Spectrochimica Acta Part B: Atomic Spectroscopy最新文献_第2页

Detection performance comparison of laser-induced breakdown spectroscopy and laser-induced breakdown spectroscopy assisted by laser-induced fluorescence for analysis of total phosphorus in facility sandy loam soil 激光诱导击穿光谱与激光诱导荧光辅助下的激光诱导击穿光谱分析设施砂壤土全磷的检测性能比较

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2025-12-29 DOI: 10.1016/j.sab.2025.107448

Bing Lu , Haibo He , Zhanjian Lin , Xufeng Wang , Can Hu , Jianfei Xing , Mingsheng Li , Long Wang , Shiping Zhu , Xiangyou Li

Rapid measurement of total phosphorus content in sandy loam soil is of great significance for the accurate management of phosphorus fertilizer in facility vegetable planting. Laser-induced breakdown spectroscopy (LIBS) is a simple and rapid optical detection technique, which has great potential in the rapid analysis of soil components. However, the variations in the composition and structure of the soil matrix can lead to changes in the correlation between characteristic spectral lines and the matrix composition, thereby reducing analytical reliability and limiting the effectiveness of LIBS for rapid soil component assessment. In this study, the LIBS univariate calibration model, LIBS multivariate model and laser-induced breakdown spectroscopy assisted by laser-induced fluorescence (LIBS-LIF) univariate calibration model were used to conduct a rapid detection study on the total phosphorus content of facility sandy loam soil. The results showed that the determination coefficients of the optimal model constructed by LIBS univariate calibration curve, LIBS multivariate modeling and LIBS-LIF univariate calibration curve were 0.6028, 0.9508 and 0.9833, respectively, and the corresponding root mean square errors were 897 mg/kg, 134 mg/kg and 104 mg/kg, respectively. The optimal LIBS-LIF calibration model was externally verified by sampling actual samples. The verification results showed that LIBS-LIF had excellent detection performance, and its determination coefficient and root mean square error were 0.9664 and 130 mg/kg, respectively. In conclusion, LIBS-LIF could eliminate the interference of matrix changes on the detection of total phosphorus in facility sandy loam soil to the greatest extent, and the LIBS-LIF calibration model based on P I 213.62 nm spectral line data would realize the rapid detection and analysis of total phosphorus in facility sandy loam soil. This study would provide a reference for the rapid detection of facility soil with complex matrix compositions.

快速测定砂壤土全磷含量对设施蔬菜种植中磷肥的准确施用具有重要意义。激光诱导击穿光谱（LIBS）是一种简单、快速的光学检测技术，在土壤成分的快速分析中具有很大的潜力。然而，土壤基质成分和结构的变化会导致特征谱线与基质成分之间的相关性发生变化，从而降低了分析的可靠性，限制了LIBS快速评估土壤成分的有效性。本研究采用LIBS单变量校准模型、LIBS多变量模型和激光诱导击穿光谱辅助激光诱导荧光（LIBS- lif）单变量校准模型对设施砂壤土全磷含量进行快速检测研究。结果表明，LIBS单变量校准曲线、LIBS多变量建模和LIBS- lif单变量校准曲线构建的最优模型的决定系数分别为0.6028、0.9508和0.9833，相应的均方根误差分别为897、134和104 mg/kg。通过实际样品取样，对优化后的LIBS-LIF标定模型进行了外部验证。验证结果表明，LIBS-LIF具有优良的检测性能，其测定系数为0.9664，均方根误差为130 mg/kg。综上所述，LIBS-LIF能最大程度地消除基质变化对设施砂壤土全磷检测的干扰，基于p213.62 nm谱线数据的LIBS-LIF校准模型将实现设施砂壤土全磷的快速检测与分析。本研究可为复杂基质组成设施土的快速检测提供参考。

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引用次数: 0

Real-time quantification of KCl in salt lake brine using an online EDXRF system with optimized intermittent measurement mode 采用优化间歇测量模式的在线EDXRF系统实时定量盐湖盐水中的KCl

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2026-01-17 DOI: 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.

传统的盐湖卤水成分人工分析存在时间延迟大、代表性差等问题，影响了钾盐资源的有效开发。为了解决这些限制，本研究提出了一种基于能量色散x射线荧光（EDXRF）技术的新型在线测量系统，用于快速，无损和实时检测关键卤水成分，如钾(K)和氯（Cl）。该系统将自动采样、EDXRF分析和管道控制集成到一个内聚平台中。一项关键的创新是优化的间歇测量模式，通过定期冲洗管道有效地减少离子积累，实现了K和Cl的相对标准偏差（RSD）低于1.7%的显著稳定性。此外，为了克服高盐度盐水固有的显著基质效应，采用经验影响系数法进行校准。该方法大大提高了定量精度，将相对误差降低到8%以下，与误差高达45%的散射内标法相比有了显著的提高。使用标准氯化钾（KCl）样品（0.15-1.25 wt%）进行验证实验，检测限（LOD）为0.008 wt%，重复性低于1.7%。这项工作为整个钾肥生产过程中卤水成分的动态监测建立了一个强大的高精度工具，显示了提高盐湖工业资源效率的巨大潜力。

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引用次数: 0

A Monte Carlo–driven genetic algorithm and digital twin approach for quantitative X-ray fluorescence spectroscopy 定量x射线荧光光谱的蒙特卡罗驱动遗传算法和数字孪生方法

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2025-12-16 DOI: 10.1016/j.sab.2025.107428

Allison O’Brien , Samuel Webb , Rebecca Abergel

Traditional X-ray fluorescence (XRF) quantification approaches often rely on spectral fitting and simplified attenuation models, which can introduce systematic errors for thick, heterogeneous, or geometry-dependent samples. Here we present a genetic algorithm (GA) framework, coupled with Monte Carlo (MC) radiation transport, that applies evolutionary optimization to both composition estimation and experimental parameter selection. Using Geant4 simulations as physics-accurate references, the GA iteratively optimizes elemental fractions and beam conditions based on spectral agreement.

The composition GA consistently converges for simulated samples containing up to seven elements, outperforming random sampling and maintaining accuracy in low-information scenarios. An experiment-planning GA improves spectral quality by adjusting excitation energy, yielding more than an 80% increase in peak signal-to-noise ratio. Combined in a digital twin approach, the two stages reduce mean absolute error by 14.5% while refining experimental setup. Parallelization studies on high performance computing systems demonstrate that optimized multiprocessing and multithreading halve runtime, enabling scalability to larger problem sizes.

This work demonstrates genetic algorithm-driven optimization with MC simulations as a powerful digital twin framework for XRF, enhancing both experimental planning and post-experimental analysis.

传统的x射线荧光（XRF）定量方法通常依赖于光谱拟合和简化的衰减模型，这可能会对厚的、非均匀的或几何相关的样品引入系统误差。在这里，我们提出了一个遗传算法（GA）框架，结合蒙特卡罗（MC）辐射输运，将进化优化应用于成分估计和实验参数选择。使用Geant4模拟作为物理精确参考，遗传算法迭代优化元素分数和基于光谱一致性的光束条件。对于包含多达七个元素的模拟样本，组合遗传算法始终收敛，优于随机抽样，并在低信息场景中保持准确性。实验规划遗传算法通过调节激发能量来提高光谱质量，使峰值信噪比提高80%以上。结合数字孪生方法，两个阶段在改进实验设置的同时减少了14.5%的平均绝对误差。对高性能计算系统的并行化研究表明，优化后的多处理和多线程使运行时减半，从而使可伸缩性能够适用于更大的问题规模。这项工作展示了遗传算法驱动的优化与MC模拟作为XRF的强大数字孪生框架，增强了实验计划和实验后分析。

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引用次数: 0

Determination of trace elements in Inconel718 by non-weighing micro-reaction high-resolution inductively coupled plasma mass spectrometry 非称重微反应高分辨率电感耦合等离子体质谱法测定Inconel718中的微量元素

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2025-12-18 DOI: 10.1016/j.sab.2025.107429

Dandan Su , Xuejing Shen , Jingyu Hu , Yunhai Jia , Suibin Luo , Haizhou Wang

As a newly proposed green and efficient method, non-weighing micro-reaction method has been preliminarily applied using ICP-OES. To further improve the detection limits, the non-weighing micro-reaction method was combined with high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). The quantification of trace elements in Inconel718 (IN718) was studied. Potential mass spectral interferences were evaluated, and optimal resolution settings and mass-to-charge ratios (m/z) were selected. Different quantification methodologies were investigated and compared to establish a robust calibration strategy. The feasibility of substituting certified reference materials (CRMs) with standard solutions to draw calibration was also examined. The minimization of sample weights substantially reduced reagent and water consumption. Consequently, accurate analysis of B, P, Mn, Co, Cu, Ga, As, In, Sn, Sb, Hf, Ta, Tl, Pb, and Bi was performed, with limits of detection (LODs) and limits of quantification (LOQs) reaching the μg/g level. Excellent experimental precision was demonstrated with relative standard deviations (RSDs) consistently below 25 %, most of which were less than 10 %. The established quantitative method demonstrates its broader application potential in analytical chemistry. The unique capabilities of HR-ICP-MS were leveraged to significantly improve the detection limits of non-weighing micro-reaction method, thereby expanding its applicability. Furthermore, the green and efficient nature of this pretreatment makes it a valuable reference for low-pollution and high-efficiency wet chemical analysis.

不称重微反应法作为一种绿色高效的新方法，已初步应用于ICP-OES。为进一步提高检测限，将非称重微反应法与高分辨率电感耦合等离子体质谱法（HR-ICP-MS）相结合。对Inconel718 （IN718）中微量元素的定量进行了研究。评估了潜在的质谱干扰，并选择了最佳分辨率设置和质荷比（m/z）。研究并比较了不同的定量方法，以建立稳健的校准策略。研究了用标准溶液代替标准物质进行图纸标定的可行性。样品重量的最小化大大减少了试剂和水的消耗。结果表明，B、P、Mn、Co、Cu、Ga、As、In、Sn、Sb、Hf、Ta、Tl、Pb、Bi的检测限（lod）和定量限（loq）均达到μg/g。实验精度高，相对标准偏差（rsd）均小于25%，多数小于10%。所建立的定量方法在分析化学中具有广泛的应用潜力。利用HR-ICP-MS的独特功能，显著提高了非称重微反应法的检出限，扩大了其适用性。该预处理技术绿色高效，为低污染、高效的湿法化学分析提供了有价值的参考。

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引用次数: 0

LIBS plasma control by 2D structured light: Merging the temporal windows for optimal spectral SNR and repeatability 利用二维结构光控制LIBS等离子体：合并时间窗口以获得最佳的光谱信噪比和可重复性

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2026-01-09 DOI: 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.

激光诱导击穿光谱（LIBS）的分析优点是低检测限（LOD）和降低信号不确定性，这需要在相同的采集窗口内具有良好的信噪比（SNR）和可重复的等离子体形态。在这项研究中，我们特意用结构光设计了甜甜圈状的焦点图案，通过等离子体屏蔽减少、轴向碰撞损失抑制和侧面碰撞增强来控制等离子体特性。利用环形激光图案，快速成像表明等离子体形态波动减小50%以上，可重复形态窗口从0.04 ~ 0.3 μs延长到至少0.04 ~ 2 μs。基于时间分辨光谱，纯铝样品的优化信噪比窗口从0.4 μs开始，调制后的信噪比提高了50 ~ 100%。结果，光谱信号强度显著增强约3倍，不确定度降低2-3倍。使用标准合金钢样品进一步评估表明，Si, Cu, Mn， Cr的LOD提高了3-5倍，同时信号RSD降低了约50%。本研究以LIBS为例，论证了合理设计二维结构光在激光诱导等离子体控制中的潜力。

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引用次数: 0

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 ICP-OES法精确定量天然水中稀土元素——以美国新墨西哥州矿山废渣场为例

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2026-01-07 DOI: 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.

电感耦合等离子体技术如ICP-OES和ICP-MS通常用于测定水样中稀土元素（REE）的浓度。然而，它们在浅成热液脉状和斑岩型铜矿矿区矿水中稀土浓度测定中的应用尚未得到广泛评价。在这项工作中，我们在Agilent 5900 ICP-OES仪器上开发了一种稀土元素分析方法，并评估了从美国新墨西哥州steple Rock和Hillsboro矿区的矿井巷道和酸性渗漏中收集的自然水中稀土元素定量的准确性和精密度。采用ICP-OES和ICP-MS两种方法测量水样中总REE浓度。新的ICP-OES方法的强大之处在于常规分析通常使用ICP-MS分析的μg/L水平浓度，包括美国地质调查局标准参比样品，添加了国家标准与技术研究所可追溯标准的实验室空白样品，以及矿山废弃地的地表水样品。ICP-OES方法定量限为0.2 ~ 5 μg/L，分析准确度和精密度较高。在平均浓度高于5±4 μg/L和3±2 μg/L时，轻（La-Gd）和重（Tb-Lu）稀土元素分析的精密度分别优于5%和3%；在平均浓度高于10±9 μg/L和5±4 μg/L时，该方法的精密度分别优于5%和3%。该方法对实验室和现场样品也显示出良好的灵敏度和重复性。

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引用次数: 0

X-ray fluorescence determination of fluorine in snow cover solid phase for investigation of aluminum industry emissions 铝工业排放物中积雪固相氟的x射线荧光测定

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2025-12-04 DOI: 10.1016/j.sab.2025.107404

Alena A. Amosova, Victor M. Chubarov, Julia V. Sokolnikova, Sergey N. Prosekin, Alexandr L. Finkelshtein

X-ray fluorescence analysis of snow cover solid phase samples collected near aluminum smelter facilities is a promising method for investigating environmental pollution. Key issues in determining fluorine by X-ray fluorescence method in these samples are the lack of matrix-matched reference materials and the strong dependence of the FKα line intensity on fluorine's chemical state. To address this, we considered artificial mixtures for calibration, prepared from soil reference materials, alumina, and various fluorine compounds (such as fluorite, synthetic cryolite, and aluminum fluoride), along with reference materials of apatite ores and granites. Measurements were performed using a wavelength-dispersive spectrometer. The selection of optimal measurement conditions minimized the influence of spectral overlaps and other factors affecting the FKα line intensity. Artificial mixtures based on both aluminum fluoride and synthetic cryolite were chosen as optimal calibration set. For snow cover solid phase samples collected near the Irkutsk Aluminum Smelter (Irkutsk district, Russia), a comparison of the proposed X-ray fluorescence analysis method with potentiometry showed a root mean square deviation of 0.15 wt% for fluorine content range from 0.4 to 1.6 wt%. Furthermore, comparing the data from these two techniques allows for inferences regarding the probable chemical forms of fluorine present in analyzed samples.

对铝厂附近积雪固相样品进行x射线荧光分析是一种很有前途的环境污染调查方法。用x射线荧光法测定这些样品中的氟的关键问题是缺乏基质匹配的标准物质和FKα线强度对氟的化学状态的依赖性强。为了解决这个问题，我们考虑了用于校准的人工混合物，这些混合物由土壤标准物质、氧化铝和各种氟化合物（如萤石、合成冰晶石和氟化铝）以及磷灰石矿石和花岗岩的标准物质制备而成。使用波长色散光谱仪进行测量。最佳测量条件的选择使光谱重叠和其他因素对FKα线强度的影响最小化。选择基于氟化铝和合成冰晶石的人工混合物作为最优标定集。对于在伊尔库茨克铝厂（俄罗斯伊尔库茨克地区）附近收集的积雪固相样品，将提议的x射线荧光分析方法与电位测定法进行比较，发现氟含量在0.4至1.6 wt%范围内的均方根偏差为0.15 wt%。此外，比较这两种技术的数据可以推断分析样品中存在的氟的可能化学形式。

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引用次数: 0

Arc discharge-assisted enhancement of femtosecond LIBS for improved sensitivity in trace Cu detection in aqueous solutions 电弧放电辅助增强飞秒LIBS对水溶液中痕量铜检测的灵敏度

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2025-12-23 DOI: 10.1016/j.sab.2025.107445

Xin Yu , Yuanfei Jiang , Hongxia Qi , Jianhui Han , Anmin Chen , Mingxing Jin

This study combines arc discharge with femtosecond laser-induced breakdown spectroscopy (fs-LIBS) to investigate the time-integrated and time-resolved spectra of aluminum atoms and AlO molecules in aluminum targets. A dried droplet method was further employed to analyze the emission spectra and calibration curves of Cu in aqueous solutions. Under arc-assisted fs-LIBS, at a laser energy of 0.5 mJ, the spectral enhancement factors reached up to 14 and 5 for Al and AlO, respectively. Vibrational temperatures of AlO were calculated as functions of laser energy and detection delay, showing consistently higher values in the presence of arc discharge. For Cu detection, the results revealed that, at a laser energy of 1 mJ, arc-assisted fs-LIBS reduced the limit of detection (LOD) of Cu (I) at 324.75 nm from 187 ng/mL to 25 ng/mL, and at 327.40 nm from 191 ng/mL to 31 ng/mL—corresponding to an improvement of ∼7 and 6-fold respectively over conventional fs-LIBS. The correlation coefficient (R²) of the calibration curve also improved, from 0.949 to 0.951 at 324.75 nm and from 0.896 to 0.957 at 327.40 nm. These results indicate that at relatively low laser energy, arc discharge-assisted fs-LIBS not only enhances the detection sensitivity of Al and AlO species, but also significantly improves the analytical performance of trace Cu in liquids, thereby expanding the applicability of femtosecond LIBS in high-sensitivity spectroscopic analysis.

本研究将电弧放电与飞秒激光诱导击穿光谱（fs-LIBS）相结合，研究了铝靶中铝原子和AlO分子的时间积分和时间分辨光谱。采用干滴法分析了水溶液中Cu的发射光谱和标定曲线。在电弧辅助fs-LIBS下，激光能量为0.5 mJ时，Al和AlO的光谱增强因子分别达到14和5。计算了激光能量和检测延迟对AlO振动温度的影响，结果表明电弧放电时的振动温度始终较高。对于Cu的检测，结果表明，在激光能量为1 mJ时，电弧辅助fs-LIBS将Cu (I)在324.75 nm处的检出限（LOD）从187 ng/mL降低到25 ng/mL，将327.40 nm处的检出限（LOD）从191 ng/mL降低到31 ng/mL，分别比传统fs-LIBS提高了约7倍和6倍。校正曲线的相关系数（R2）在324.75 nm处由0.949提高到0.951，在327.40 nm处由0.896提高到0.957。这些结果表明，在相对较低的激光能量下，电弧放电辅助fs-LIBS不仅提高了Al和AlO的检测灵敏度，而且显著提高了液体中痕量Cu的分析性能，从而扩大了飞秒LIBS在高灵敏度光谱分析中的适用性。

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引用次数: 0

Elemental analysis of healthy and pathological human vertebrae using laser-induced breakdown spectroscopy and inductively coupled plasma optical emission spectroscopy 使用激光诱导击穿光谱和电感耦合等离子体发射光谱对健康和病理人体椎骨进行元素分析

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2025-12-11 DOI: 10.1016/j.sab.2025.107426

H. Sobral , M. Joaquín Robles-Ortiz , C. Márquez-Herrera , Carla García-Ramos , Alejandro A. Reyes-Sanchez

In this study, the elemental composition of human vertebrae obtained from surgical procedures and biopsies was investigated using Laser-Induced Breakdown Spectroscopy (LIBS) and Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). A total of 23 samples were analyzed, including healthy controls, and specimens diagnosed with cancer and chronic osteomyelitis. ICP-OES was applied to larger samples, and these data were used to predict the composition of the entire set through LIBS combined with artificial neural networks. The results revealed a significant reduction in the Ca/P ratio concentration in cancer samples, suggesting disorganized mineralization. In addition, elevated concentrations of several trace elements, namely Zn, Ba, Fe, and Cu, were detected in patients diagnosed with cancer and chronic inflammation, which may be associated with regenerative or osteoblastic activity. These findings demonstrate the potential of LIBS to detect alterations in pathological human vertebral tissue with high sensitivity, even in biopsies weighing only a few milligrams.

在这项研究中，使用激光诱导击穿光谱（LIBS）和电感耦合等离子体光学发射光谱（ICP-OES）研究了从外科手术和活检中获得的人类椎骨的元素组成。总共分析了23个样本，包括健康对照，以及诊断为癌症和慢性骨髓炎的样本。ICP-OES应用于更大的样本，这些数据通过LIBS结合人工神经网络预测整个集合的组成。结果显示癌样中Ca/P比值浓度显著降低，表明矿化无序。此外，在诊断为癌症和慢性炎症的患者中检测到几种微量元素的浓度升高，即Zn， Ba， Fe和Cu，这可能与再生或成骨细胞活性有关。这些发现表明，LIBS具有高灵敏度检测病理人类椎组织变化的潜力，即使在仅重几毫克的活组织检查中也是如此。

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引用次数: 0

Precise determination of 204Pb-based lead isotopic ratios in geological rock samples using quadrupole ICP–MS: A statistics-based procedure for optimizing acquisition parameters 使用四极ICP-MS精确测定地质岩石样品中204pb基铅同位素比率：优化采集参数的基于统计的程序

IF 3.8 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part B: Atomic Spectroscopy

Pub Date : 2026-03-01 Epub Date: 2026-01-09 DOI: 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.

铅（Pb）同位素比值（206Pb/204Pb、207Pb/204Pb、208Pb/204Pb）广泛用于地质、考古和环境科学中物质来源的追踪。同位素比分析的精度取决于有效的样品制备和测量技术。虽然多收集器质谱技术，如热电离质谱（TIMS）和多收集器电感耦合等离子体质谱（MC-ICP-MS），提供最高的精度，但并不总是需要这样的精度水平。四极杆电感耦合等离子体质谱（Q-ICP-MS）可以提供有效的，同时，更实惠和易于获得的分析优化。本研究首次提出了优化Q-ICP-MS采集参数以最大化分析时间效率的详细步骤。与先前发表的研究相比，该技术的应用以及仪器稳定性和灵敏度的提高，显著提高了Q-ICP-MS分析的精度。在不同铅浓度（2 ~ 30 mg/kg）的岩石样品中，包括安山岩JA-2、花岗岩JG-2、玄武岩JB-3和天然玄武岩样品，进行了204pb基铅同位素比值的测定。测定结果的重复性和再现性分别为0.07 ~ 0.13%和0.10 ~ 0.15%。Pb浓度为2 ~ 4 mg/kg的玄武岩样品分析的重复性为0.08 ~ 0.18%。这些值对于低铅浓度样品中204pb基铅同位素比值的Q-ICP-MS分析是例外的。这里描述的基于统计的程序是通用的，可以应用于任何Q-ICP-MS，用于不同样品类型的同位素比率分析，包括环境，考古和地质材料。

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