most effective for noise control. Given the minimal impact of algorithm choice on the final result, simple and easy-to-implement methods like “Onion Peeling” are recommended to be combined with regularization. Furthermore, transforms with regularization were the most stable for reconstructing complex profiles. Summarizing the results for all considered cases, “Hankel-Fourier” and “Cubic Spline” are the most accurate for noiseless data with limited number of spatial points, while for cases with a large amount of data, “Polynomial”, “Piessens-Verbaeten”, and “Minerbo-Levy” are better, especially for noisy data.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107079"},"PeriodicalIF":3.2,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747125","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 : 2024-11-16DOI: 10.1016/j.sab.2024.107075
Kaikai Kou , Weiran Song , Zongyu Hou , Zhe Wang
Laser-induced breakdown spectroscopy (LIBS) has been demonstrated as a promising technique for real-time combustion diagnosis due to its capacity for simultaneous multi-species analysis. The gradient of species concentration in reacting flows often coupled with variations in gas temperature which prevented accurate concentration measurement. The effect of gas temperature on spectral emission intensity and plasma property was comprehensively investigated by employing a Bunsen flame. With the increasing of gas temperature, less laser energy was deposited into the plasma, resulting in a monotonic decline in plasma volume, brightness and atomic emission intensity. Conversely, the plasma temperature improved due to fewer gas molecules being excited. The intensity of ionic lines and electron density were initially increased but subsequently decreased, with the reduction in gas density playing a dominant role at higher gas temperature. Intensity ratio pairs of C/O and H/O were found to be susceptible to gas temperature. The deviation of C/O ratio caused by gas temperature from burner nozzle to Bunsen tip (∼1100 °C) was about 28.4 %. Clear elucidation of the effect of gas temperature provides reliable basis to accurate combustion diagnosis with LIBS.
{"title":"Effects of gas temperature on equivalence ratio measurement in premixed methane–Air flame using laser-induced breakdown spectroscopy","authors":"Kaikai Kou , Weiran Song , Zongyu Hou , Zhe Wang","doi":"10.1016/j.sab.2024.107075","DOIUrl":"10.1016/j.sab.2024.107075","url":null,"abstract":"<div><div>Laser-induced breakdown spectroscopy (LIBS) has been demonstrated as a promising technique for real-time combustion diagnosis due to its capacity for simultaneous multi-species analysis. The gradient of species concentration in reacting flows often coupled with variations in gas temperature which prevented accurate concentration measurement. The effect of gas temperature on spectral emission intensity and plasma property was comprehensively investigated by employing a Bunsen flame. With the increasing of gas temperature, less laser energy was deposited into the plasma, resulting in a monotonic decline in plasma volume, brightness and atomic emission intensity. Conversely, the plasma temperature improved due to fewer gas molecules being excited. The intensity of ionic lines and electron density were initially increased but subsequently decreased, with the reduction in gas density playing a dominant role at higher gas temperature. Intensity ratio pairs of C/O and H/O were found to be susceptible to gas temperature. The deviation of C/O ratio caused by gas temperature from burner nozzle to Bunsen tip (∼1100 °C) was about 28.4 %. Clear elucidation of the effect of gas temperature provides reliable basis to accurate combustion diagnosis with LIBS.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107075"},"PeriodicalIF":3.2,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747124","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 : 2024-11-15DOI: 10.1016/j.sab.2024.107078
Gyula Kajner , Ádám Bélteki , Martin Cseh , Zsolt Geretovszky , Imre Szenti , Ákos Kukovecz , Tibor Ajtai , Gábor Galbács
We have designed and successfully fabricated a fully 3D-printed concentric nebulizer made of an acrylicate-based resin using material jetting technology. Computer tomography images confirmed that the details of the nebulizer design were fairly well preserved during the printing. The aerosol quality and the inductively coupled plasma mass spectrometry (ICP-MS) analytical performance of the nebulizer were investigated in detail and compared to that of a borosilicate glass MicroMist nebulizer. It was found that the aerosol quality and production efficiency was similar to that of the glass nebulizer in the most important particle size range below ca. 7 μm. The chemical resistance and purity of the resin was tested by leaching experiments and laser induced breakdown spectroscopy measurements and it was found to only give rise to some very low level contamination from alkali elements, thus it is suitable for trace analytical ICP-MS use. The 3D-printed plastic and the glass nebulizer gave a comparable performance in terms of background signal intensites, limit of detection and background equivalent concentration values. After 50 h of net service time with acidified aqueous solutions, the 3D-printed nebulizer's performance was re-assessed and only a minor deterioration was found, which indicates that there are no serious issues with aging or erosion, at least during short-term use. Our results therefore suggest that 3D-printing technology is now capable of producing useful sample introduction devices for ICP-MS use.
{"title":"Performance assessment of a fully 3D-printed, plastic concentric nebulizer meant for short-term ICP-MS trace analytical use","authors":"Gyula Kajner , Ádám Bélteki , Martin Cseh , Zsolt Geretovszky , Imre Szenti , Ákos Kukovecz , Tibor Ajtai , Gábor Galbács","doi":"10.1016/j.sab.2024.107078","DOIUrl":"10.1016/j.sab.2024.107078","url":null,"abstract":"<div><div>We have designed and successfully fabricated a fully 3D-printed concentric nebulizer made of an acrylicate-based resin using material jetting technology. Computer tomography images confirmed that the details of the nebulizer design were fairly well preserved during the printing. The aerosol quality and the inductively coupled plasma mass spectrometry (ICP-MS) analytical performance of the nebulizer were investigated in detail and compared to that of a borosilicate glass MicroMist nebulizer. It was found that the aerosol quality and production efficiency was similar to that of the glass nebulizer in the most important particle size range below ca. 7 μm. The chemical resistance and purity of the resin was tested by leaching experiments and laser induced breakdown spectroscopy measurements and it was found to only give rise to some very low level contamination from alkali elements, thus it is suitable for trace analytical ICP-MS use. The 3D-printed plastic and the glass nebulizer gave a comparable performance in terms of background signal intensites, limit of detection and background equivalent concentration values. After 50 h of net service time with acidified aqueous solutions, the 3D-printed nebulizer's performance was re-assessed and only a minor deterioration was found, which indicates that there are no serious issues with aging or erosion, at least during short-term use. Our results therefore suggest that 3D-printing technology is now capable of producing useful sample introduction devices for ICP-MS use.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"223 ","pages":"Article 107078"},"PeriodicalIF":3.2,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747123","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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