Pub Date : 2026-01-20DOI: 10.1016/j.sab.2026.107460
Katarzyna Gałczyńska , Kinga Skrzyniarz , Aneta Węgierek-Ciuk , Ilona Stabrawa , Sławomir Wąsik , Ewa Trybus , Krystyna Kurdziel , Karol Ciepluch , Michał Arabski
Understanding how copper complexes with anticancer properties penetrate cellular barriers is essential for evaluating their therapeutic potential. This study investigates the transport and cellular uptake of a copper(II)–1-allylimidazole complex across biological boundaries, including a eukaryotic cell monolayer and the plasma membrane of cancer cells. Using complementary techniques—laser interferometry, total reflection X-ray fluorescence (TXRF), flow cytometry, and transmission electron microscopy (TEM)—we demonstrate that the complex rapidly diffuses through a confluent CHO-K1 monolayer and subsequently interacts with A549 lung cancer cells. The results show that the complex first reaches the cell surface, followed by its internalization via endocytosis and accumulation inside the cells. Additional studies using lipid membrane models revealed concentration-dependent interactions, with surface binding at low concentrations and membrane perturbation at higher concentrations, as indicated by changes in fluorescence anisotropy, liposome size, and fluorescence quenching. Altogether, these findings provide a coherent picture of the mechanism underlying cellular uptake of the copper(II) complex and enhance the understanding of how such compounds penetrate and affect cancer cells.
{"title":"Mechanism underlying transport of an anticancer copper(II) complex into A549 lung cancer cells and across cell monolayers","authors":"Katarzyna Gałczyńska , Kinga Skrzyniarz , Aneta Węgierek-Ciuk , Ilona Stabrawa , Sławomir Wąsik , Ewa Trybus , Krystyna Kurdziel , Karol Ciepluch , Michał Arabski","doi":"10.1016/j.sab.2026.107460","DOIUrl":"10.1016/j.sab.2026.107460","url":null,"abstract":"<div><div>Understanding how copper complexes with anticancer properties penetrate cellular barriers is essential for evaluating their therapeutic potential. This study investigates the transport and cellular uptake of a copper(II)–1-allylimidazole complex across biological boundaries, including a eukaryotic cell monolayer and the plasma membrane of cancer cells. Using complementary techniques—laser interferometry, total reflection X-ray fluorescence (TXRF), flow cytometry, and transmission electron microscopy (TEM)—we demonstrate that the complex rapidly diffuses through a confluent CHO-K1 monolayer and subsequently interacts with A549 lung cancer cells. The results show that the complex first reaches the cell surface, followed by its internalization via endocytosis and accumulation inside the cells. Additional studies using lipid membrane models revealed concentration-dependent interactions, with surface binding at low concentrations and membrane perturbation at higher concentrations, as indicated by changes in fluorescence anisotropy, liposome size, and fluorescence quenching. Altogether, these findings provide a coherent picture of the mechanism underlying cellular uptake of the copper(II) complex and enhance the understanding of how such compounds penetrate and affect cancer cells.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"238 ","pages":"Article 107460"},"PeriodicalIF":3.8,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146080988","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 : 2026-01-19DOI: 10.1016/j.sab.2026.107458
J. Ghani , A. Bisciotti , G. Bianchini , R. Tassinari , G. Iezzi , F. Radica , G. Cruciani
Laser-induced breakdown spectroscopy (LIBS) is a fast, and non-destructive technique for real-time elemental analysis, ideal for in-line characterization of construction and demolition waste (CDW). This study evaluates and improves the accuracy of portable LIBS for elemental quantification in pressed pellets from CDW. Pressed powder pellets of different CDW categories (i.e., cements, concrete, masonry), previously analysed by X-ray fluorescence (XRF), were measured using the SciAps Z900 handheld LIBS spectrometer. Total of 71 selected samples were used to build a new library dataset based on a matrix-matching calibration (MMC) approach. The resulting MMC library was then compared with the built-in SciAps “Geochem” library, which is designed for inorganic-mineral rock matrices. MMC method shows higher Si and Ca levels with similar concentrations, as main components of mixed CDW materials. Results show that MMC reduces matrix effects and analyte signal interference, enabling accurate elemental quantification, particularly for CDW samples dominated by high Si (20–70 wt%), and Ca contents (10–75 wt%). The accuracy and measurements of Ca contents are better for both MMC and Geochem calibration (GC) models, although the average relative difference decreases from 10.9% (GC) to 4.55% (MMC). Comparable accuracy improvements are found for other major elements (Si, Al, Ti, Fe, Mn, Mg, Na, K). To further validate MMC-library performance, certified reference materials from the National Institute of Standards and Technology (NIST) for building materials were also analysed. Our findings suggest that the MMC approach improves both the accuracy and precision of LIBS measurements on pressed pellets from CDW.
{"title":"Laser-induced breakdown spectroscopy (LIBS) for the characterization of demolition waste: an exploratory study","authors":"J. Ghani , A. Bisciotti , G. Bianchini , R. Tassinari , G. Iezzi , F. Radica , G. Cruciani","doi":"10.1016/j.sab.2026.107458","DOIUrl":"10.1016/j.sab.2026.107458","url":null,"abstract":"<div><div>Laser-induced breakdown spectroscopy (LIBS) is a fast, and non-destructive technique for real-time elemental analysis, ideal for in-line characterization of construction and demolition waste (CDW). This study evaluates and improves the accuracy of portable LIBS for elemental quantification in pressed pellets from CDW. Pressed powder pellets of different CDW categories (i.e., cements, concrete, masonry), previously analysed by X-ray fluorescence (XRF), were measured using the SciAps Z900 handheld LIBS spectrometer. Total of 71 selected samples were used to build a new library dataset based on a matrix-matching calibration (MMC) approach. The resulting MMC library was then compared with the built-in SciAps “Geochem” library, which is designed for inorganic-mineral rock matrices. MMC method shows higher Si and Ca levels with similar concentrations, as main components of mixed CDW materials. Results show that MMC reduces matrix effects and analyte signal interference, enabling accurate elemental quantification, particularly for CDW samples dominated by high Si (20–70 wt%), and Ca contents (10–75 wt%). The accuracy and measurements of Ca contents are better for both MMC and Geochem calibration (GC) models, although the average relative difference decreases from 10.9% (GC) to 4.55% (MMC). Comparable accuracy improvements are found for other major elements (Si, Al, Ti, Fe, Mn, Mg, Na, K). To further validate MMC-library performance, certified reference materials from the National Institute of Standards and Technology (NIST) for building materials were also analysed. Our findings suggest that the MMC approach improves both the accuracy and precision of LIBS measurements on pressed pellets from CDW.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"238 ","pages":"Article 107458"},"PeriodicalIF":3.8,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146015549","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 : 2026-01-17DOI: 10.1016/j.sab.2026.107457
Bo Wang , Wenbao Jia , Kai Zeng , Cheng Chu , Qing Shan , Yijie Wang , Shikang Xu , Yongsheng Ling
Traditional manual analysis of salt-lake brine composition is hampered by significant time delays and poor representativeness, hindering the efficient exploitation of potassium resources. To address these limitations, this study presents a novel online measurement system based on energy-dispersive X-ray fluorescence (EDXRF) technology for the rapid, non-destructive, and real-time detection of key brine components such as potassium (K) and chlorine (Cl). The system integrates automated sampling, EDXRF analysis, and pipeline control into a cohesive platform. A key innovation is an optimized intermittent measurement mode that effectively mitigates ion accumulation through periodic pipeline flushing, achieving remarkable stability with relative standard deviations (RSD) below 1.7% for both K and Cl. Furthermore, to overcome significant matrix effects inherent in high-salinity brines, an empirical influence coefficient method was employed for calibration. This approach substantially improved quantitative accuracy, reducing relative errors to below 8%, a marked enhancement over the scattering internal standard method which exhibited errors up to 45%. Validation experiments using standard potassium chloride (KCl) samples (0.15–1.25 wt%) confirmed a detection limit (LOD) of 0.008 wt% and repeatability under 1.7%. This work establishes a robust and high-precision tool for the dynamic monitoring of brine composition throughout the potash fertilizer production process, demonstrating significant potential for enhancing resource efficiency in salt-lake industries.
{"title":"Real-time quantification of KCl in salt lake brine using an online EDXRF system with optimized intermittent measurement mode","authors":"Bo Wang , Wenbao Jia , Kai Zeng , Cheng Chu , Qing Shan , Yijie Wang , Shikang Xu , Yongsheng Ling","doi":"10.1016/j.sab.2026.107457","DOIUrl":"10.1016/j.sab.2026.107457","url":null,"abstract":"<div><div>Traditional manual analysis of salt-lake brine composition is hampered by significant time delays and poor representativeness, hindering the efficient exploitation of potassium resources. To address these limitations, this study presents a novel online measurement system based on energy-dispersive X-ray fluorescence (EDXRF) technology for the rapid, non-destructive, and real-time detection of key brine components such as potassium (K) and chlorine (Cl). The system integrates automated sampling, EDXRF analysis, and pipeline control into a cohesive platform. A key innovation is an optimized intermittent measurement mode that effectively mitigates ion accumulation through periodic pipeline flushing, achieving remarkable stability with relative standard deviations (RSD) below 1.7% for both K and Cl. Furthermore, to overcome significant matrix effects inherent in high-salinity brines, an empirical influence coefficient method was employed for calibration. This approach substantially improved quantitative accuracy, reducing relative errors to below 8%, a marked enhancement over the scattering internal standard method which exhibited errors up to 45%. Validation experiments using standard potassium chloride (KCl) samples (0.15–1.25 wt%) confirmed a detection limit (LOD) of 0.008 wt% and repeatability under 1.7%. This work establishes a robust and high-precision tool for the dynamic monitoring of brine composition throughout the potash fertilizer production process, demonstrating significant potential for enhancing resource efficiency in salt-lake industries.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107457"},"PeriodicalIF":3.8,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022490","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 : 2026-01-15DOI: 10.1016/j.sab.2026.107456
Bo-Wen Zheng , Xi-Ming Zhu , Wei Xi , Lu Wang , Da-Ren Yu
Optical emission spectroscopy (OES) method has been widely employed for monitoring ceramic channel erosion products in Hall thrusters. Analysis of OES results relies on actinometry, which requires spectral lines with similar excitation energies. However, the absence of Xe I lines matching the excitation energy of the B I lines of erosion products in Hall thrusters imposes significant limitations on traditional actinometry. To address this, this work proposes a composite line actinometry method. By constructing ratios from multiple spectral lines, the method effectively decouples the relative density of boron erosion product from the electron temperature, which is a major source of uncertainty. By investigating a 100 W Hall thruster, the composite line ratio is constructed using Xe I lines at 881.94 nm and 992.32 nm, along with B I line at 249.77 nm. Results demonstrate that when the electron temperature ranges between 5 and 15 eV, the boron atoms' relative density derived from the measurements remains unaffected by electron temperature and is exclusively determined by the composite line ratio. Compared to traditional actinometry, the composite line actinometry reduces quantification deviations in erosion characteristics by 10–38% under varying acceleration voltages and by 4–25% under varying mass flow rates. This work establishes a robust OES-based framework for the relative measurement of erosion rate at different operation conditions, building a direct correlation between spectral signals and erosion characteristics, enhancing the capability of OES for real-time assessment in Hall thrusters, providing stronger support for lifetime and reliability evaluation.
{"title":"Quantitative optical emission spectroscopy monitoring of Erosion product in hall thruster channels based on composite line Actinometry","authors":"Bo-Wen Zheng , Xi-Ming Zhu , Wei Xi , Lu Wang , Da-Ren Yu","doi":"10.1016/j.sab.2026.107456","DOIUrl":"10.1016/j.sab.2026.107456","url":null,"abstract":"<div><div>Optical emission spectroscopy (OES) method has been widely employed for monitoring ceramic channel erosion products in Hall thrusters. Analysis of OES results relies on actinometry, which requires spectral lines with similar excitation energies. However, the absence of Xe I lines matching the excitation energy of the B I lines of erosion products in Hall thrusters imposes significant limitations on traditional actinometry. To address this, this work proposes a composite line actinometry method. By constructing ratios from multiple spectral lines, the method effectively decouples the relative density of boron erosion product from the electron temperature, which is a major source of uncertainty. By investigating a 100 W Hall thruster, the composite line ratio is constructed using Xe I lines at 881.94 nm and 992.32 nm, along with B I line at 249.77 nm. Results demonstrate that when the electron temperature ranges between 5 and 15 eV, the boron atoms' relative density derived from the measurements remains unaffected by electron temperature and is exclusively determined by the composite line ratio. Compared to traditional actinometry, the composite line actinometry reduces quantification deviations in erosion characteristics by 10–38% under varying acceleration voltages and by 4–25% under varying mass flow rates. This work establishes a robust OES-based framework for the relative measurement of erosion rate at different operation conditions, building a direct correlation between spectral signals and erosion characteristics, enhancing the capability of OES for real-time assessment in Hall thrusters, providing stronger support for lifetime and reliability evaluation.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107456"},"PeriodicalIF":3.8,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022600","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 : 2026-01-13DOI: 10.1016/j.sab.2026.107455
Pingsai Chu , Ye Tian , Yuanyuan Xue , Qingxi Liu , Boyang Xue , Jinjia Guo , Yuan Lu , Ronger Zheng
Quantification of submerged target using laser-induced breakdown spectroscopy (LIBS) is often limited by the lack of matrix-matched standards for building the calibration curves. Traditional underwater single-pulse LIBS (SP-LIBS) is characterized by strong continuum background and few spectral lines, making it difficult to apply the calibration-free method which has been widely used in the air environment. In this work, we applied the calibration-free method (CF-LIBS) and the one-point calibration method (OPC-LIBS) for the quantification of submerged alloys using underwater double-pulse LIBS (DP-LIBS) technique. Underwater DP-LIBS utilizes a first laser pulse to generate a bubble on the target surface and then induce a plasma inside the bubble by a second laser pulse. It shows a significant enhancement in the spectral quality compared to the traditional SP-LIBS, with sufficient lines available in the spectrum for calculating the plasma temperature with the Boltzmann plot. The well-known McWhirter criterion, together with two additional criteria based on the relaxation time and the diffusion length, were used to verify the local thermodynamic equilibrium (LTE) conditions in the plasma of underwater DP-LIBS. By applying the OPC-LIBS method with one standard of known composition, the quantification performance is remarkably improved compared to the CF-LIBS method. The average relative errors of Zn, Mn, Cu of the six samples were reduced from 4.31%, 75.96%, 57.07% to 0.75%, 11.94%, 8.86%, and the average value was also reduced from 8.01 wt% to 1.42 wt%. This work reveals the ideal plasma state in underwater DP-LIBS that is suitable for the calibration-free analysis, and demonstrates the feasibility of OPC-LIBS method in the underwater DP-LIBS quantitative analysis.
{"title":"One-point calibration of underwater double-pulse laser-induced breakdown spectroscopy","authors":"Pingsai Chu , Ye Tian , Yuanyuan Xue , Qingxi Liu , Boyang Xue , Jinjia Guo , Yuan Lu , Ronger Zheng","doi":"10.1016/j.sab.2026.107455","DOIUrl":"10.1016/j.sab.2026.107455","url":null,"abstract":"<div><div>Quantification of submerged target using laser-induced breakdown spectroscopy (LIBS) is often limited by the lack of matrix-matched standards for building the calibration curves. Traditional underwater single-pulse LIBS (SP-LIBS) is characterized by strong continuum background and few spectral lines, making it difficult to apply the calibration-free method which has been widely used in the air environment. In this work, we applied the calibration-free method (CF-LIBS) and the one-point calibration method (OPC-LIBS) for the quantification of submerged alloys using underwater double-pulse LIBS (DP-LIBS) technique. Underwater DP-LIBS utilizes a first laser pulse to generate a bubble on the target surface and then induce a plasma inside the bubble by a second laser pulse. It shows a significant enhancement in the spectral quality compared to the traditional SP-LIBS, with sufficient lines available in the spectrum for calculating the plasma temperature with the Boltzmann plot. The well-known McWhirter criterion, together with two additional criteria based on the relaxation time and the diffusion length, were used to verify the local thermodynamic equilibrium (LTE) conditions in the plasma of underwater DP-LIBS. By applying the OPC-LIBS method with one standard of known composition, the quantification performance is remarkably improved compared to the CF-LIBS method. The average relative errors of Zn, Mn, Cu of the six samples were reduced from 4.31%, 75.96%, 57.07% to 0.75%, 11.94%, 8.86%, and the average <span><math><mi>dist</mi></math></span> value was also reduced from 8.01 wt% to 1.42 wt%. This work reveals the ideal plasma state in underwater DP-LIBS that is suitable for the calibration-free analysis, and demonstrates the feasibility of OPC-LIBS method in the underwater DP-LIBS quantitative analysis.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107455"},"PeriodicalIF":3.8,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976805","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 : 2026-01-13DOI: 10.1016/j.sab.2026.107454
V. Lazic , M. Markovic , B.D. Stankov , F. Andreoli , C. Ulrich , M. Kuzmanovic
This work establishes a framework for testing and developing calibration coefficients for multi-elemental analysis by LIBS, that are transferrable to various instruments under specific experimental conditions: measurements in air, full optical collection of the plasma plume, apparent plasma temperature and electron density within 6500–7500 K and 1–2 × 1017 cm−3, respectively. Here, the plasma was produced by ns laser pulses at 1064 nm, with energy of 30 mJ while for its detection we used high resolution compact spectrometers. Calibration coefficients for 14 elements were derived respect to one Ca I line (443.50 nm) considering that Ca is a common element in natural samples. The calibration coefficients were obtained from: (i) extrapolated linear peak growths, produced by changing the sample mass on a solid support (Si wafer or Al); (ii) peaks normalized on the Ca line. Their validity interval is specified while the inherent variations with the element abundance and plasma parameters are explained. The initial calibration involved nine different samples, including a multi-element standard, rock, soils ash, coal, and carbonate's mixture, while the validation was applied on two soil samples, both in form of particles on wafer and pressed into pellets. Calibration coefficients based on the linear slope produced quantification of 13 elements within accuracy of ±30% while the use of the line ratios increased the error for some considered elements. To facilitate transfer of the coefficients to other experiments, we provide practical instructions and limits of applicability. The transition from relative to absolute element concentration measurements is also explained in the text.
{"title":"Transferable calibration coefficients for semi-quantitative analysis by Laser Induced Breakdown Spectroscopy (LIBS) in samples containing calcium","authors":"V. Lazic , M. Markovic , B.D. Stankov , F. Andreoli , C. Ulrich , M. Kuzmanovic","doi":"10.1016/j.sab.2026.107454","DOIUrl":"10.1016/j.sab.2026.107454","url":null,"abstract":"<div><div>This work establishes a framework for testing and developing calibration coefficients for multi-elemental analysis by LIBS, that are transferrable to various instruments under specific experimental conditions: measurements in air, full optical collection of the plasma plume, apparent plasma temperature and electron density within 6500–7500 K and 1–2 × 10<sup>17</sup> cm<sup>−3</sup>, respectively. Here, the plasma was produced by ns laser pulses at 1064 nm, with energy of 30 mJ while for its detection we used high resolution compact spectrometers. Calibration coefficients for 14 elements were derived respect to one Ca I line (443.50 nm) considering that Ca is a common element in natural samples. The calibration coefficients were obtained from: (i) extrapolated linear peak growths, produced by changing the sample mass on a solid support (Si wafer or Al); (ii) peaks normalized on the Ca line. Their validity interval is specified while the inherent variations with the element abundance and plasma parameters are explained. The initial calibration involved nine different samples, including a multi-element standard, rock, soils ash, coal, and carbonate's mixture, while the validation was applied on two soil samples, both in form of particles on wafer and pressed into pellets. Calibration coefficients based on the linear slope produced quantification of 13 elements within accuracy of ±30% while the use of the line ratios increased the error for some considered elements. To facilitate transfer of the coefficients to other experiments, we provide practical instructions and limits of applicability. The transition from relative to absolute element concentration measurements is also explained in the text.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107454"},"PeriodicalIF":3.8,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976806","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 : 2026-01-10DOI: 10.1016/j.sab.2026.107453
Dominik Blaimer , Christopher Leist , Ute Kaiser , Kerstin Leopold
Gold nanoparticles (AuNPs) exhibit unique properties due to their high surface-to-volume ratio, opening a wide range of innovative applications and requiring fast, sensitive and robust analytical techniques for their monitoring. In recent years, high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS-GFAAS) has proven to be useful for this task. In this study, its applicability to detect and size very small AuNPs in the single-digit size range is shown. This is of particular interest, given that alternative techniques often lack sufficiently low size detection limits. The time of first inflection point (tip) was introduced as a new sizing parameter in GFAAS, particularly sensitive within the tested size range of 2.2 nm to 10.1 nm regardless of the coating of the AuNPs and moreover not significantly affected by the presence of Au(III) ions. Experimentally, a minimum distinguishable size difference of 1.6 nm could be demonstrated, and we predict a theoretical value of 0.4 nm. As a reference method to determine the size of the very small AuNPs, high-resolution transmission electron microscopy (HRTEM) was used. Additionally, the mass proportions of bimodal mixtures of AuNP suspensions were recovered by deconvolution of the transient absorbance signals. For total gold quantification, a mass quantification limit of 0.8 pg was achieved, equivalent to 20 ng L−1 in liquid samples and independent of the introduced gold species. In summary, the proposed method has demonstrated its significant potential as a screening tool for the simultaneous speciation, quantification and sizing of very small AuNPs with minimal sample preparation requirements.
金纳米颗粒（AuNPs）由于其高表面体积比而表现出独特的性质，开辟了广泛的创新应用，并需要快速，敏感和强大的分析技术来监测它们。近年来，高分辨率连续源石墨炉原子吸收光谱法（HR-CS-GFAAS）已被证明是有效的。在本研究中，显示了它在个位数大小范围内的非常小的aunp的检测和大小的适用性。这是特别有趣的，因为替代技术往往缺乏足够低的尺寸检测限制。首次拐点时间（尖端）作为一种新的上浆参数被引入GFAAS中，在测试的尺寸范围（2.2 ~ 10.1 nm）内，无论AuNPs的涂层如何，都特别敏感，而且不受Au（III）离子存在的显著影响。实验证明，最小可区分的尺寸差异为1.6 nm，我们预测的理论值为0.4 nm。作为确定非常小的AuNPs大小的参考方法，使用高分辨率透射电镜（HRTEM）。此外，通过对瞬态吸光度信号的反卷积恢复了AuNP悬浮液双峰混合物的质量比例。对于总金的定量，达到了0.8 pg的质量定量限，相当于液体样品中的20 ng L−1，与引入的金种类无关。总之，所提出的方法已经证明了其作为一种筛选工具的巨大潜力，可以在最小的样品制备要求下同时形成、定量和确定非常小的aunp。
{"title":"Exploring the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for the analysis of gold nanoparticles in the single-digit size range","authors":"Dominik Blaimer , Christopher Leist , Ute Kaiser , Kerstin Leopold","doi":"10.1016/j.sab.2026.107453","DOIUrl":"10.1016/j.sab.2026.107453","url":null,"abstract":"<div><div>Gold nanoparticles (AuNPs) exhibit unique properties due to their high surface-to-volume ratio, opening a wide range of innovative applications and requiring fast, sensitive and robust analytical techniques for their monitoring. In recent years, high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS-GFAAS) has proven to be useful for this task. In this study, its applicability to detect and size very small AuNPs in the single-digit size range is shown. This is of particular interest, given that alternative techniques often lack sufficiently low size detection limits. The time of first inflection point (t<sub>ip</sub>) was introduced as a new sizing parameter in GFAAS, particularly sensitive within the tested size range of 2.2 nm to 10.1 nm regardless of the coating of the AuNPs and moreover not significantly affected by the presence of Au(III) ions. Experimentally, a minimum distinguishable size difference of 1.6 nm could be demonstrated, and we predict a theoretical value of 0.4 nm. As a reference method to determine the size of the very small AuNPs, high-resolution transmission electron microscopy (HRTEM) was used. Additionally, the mass proportions of bimodal mixtures of AuNP suspensions were recovered by deconvolution of the transient absorbance signals. For total gold quantification, a mass quantification limit of 0.8 pg was achieved, equivalent to 20 ng L<sup>−1</sup> in liquid samples and independent of the introduced gold species. In summary, the proposed method has demonstrated its significant potential as a screening tool for the simultaneous speciation, quantification and sizing of very small AuNPs with minimal sample preparation requirements.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107453"},"PeriodicalIF":3.8,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022599","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 : 2026-01-09DOI: 10.1016/j.sab.2026.107452
Aochen Li , Shu Chai , Haimeng Peng , Ziqing Zhao , Wendong Wu
The analytical merit of laser-induced breakdown spectroscopy (LIBS), namely low limit of detection (LOD) and reduced signal uncertainty, requires good signal-to-noise (SNR) ratio and repeatable plasma morphology within the same acquisition window. In this study, we purposely designed the doughnut-like focal pattern by structured light, to control plasma properties by plasma shielding reduction, axial collision loss suppression, and collateral collision enhancement. Using the doughnut-like laser patterns, fast imaging showed that the plasma morphology fluctuation was reduced by more than 50% and the window for repeatable morphology was prolonged from 0.04 to 0.3 μs to at least 0.04–2 μs. Based on the time-resolved spectra, the optimized SNR window for pure Al sample began from 0.4 μs and the SNR was enhanced by 50–100% after modulation. As a result, the spectral signal intensity was significantly enhanced by about 3 times along with 2–3 times of uncertainty reduction. Further evaluation using standard alloy steel samples demonstrated that the LOD of Si, Cu, Mn, Cr was improved by 3–5 times, and the signal RSD was reduced by about 50% in the meanwhile. Using LIBS as an example, this study demonstrated the potential of rationally designed 2D structured light in laser induced plasma (LIP) control.
{"title":"LIBS plasma control by 2D structured light: Merging the temporal windows for optimal spectral SNR and repeatability","authors":"Aochen Li , Shu Chai , Haimeng Peng , Ziqing Zhao , Wendong Wu","doi":"10.1016/j.sab.2026.107452","DOIUrl":"10.1016/j.sab.2026.107452","url":null,"abstract":"<div><div>The analytical merit of laser-induced breakdown spectroscopy (LIBS), namely low limit of detection (LOD) and reduced signal uncertainty, requires good signal-to-noise (SNR) ratio and repeatable plasma morphology within the same acquisition window. In this study, we purposely designed the doughnut-like focal pattern by structured light, to control plasma properties by plasma shielding reduction, axial collision loss suppression, and collateral collision enhancement. Using the doughnut-like laser patterns, fast imaging showed that the plasma morphology fluctuation was reduced by more than 50% and the window for repeatable morphology was prolonged from 0.04 to 0.3 μs to at least 0.04–2 μs. Based on the time-resolved spectra, the optimized SNR window for pure Al sample began from 0.4 μs and the SNR was enhanced by 50–100% after modulation. As a result, the spectral signal intensity was significantly enhanced by about 3 times along with 2–3 times of uncertainty reduction. Further evaluation using standard alloy steel samples demonstrated that the LOD of Si, Cu, Mn, Cr was improved by 3–5 times, and the signal RSD was reduced by about 50% in the meanwhile. Using LIBS as an example, this study demonstrated the potential of rationally designed 2D structured light in laser induced plasma (LIP) control.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107452"},"PeriodicalIF":3.8,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976804","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 : 2026-01-09DOI: 10.1016/j.sab.2026.107450
Klimentsi Cherviakouski , Om Prakash Pandey , Ma'an Amad , Froukje M. van der Zwan
Lead (Pb) isotope ratios (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb) are widely used to trace material sources in geology, archaeology, and environmental sciences. The precision of isotope ratio analysis depends on efficient sample preparation and measurement technique. While multi-collector mass spectrometry techniques, like thermal ionization mass spectrometry (TIMS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), offer the highest precision, such a level of precision is not always required. Quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) can provide effective and, at the same time, more affordable and accessible analysis when optimized. This study, for the first time, presents a detailed procedure for optimizing acquisition parameters in Q-ICP-MS to maximize analytical time efficiency. Its application, together with improvements in instrument stability and sensitivity, has significantly enhanced the precision of Q-ICP-MS analyses compared with previously published studies. The determination of 204Pb-based lead isotope ratios was performed in various rock samples with different lead concentrations (2–30 mg/kg), including certified reference materials (CRMs): andesite JA-2, granite JG-2, and basalt JB-3, as well as natural basalt samples. The repeatability and reproducibility of the CRM measurements were within the ranges of 0.07–0.13% and 0.10–0.15%, respectively. The repeatability of the analyses of basalt samples with Pb concentrations of 2–4 mg/kg was 0.08–0.18%. These values are exceptional for Q-ICP-MS analysis of 204Pb-based lead isotope ratios in samples with low Pb concentration. The statistics-based procedure described here is universal and can be applied to any Q-ICP-MS for isotope ratios analysis across diverse sample types, including environmental, archaeological, and geological materials.
{"title":"Precise determination of 204Pb-based lead isotopic ratios in geological rock samples using quadrupole ICP–MS: A statistics-based procedure for optimizing acquisition parameters","authors":"Klimentsi Cherviakouski , Om Prakash Pandey , Ma'an Amad , Froukje M. van der Zwan","doi":"10.1016/j.sab.2026.107450","DOIUrl":"10.1016/j.sab.2026.107450","url":null,"abstract":"<div><div>Lead (Pb) isotope ratios (<sup>206</sup>Pb/<sup>204</sup>Pb, <sup>207</sup>Pb/<sup>204</sup>Pb, <sup>208</sup>Pb/<sup>204</sup>Pb) are widely used to trace material sources in geology, archaeology, and environmental sciences. The precision of isotope ratio analysis depends on efficient sample preparation and measurement technique. While multi-collector mass spectrometry techniques, like thermal ionization mass spectrometry (TIMS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), offer the highest precision, such a level of precision is not always required. Quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) can provide effective and, at the same time, more affordable and accessible analysis when optimized. This study, for the first time, presents a detailed procedure for optimizing acquisition parameters in Q-ICP-MS to maximize analytical time efficiency. Its application, together with improvements in instrument stability and sensitivity, has significantly enhanced the precision of Q-ICP-MS analyses compared with previously published studies. The determination of <sup>204</sup>Pb-based lead isotope ratios was performed in various rock samples with different lead concentrations (2–30 mg/kg), including certified reference materials (CRMs): andesite JA-2, granite JG-2, and basalt JB-3, as well as natural basalt samples. The repeatability and reproducibility of the CRM measurements were within the ranges of 0.07–0.13% and 0.10–0.15%, respectively. The repeatability of the analyses of basalt samples with Pb concentrations of 2–4 mg/kg was 0.08–0.18%. These values are exceptional for Q-ICP-MS analysis of <sup>204</sup>Pb-based lead isotope ratios in samples with low Pb concentration. The statistics-based procedure described here is universal and can be applied to any Q-ICP-MS for isotope ratios analysis across diverse sample types, including environmental, archaeological, and geological materials.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107450"},"PeriodicalIF":3.8,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976807","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 : 2026-01-07DOI: 10.1016/j.sab.2026.107451
Hannah Juan Han , Alexander P. Gysi , Bonnie Frey
Inductively coupled plasma techniques such as ICP-OES and ICP-MS are routinely used to determine the concentrations of rare earth elements (REE) in water samples. However, their performance for the determination of REE concentration in mine drainage waters from epithermal vein and porphyry copper mining districts has not been evaluated extensively. In this work, we develop an REE analysis method on an Agilent 5900 ICP-OES instrument and assess the accuracy and precision for the quantification of REE in the natural waters collected from mine adits and an acid seep of mine sites in the Steeple Rock and Hillsboro mining districts, New Mexico, USA. The total REE concentrations in the water samples were measured using the methods we developed for both ICP-OES and ICP-MS. The power of the new ICP-OES method lies in routine analysis of μg/L level concentrations normally analyzed using ICP-MS, including a U.S. Geological Survey standard reference sample, laboratory blank samples spiked with a National Institute of Standards and Technology traceable standard, and surface water samples from mine waste sites. This ICP-OES method achieves low quantification limits ranging from 0.2 to 5 μg/L and excellent analytical accuracy and precision for REE analysis. The precision of light (La-Gd) and heavy (Tb-Lu) REE analysis using this method are better than 5% at average concentrations above 5 ± 4 μg/L and 3 ± 2 μg/L, respectively, and 3% at average concentrations above 10 ± 9 μg/L and 5 ± 4 μg/L, respectively. This method also shows excellent sensitivity and reproducibility for our laboratory and field samples.
{"title":"An ICP-OES method for the precise and accurate quantification of rare earth elements in natural water: A comparative study from mine waste sites in New Mexico, USA","authors":"Hannah Juan Han , Alexander P. Gysi , Bonnie Frey","doi":"10.1016/j.sab.2026.107451","DOIUrl":"10.1016/j.sab.2026.107451","url":null,"abstract":"<div><div>Inductively coupled plasma techniques such as ICP-OES and ICP-MS are routinely used to determine the concentrations of rare earth elements (REE) in water samples. However, their performance for the determination of REE concentration in mine drainage waters from epithermal vein and porphyry copper mining districts has not been evaluated extensively. In this work, we develop an REE analysis method on an Agilent 5900 ICP-OES instrument and assess the accuracy and precision for the quantification of REE in the natural waters collected from mine adits and an acid seep of mine sites in the Steeple Rock and Hillsboro mining districts, New Mexico, USA. The total REE concentrations in the water samples were measured using the methods we developed for both ICP-OES and ICP-MS. The power of the new ICP-OES method lies in routine analysis of μg/L level concentrations normally analyzed using ICP-MS, including a U.S. Geological Survey standard reference sample, laboratory blank samples spiked with a National Institute of Standards and Technology traceable standard, and surface water samples from mine waste sites. This ICP-OES method achieves low quantification limits ranging from 0.2 to 5 μg/L and excellent analytical accuracy and precision for REE analysis. The precision of light (La-Gd) and heavy (Tb-Lu) REE analysis using this method are better than 5% at average concentrations above 5 ± 4 μg/L and 3 ± 2 μg/L, respectively, and 3% at average concentrations above 10 ± 9 μg/L and 5 ± 4 μg/L, respectively. This method also shows excellent sensitivity and reproducibility for our laboratory and field samples.</div></div>","PeriodicalId":21890,"journal":{"name":"Spectrochimica Acta Part B: Atomic Spectroscopy","volume":"237 ","pages":"Article 107451"},"PeriodicalIF":3.8,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976803","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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