Atomic Spectroscopy

The Atomic Spectroscopy (ISSN: 0195-5373) is a peer-reviewed journal for rapidly publishing innovative research on fundamentals, instrumentation, methods and applications in the all fields of atomic spectroscopy and mass spectrometry. All published papers can be downloaded freely from the journal website (https://www.at-spectrosc.com), and authors are not required to pay any publication fees (or APC).

Editor-in-Chief: Prof. Xian-Hua Li

Executive Editor: Prof. Wei Guo

Associate Editors: Prof. Michael Dürr, Prof. Wei Hang, Prof. Zhaochu Hu

Editorial Board

Indexed in: Web of Science (JCR, Q2), Scopus

Call for papers:

The 14th international Conference on Laser-Induced Breakdown Spectroscopy (LIBS 2026)

Special issue: Recent Advances in Laser-Induced Breakdown Spectroscopy

Guest editors: Meirong Dong & Shunchun Yao

Submission deadline: 01 July 2026

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Vol.46,2025,NO.6
Pages: 565-674

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Lead Cycling in Plant System: Insights from Pb Isotopes in Elsholtzia Splendens Nakai

Shizhen Li, Xiangkun Zhu*, Aiguo Dong, Jianxiong Ma

DOI: 10.46770/AS.2025.106

[Abstract] (9) [PDF 5.30 M] (59)

Abstract:
A study on Pb isotopes was conducted within the soil–plant–aerosol system. The results indicate that Pb isotopes serve as a suitable tool not only for tracing atmospheric pollution sources but also for tracking the Pb transfer process into and within plants. The main findings are as follows: 1) Pb isotopes in plants are a powerful tool for tracing Pb sources. When plants are removed from their original location, Pb isotopes in the whole plant or roots are suitable for tracing their growth sites; Pb isotopes in leaves are suitable for tracing aerosol particles in the surrounding environment; however, Pb isotopes in stems are not suitable for tracing Pb sources. 2) Pb isotopic fractionation occurs during the growth process of E. splendens Nakai (δ208Pb?????–???? = -4.31 to 0.30‰), and the extent of fractionation is larger than that of most mineral nutrients. This study also demonstrates that Pb isotopes in plants are a powerful tool for tracing the absorption and transport processes of Pb into and within the plant. Regardless of whether Pb is absorbed through the roots or leaves, lighter isotopes tend to be preferentially enriched in the subsequent tissues (from soil to root, from root to stem, and from leaf to stem within the plant), indicating non-selective absorption of Pb through ion channels. This is consistent with the diffusion effect on isotope ratio variation. Pb absorbed through the roots constitutes the main source of Pb in the plant. 3) The correlation between Pb isotope ratios could verify Pb pathways. Whether the correlation conforms to the principle of mass fractionation depends on whether Pb comes from one path or multiple pathways. This provides a new insight into understanding Pb sources in any physicochemical process or geological sample. 4) The addition of ethylene diamine disuccinic acid (EDDS, C??H??N?O?) promotes the uptake of Pb in the plant. However, it only affects the Pb concentration in the root and stem, but not in the leaf. This shows that altering soil state and promoting plant absorption are not ideal for reducing Pb pollution in soil for non-accumulator plants. The addition of EDDS in the soil also affects the variation in Pb isotope ratios within the plant. Compared with CK plants, heavier Pb isotopes were enriched in the EDDS-treated plants, which suggests a plant protection mechanism whereby heavier Pb isotopes are stored in biological macromolecules such as Pb-proteins/ligands to mitigate toxicity.

Simultaneous Determination of Be and U in Uranium-Beryllium Ore Cores via LIBS-XRF Fusion

Xiang Yu, Xuebin Su*, Weiran Song, Boping Li, Dan Zhao, Rui Yang, Zongyu Hou, Zhe Wang*

DOI: 10.46770/AS.2025.279

[Abstract] (13) [PDF 5.35 M] (84) [Supporting Information]

Abstract:
Exploration for critical minerals, such as beryllium (Be) and uranium (U), requires accurate reserve assessment, for which drill core analysis is essential. Techniques like laser-induced breakdown spectroscopy (LIBS) and X-ray fluorescence spectroscopy (XRF) are widely used for rapid core analysis but have some limitations. LIBS suffers from poor sensitivity for low-concentration U, while XRF cannot detect Be. Furthermore, matrix effects in both techniques hinder the accurate simultaneous quantification of Be and U. We introduce a novel LIBS-XRF method for the simultaneous measurement of Be and low-concentration U. The methodology involves first analyzing samples with XRF and LIBS. Subsequently, a support vector machine (SVM) algorithm classifies the samples based on the XRF data. A separate predictive model is then developed for each category. A basic linear model is constructed using the spectral line of the target elements as the dominant factor based on dominant factor (DF) modeling strategy, and machine learning algorithms are then used to compensate for the residuals of this basic model. Tests on ore cores demonstrated that this method significantly reduces quantification errors. The achieved mean relative errors were 7.58% for Be and 7.02% for U. These results represent improvements of 61.42%/77.20% and 69.77%/72.48% over conventional unclassified and experience-based methods, respectively. This work is the first to use a LIBS-XRF approach for the highly accurate and simultaneous detection of Be and low-concentration U in ore cores, proving its high practical utility for this application.

A Correlative Microanalytical Protocol Integrating FIB-SEM, TOF-SIMS, AFM-IR, and NanoSIMS for Mars-analog Basalt

Jingbo Nan*, Jun-Heng Wang, Yilin Wang, Zongjun Yin*

DOI: 10.46770/AS.2025.203

[Abstract] (12) [PDF 6.25 M] (78) [Supporting Information]

Abstract:
The search for carbonaceous matter in Martian rocks is the key to evaluating their potential biosignatures. Studying carbonaceous matter preserved within Earth’s basaltic analogs provides critical insights into the mineral–organic interactions that may also occur on Mars. To characterize molecular-level chemical information of carbonaceous matter, correlative surface-sensitive approaches such as Focused Ion Beam Scanning Electron Microscopy (FIB-SEM), Secondary Ion Mass Spectrometry (SIMS), and Atomic Force Microscopy Infrared Spectroscopy (AFM-IR) are employed. In this study, we developed a correlative microanalytical protocol starting with the ex-situ FIB-SEM lift-out, in which lamellae from a Mars-analog basalt were transferred onto a clean silicon substrate using a glass-needle nanomanipulator. The lamellae were then analyzed sequentially by Time-of-Flight SIMS (TOF-SIMS), AFM-IR, and Nano-scale Secondary Ion Mass Spectrometry (NanoSIMS). Specifically, spatially and chemically co-registered TOF-SIMS, AFM-IR, and NanoSIMS analyses provided complementary insights into the same region, correlating organic distribution, molecular vibrations, and isotopic compositions within mineral matrices. Together, these results demonstrate that the established correlative microanalytical protocol in this study effectively integrates sample preparation and multi-modal surface analyses, providing a framework for investigating planetary materials and future Mars samples.

Precise Determination of Sulfur Isotopes in Organic Matters with 300 nmol Sulfur by An Improved Elemental Analyzer - Isotope Ratio Mass Spectrometry (EA-IRMS)

Pengcheng Sun, Changfu Fan*, Yanhe Li, Bin Hu*, Kejun Hou

DOI: 10.46770/AS.2025.107

[Abstract] (17) [PDF 769.71 K] (101) [Supporting Information]

Abstract:
Elemental analyzer - isotope ratio mass spectrometry (EA-IRMS) is the most popular method for the measurement of sulfur isotopes in various samples including sulfide, sulfate and organosulfur compounds. The precision of ~±0.3‰ (1σ) can be achieved for samples with ~100 μg S. However, for samples with low sulfur content, or organic matter in particular (e.g., animal bone collagen), the precise and accurate sulfur isotope analysis remains challenging, with typical δ34S precision ranging from ±0.3‰ to ±1‰. In this study, we applied an improved EA-IRMS with a custom-built cryofocus device for the analysis of sulfur isotopes in organic matter. After sample combustion, all the product gases were transferred into a cold trap by a fast helium flow (100 mL/min). SO2 was then separated from other gases through a packed gas chromatographic (GC) column at lower flow rate (10 mL/min). The sample size of this method is ~300 nmol S, which is only 1/10 of that required by the conventional method. Lowered sample size allows fully oxygen isotope homogenization of sample SO2 with oxygen buffers during combustion. With this method, the δ34S precision from the measurement of organosulfur standards was better than ±0.3‰.

Perilla Zircon Megacryst: A New Cenozoic Natural Reference Material for In Situ U-Pb Dating and Hf-O Isotopes Analysis

Yan-Guang Li, Hai-Ou Gu, Dong-Yong Li, Xiao-Yan Gu Guo-Chao Sun, Jian-Dong Sun, Jia-Run Tu, Ke-Jun Hou, Run-Long Fan, Meng-Qi Jin, Lan-Lan Tian, Xing-Xiang Zhang, Yan-Jie Zhang, Li-Qun Dai, Ren-Xu Chen, Zi-Fu Zhao

DOI: 10.46770/AS.2025.111

[Abstract] (18) [PDF 9.16 M] (113) [Supporting Information]

Abstract:
Zircon U-Pb and Hf-O isotope compositions preserve valuable records of the formation and evolution of geological processes. To obtain accurate and precise zircon geochronology and Hf-O isotope ratios using in situ techniques, matrix-matched reference materials are essential. In this study, we introduce a new potential zircon reference material, the Perilla megacryst, which has homogeneous U-Pb ages and Hf-O isotopic compositions, as demonstrated by multiple analytical techniques. The chemical abrasion isotope dilution thermal ionization mass spectrometry (CA-ID-TIMS) method presents a weighted mean 206Pb/238U age of 42.40 ± 0.06 Ma (2σ, n = 8). Further examination of the heterogeneity of U-Pb ages of the Perilla zircon megacryst was conducted by secondary ion mass spectrometry (SIMS) and laser ablation (multiple collector) inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) among six laboratories. We obtained mean 206Pb/238U ages of 42.6 ± 0.3 Ma (2σ, n = 23) using SIMS (SHRIMP), 42.6 ± 0.3 Ma (2σ, n = 20) using SIMS (CAMECA), 42.2 ± 0.3 Ma (2σ, n = 14) using LA-MC-ICP-MS, and 42.6 ± 0.1 Ma (2σ, n = 207) using LA-Q-ICP-MS, respectively. The Hf isotopic compositions of Perilla were evaluated using LA-MC-ICP-MS, yielding a uniform mean 176Hf/177Hf ratio of 0.282565 ± 0.000040 (2SD, n = 149) among four laboratories. Oxygen isotope analysis using laser fluorination yielded results consistent with SIMS data, providing a recommended mean δ18O value of 6.53 ± 0.34 ‰ (2SD, n = 5). The reproducibility of results obtained from multiple analytical techniques across different laboratories demonstrate the homogeneity of U-Pb ages and Hf-O isotopic compositions in the Perilla zircon megacryst. Based on these results, we propose the Perilla zircon megacryst as a potential secondary reference material for external monitoring or analytical validation of Cenozoic U-Pb geochronology and Hf-O isotopic measurements.

Magnesium Separation and Purification from Routine and High-Mn Geological Samples for high-precision Isotope Ratio Measurement by MC-ICP-MS

Xinyue Yan, Shizhen Li, Aiguo Dong*, Brian Kendall, Liang-Liang Zhang, Jianxiong Ma, Yuan He, Zhi-Yong Zhu, Simon W. Poulton, Xiang-Kun Zhu

DOI: 10.46770/AS.2025.101

[Abstract] (20) [PDF 8.28 M] (249) [Supporting Information]

Abstract:
High precision magnesium isotope data have been widely used in geological and astrochemical research. Previous studies used cation-exchange resins (e.g., AG50W-X8, AG50W-X12, AGMP-50) for Mg purification of routine geological samples, and these Mg purification protocols yield solutions meeting multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) analytical requirements, but one problem with the reported protocols is that the elution procedure is complex and time-consuming. In addition, some manganese nodule and shale samples have high Mn/Mg mass ratios. Previous studies have used highly concentrated HCl (e.g., 9–12 mol·L?1 HCl) or acetone (95%) to separate Mg from Mn and other elements. However, a low Mn removal efficiency, alongside the toxicity of acetone, may limit the purification of Mg in high-Mn samples (Mn/Mg >16), suggesting that further improvements should be made to the protocol. Here, we developed an efficient, user-friendly, and highly robust protocol for Mg isotope purification and analysis by MC-ICP-MS. Briefly, to isolate Mg from high-Mn matrices, an initial separation from matrix elements (e.g., Mn, Cu, Zn) was performed using AGMP-1M resin (100–200 mesh) eluted with 4.5 mL of 10 mol·L?1 HCl. A subsequent purification step using AG50W-X12 resin (200–400 mesh) was applied to remove major residual matrix elements with a mixed HNO?–HF solution, and Mg was finally collected by elution with 8 mL of 2 mol·L?1 HNO?. With this method, the yield during Mg purification was ~100%, and after one column or a two-column pass, most geological samples were suitable for high-precision Mg isotope analysis. We demonstrate that our method yields accurate Mg isotope ratios with a precision of ±0.07‰ for δ2?Mg, based on analyses of seawater, basalt, granodiorite, shale, manganese nodule, and carbonate reference materials.

Certified Matrix-matched Sulfide Reference Materials for Direct Fe, Cu, and Zn Isotopic Analysis of Simple-matrix Minerals

Xiaojuan Nie, Zhian Bao, Kaiyun Chen, Yan Zhang, Chunlei Zong, Honglin Yuan*

DOI: 10.46770/AS.2025.110

[Abstract] (19) [PDF 3.92 M] (255) [Supporting Information]

Abstract:
Stable isotope systems of iron, copper, and zinc have emerged as powerful tracers in understanding metal sources, migration, and deposit formation processes. Accurate and precise determination of Fe, Cu, and Zn isotopic compositions in sulfide minerals, especially in simple-matrix minerals characterized by their relatively pure composition, with low content of impurity elements and few interfering components, requires matrix-matched reference materials to validate analytical methods, particularly for direct analysis protocols without column chromatography. This study introduces a suite of novel secondary reference materials (NWU-Fe, NWU-Cu, and NWU-Zn sulfide powders) developed to address the critical gap in calibration standards for direct isotopic analysis without column chemistry of simple-matrix minerals. These sulfide powders exhibit excellent homogeneity and stability, fulfilling the requirements for high-precision determination of Fe, Cu, and Zn isotope ratios using MC-ICP-MS without column chemistry. Reference values were derived from interlaboratory comparisons across three independent laboratories. The isotopic compositions (δ-values), reported in per mil notation relative to international standards (IRMM-014 for Fe, NIST SRM-976 for Cu, and JMC-Lyon for Zn), are as follows: δ56Fe = -0.38 ± 0.03‰ (2s), δ65Cu = 0.44 ± 0.04‰ (2s), δ66Zn = -0.04 ± 0.02‰ (2s). This study provides a robust calibration framework for Fe-Cu-Zn isotopic studies in geochemistry and environmental science.

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Wen Zhang Honored with Atomic Spectroscopy 2025 Best Paper Award

Ming Li, Wei Guo*

2025,46(6),565-567,

DOI: 10.46770/AS.2025.171

[Abstract] (12) [PDF 6.99 M] (158)

Abstract:

Article

Micro-area Quantitative and Imaging Analysis of the Qin Terracotta Warriors via Laser Ablation Inductively Coupled Plasma Mass Spectrometry

Guoxia Zhang, Xiaoxi Li, Desheng Lan, Yin Xia, Ping Zhou, Qing Li, Zheng Wang*

2025,46(6),568-576,

DOI: 10.46770/AS.2025.157

[Abstract] (21) [PDF 3.99 M] (155) [Supporting Information]

Abstract:
The Terracotta Warriors, one of the most remarkable archaeological discoveries of the 20th century, provide critical insights into the artistic, technological, and military achievements of the Qin Dynasty. This study established a micro-area quantitative and imaging analysis method for the Qin Terracotta Warriors using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Matrix-matched calibration standards were produced using the powder–pellet method, thereby ensuring the reliable quantification of both major and trace elements. Optimized ablation parameters (energy density of 8.3 J cm?2, repetition rate of 20 Hz, and spot size of 100 μm) yielded stable signal intensities with relative standard deviations below 10%. The application of this method to multiple fragments of the Terracotta Warriors revealed compositional variations associated with color differences, structural layering, and excavation contexts. Quantitative accuracy ranged from 80% to 120%, and elemental imaging was achieved at a spatial resolution of 100 μm. High-resolution multielement maps illustrated the heterogeneous distributions of Cu, As, and Co linked to the pigment residues, offering new insights into pigment preparation techniques and post-burial alteration processes. Overall, the results demonstrate that LA-ICP-MS is a minimally destructive and high-resolution analytical tool that is well suited for the compositional and technological investigation of archaeological ceramics.

Magnesium Isotopic Analysis of Biochemical Reference Materials Using MC-ICP-MS: A Dataset for Dietary and Human Tissue

Di Wang, Guilin Han*, Qian Zhang, Wenqian Sun

2025,46(6),577-585,

DOI: 10.46770/AS.2025.112

[Abstract] (17) [PDF 2.78 M] (179)

Abstract:
Magnesium (Mg) isotopic compositions help decode the complex biogeochemical cycling of Mg in surficial environments. Accurate measurement of Mg isotopes in biological samples requires reference materials with established isotopic compositions, which ensure analytical quality and allow interlaboratory comparison. By employing Nu Plasma III multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), this study establishes a high-precision Mg isotopic dataset for sixteen biological reference materials. The measured δ26Mg values of extra nine reference materials (plant leaves, rocks, and seawater) consistently agree well with references values, confirming the reliability of analytical methodology used in this study. The results reveal the variations for δ26Mg values exceeding 2.2‰ across the food web. Plant leaves are characterized by low δ26Mg values (–0.52‰ ± 0.04‰ ~ –1.28‰ ± 0.03‰), whereas cereals and animal organs exhibit heavier values (up to 0.97‰ ± 0.05‰ for pork liver). The δ26Mg values of scallops (GSB-15), spirulina (GSB-16), and prawn (GSB-28) cluster together with lighter values, representing a marine-derived isotopic end-member for coastal populations. Human hairs (–0.88‰ ± 0.04‰) present an integrated isotopic signature intermediate between major dietary end-members. This dataset expands the Mg isotopic compositions of major dietary and human tissue reference materials, supporting the essential laboratory comparison of isotope analyses and facilitating researches into the Mg biogeochemical cycle.

Typical Factors Influencing the Evolution of Laser-Induced Plasma Radiation and Their Underlying Mechanisms

Chao Li, Yunfeng Bi*, Tao Zhang, Zhongyi Bao, Caijie Liu, Meili Guo, Man Wang

2025,46(6),586-598,

DOI: 10.46770/AS.2025.204

[Abstract] (5) [PDF 8.43 M] (111) [Supporting Information]

Abstract:
Laser energy fluctuations, focal plane position errors, and sample matrix variations are major sources of uncertainty in Laser-Induced Breakdown Spectroscopy (LIBS). A systematic investigation of plasma characteristics under varying laser energies, focal positions, and sample matrices is essential for understanding plasma evolution and the mechanisms underlying measurement uncertainty. Although radiation evolution directly reflects plasma dynamics, its response to these factors remains insufficiently explored. In this study, we experimentally monitored radiation evolution under different laser energies, focal plane positions, and sample matrices, revealing a consistent bimodal pattern: the first peak, dominated by background radiation, exhibited a pulsed profile, while the second peak, governed by excited-state de-excitation radiation, followed a log-normal distribution. The onset time, intensity, and decay rate of the second peak varied across conditions, reflecting inherent uncertainty in LIBS radiation evolution. By integrating multi-wavelength radiation data, spectroscopic measurements, ablation crater volumes, and plasma parameters, we found that higher initial plasma temperatures delayed the second peak, higher initial total population densities increased its intensity, and the decay after the second peak was jointly influenced by the initial electron density and ionization level. These findings provide direct evidence for the dynamic evolution mechanisms of laser-induced plasmas and offer insights for refining temporal plasma models, optimizing LIBS acquisition strategies, and enhancing measurement stability and precision.

Assessment of Four Potential Reference Materials for Simultaneous Determination of in Situ U-Pb Isotopes and Trace Elements in Vesuvianite

Qing-Qing Zhang, Jian-Feng Gao*, Yan-Wen Tang*, You-Wei Chen, Jun-Jie Han

2025,46(6),599-613,

DOI: 10.46770/AS.2024.099

[Abstract] (19) [PDF 12.53 M] (153) [Supporting Information]

Abstract:
Vesuvianite is a prevalent mineral in skarn system and has become an indispensable U-Pb geochronometer due to its capable of directly constraining the timing of skarn mineralization. However, the matrix effects between various potential primary reference materials and vesuvianite are not yet fully understood. This study evaluates four potential reference materials: vesuvianite Wilui, garnet PL57, garnet Willsboro, and zircon 91500, for vesuvianite U-Pb dating. The results indicate that the matrix effect between Wilui and other vesuvianite samples is negligible under different ablation conditions. In contrast, PL57 exhibits a pronounced matrix effect under most analytical conditions, limiting its application as an external calibrator for U-Pb dating of vesuvianite. Both Willsboro and 91500 show insignificant matrix effect with vesuvianite at a repetition rate of 5 Hz and fluence of 3 J/cm2, across a range of spot sizes (16–44 μm). Moreover, 91500 is suitable for use with spot size ranging from 32 to 44 μm, when combined with either 10 Hz - 3 J/cm2 or 5 Hz - 5 J/cm2. Consequently, 91500 emerges as more suitable non-matrix-matched reference material in light of its high homogeneity and wide applicability. Furthermore, this study successfully and precisely determined the trace elements and U-Pb age of vesuvianite samples Bufa and M6635 using four reference materials as external calibrators at condition of 44 μm - 5 Hz - 3 J/cm2. The obtained U-Pb ages of 30–33 Ma and 225–233 Ma are in good agreement with their ID-TIMS ages within the measurement errors, respectively. This demonstrates the reliability and feasibility of the optimized calibration methods employed in this study.

Aperture Mask Assisted Depth Profiling of p-type SiC Epitaxial Wafers by Glow Discharge Mass Spectrometry

Zhenkai Sun, Runxian Yang, Xintong Liu*, Yue Zhang, Xiufang Chen

2025,46(6),614-621,

DOI: 10.46770/AS.2025.205

[Abstract] (11) [PDF 1.47 M] (120)

Abstract:
This study investigated the use of n-type SiC substrates as mask materials for the depth profiling of p-type SiC epitaxial wafers using GD-MS. The optimized glow discharge conditions for achieving a flat crater and effective signal intensity were a discharge current of 2 mA and a discharge voltage of 1000 V. The epitaxial layers prepared by chemical vapor deposition were tested, and the results demonstrated that the mask technique effectively reduced edge effects and improved the sputter crater morphology. The optimal mask conditions were a thickness of 0.35 mm with a 4 mm aperture, achieving a depth resolution of 56 nm. The accuracy and reliability of the mask technique were validated using epitaxial wafers with known doping concentrations, showing a 5% deviation from the actual values. This study provides an efficient and reliable method for determining the elemental concentration and distribution in semiconductor epitaxial layers by GD-MS.

Determination of Lithium in Seawater Samples by Tandem Quadrupole Inductively Coupled Plasma Mass Spectrometry

Yanbei Zhu*, Yuki Ota, Yasuyuki Shikamori, Kazumi Nakano, Kyoko Yamaoka

2025,46(6),622-628,

DOI: 10.46770/AS.2025.233

[Abstract] (15) [PDF 729.78 K] (155) [Supporting Information]

Abstract:
Determination of lithium was conducted by standard addition and isotope dilution, where lithium isotopes were measured by tandem quadrupole inductively coupled plasma mass spectrometry (ICP-QMS/QMS). Considering the low atomic mass of lithium, the ICP-QMS/QMS operating conditions were optimized to minimize the suppression of signal intensities due to space charge effects. Attentions were also paid to spectral interferences affecting the measurements of lithium isotopes, for which the results showed oxygen reaction help reduce related spectral interferences while lithium isotopes were measured at on-mass mode. Lower radio frequency (RF) power at 700 W provided lower background equivalent concentrations for lithium isotopes but higher RF power at 1600 W resulted in higher reliable results of lithium isotopic ratio. Lithium in multiple seawater certified reference materials (CRMs) were determined by both standard addition at lower RF power condition and isotope dilution at higher RF power condition, showing lithium concentration in the range of 150 ng/g to 170 ng/g. The results obtained by standard addition and isotope dilution were in coincidence with each other for each seawater CRM sample, confirming the reliability of these results.

Investigation of Fiber Laser–Material Interaction Mechanisms Governing Ablation Modes and Plasma Excitation in FL-LIBS

Sijie Feng, Qi Yang, Jinna Mei*, Huaiqin Qin, Shunchun Yao*

2025,46(6),629-640,

DOI: 10.46770/AS.2025.223

[Abstract] (11) [PDF 8.23 M] (150) [Supporting Information]

Abstract:
Fiber-laser-based laser-induced breakdown spectroscopy (FL-LIBS) is well suited for in-situ and rapid analysis of thermal aging steels in nuclear power systems. The unique ablation behavior of the fiber laser strongly affects plasma excitation and spectral characteristics. This study aims to investigate how ablation features influence plasma excitation and emission characteristics in the FL-LIBS process. Different ablation modes were obtained by adjusting the focal position and power density. The ablation process was characterized through crater morphology analysis and the observation of phase explosion. These results were then correlated with plasma excitation behavior. At -2mm, the laser heating efficiency reached its highest level. This allowed the plasma temperature to remain high even at low power densities. Under this condition, the spectral quality was the best, with high signal-to-noise ratio (SNR) and low relative standard deviation (RSD). At +2mm, stronger ablation was achieved at the expense of excessive ionization. The accompanying increase in bremsstrahlung emission suppressed the spectral SNR. Under both ±2mm settings, higher power density drove the ablation mode from vaporization to phase explosion. The generated vapor–droplet mixture modified the plasma excitation behavior. At 0mm, the slower decay of edge energy strengthened heat conduction around the core-ablation zone. This effect led to an expansion of the thermal-conduction zone. At high power levels, such expansion intensified pulse-to-pulse thermal interference, resulting in reduced ablation stability and a more dispersed plasma excitation distribution. These findings provide a physical basis for optimizing the FL-LIBS system and guide accurate in-situ thermal aging diagnostics of nuclear power plant steel.

Indium, Thallium, Antimony, and Bismuth in Antarctic Lichens from the Antarctic Peninsula Region

Pavel Coufalík*, Ond?ej Zvě?ina

2025,46(6),641-648,

DOI: 10.46770/AS.2025.201

[Abstract] (19) [PDF 4.15 M] (149) [Supporting Information]

Abstract:
The fragile Antarctic ecosystem is now more threatened by anthropogenic impacts than ever before, particularly in maritime Antarctica. Technology-critical elements (TCEs) produced by industrial activities can reach Antarctica by long-range atmospheric transport. This study aimed to determine the contents of indium, thallium, antimony, and bismuth in lichens from Deception Island, King George Island, Livingston Island, Nelson Island, Horseshoe Island, and James Ross Island, in order to identify potential contaminants. An analytical method employing high-resolution continuum source hydride generation atomic absorption spectrometry (HR-CS HGAAS) with a detection limit of 0.002 mg kg-1 was developed for the precise determination of bismuth. The highest observed contents of In, Tl, Sb, and Bi were 0.44 mg kg-1, 0.018 mg?kg-1, 0.257 mg kg-1, and 0.011 mg?kg-1, respectively. Knowing the current state of metal levels in this area is important for further research owing to the minimal clarification of the deposition and fate of TCEs in Antarctica.

Quantitative Analysis of Trace Samarium in Basalt Model Samples Using Laser-Induced Breakdown Spectroscopy Combined with PLS Regression for Ultraviolet Spectra

Xizhu Wang, Xuesen Xu*, Xiangfeng Liu*, Wenhao Lv, Shuqin Zhan, Ziyi Wang, Tangying Tong, Shijia Luo, Rui Xu, Weiming Xu

2025,46(6),649-658,

DOI: 10.46770/AS.2025.206

[Abstract] (13) [PDF 6.83 M] (105) [Supporting Information]

Abstract:
Efficient and precise quantification of rare earth elements (REEs) constitutes a pivotal challenge for advancing extraterrestrial resource exploration. Conventional spectral quantification models typically prioritize isolated characteristic lines, neglecting the analytical potential of full- range spectral data in complex matrices. This research addresses the quantitative determination of trace samarium (Sm) in basaltic matrices through preparation of standardized samples with Sm concentrations spanning 50-140 mg/kg, investigated and optimised the quantitative models based on Laser-Induced Breakdown Spectroscopy (LIBS) combined with Partial Least Squares Regression (PLSR). Although traditional PLSR models demonstrate quantitative feasibility, experimental results revealed that characteristic spectral line models exhibit substantial prediction deviations, while the spectral background contains diagnostically critical information that should be retained for quantitative analysis. The implementation of wavelet transformation (WT) enabled profound extraction of latent features from full-range ultraviolet (UV) spectra. The developed WT-PLSR models demonstrated substantial superiority over traditional full-range UV spectral PLSR models, with the optimal model achieving training set R2 = 0.99929 and test set R2 = 0.9928. This methodology significantly enhanced both predictive precision and model robustness, confirming the critical importance of background information utilization. This provides a novel approach for developing in situ, high-precision spectroscopic quantification techniques for trace REEs in complex matrices.

Zinc Isotopic Compositions of 23 Certified Biological Reference Materials (Plants, Animal Tissues, Foods) Measured by MC-ICP-MS

Jinrong Liu, Qian Zhang*, Ziyang Ding, Tao Liang, Guilin Han

2025,46(6),659-666,

DOI: 10.46770/AS.2025.151

[Abstract] (17) [PDF 4.07 M] (162) [Supporting Information]

Abstract:
Zinc (Zn) isotopes are increasingly applied in biogeochemistry, nutrition, and environmental sciences, but systematic data for biological reference materials remain scarce. In this study, we present high-precision Zn isotope measurements of a wide range of certified biological reference materials, including plants, animal tissues, human tissues, and processed food, using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) combined with a one-column ion-exchange purification protocol. The analytical procedure yielded excellent repeatability, with long-term precision better than ± 0.07 ‰ (2SD) for δ66/64Zn. Isotopic analyses were performed on 23 certified biological reference materials, covering plants (e.g., wheat, spinach leaves, ginseng), animal/human tissues (e.g., scallop, pork liver, human hair), and processed foods (e.g., milk powder, infant formula). The measured δ66/64Zn values span distinct ranges: plants (0.19‰ to 0.84 ‰), animal tissues (-0.61 ‰ to 0.35 ‰), human hair (-0.07 ‰ to -0.08 ‰), and food products (0.49 ‰ to 0.88 ‰). These results were consistent with previously reported data for selected standards (e.g., BCR-2, BHVO-2, GBW10051), confirming method accuracy. Importantly, this study provides the first systematic dataset of δ66/64Zn values for 18 previously unreported biological reference materials, thereby establishing robust baselines for future research in Zn biogeochemical cycling, food authenticity, nutritional assessment, paleodiet and biomedical applications.

Molybdenum Isotope Analysis Using the Neoma MS/MS MC-ICP-MS

Yan Han, Feng Liang*, Zhifang Hu, Lanping Feng*, Lian Zhou, Zhaochu Hu

2025,46(6),667-674,

DOI: 10.46770/AS.2025.202

[Abstract] (15) [PDF 1.55 M] (148) [Supporting Information]

Abstract:
Molybdenum (Mo) isotopic analysis using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has become a cornerstone technique in modern geochemistry. However, achieving accurate and precise measurements in samples with low Mo concentrations or complex matrices remains challenging due to conventional instrument limitations. This study presents the first systematic evaluation of the Thermo Scientific Neoma MS/MS MC-ICP-MS, a new and advanced platform featuring a double-Wien filter and an advanced collision/reaction cell (CRC) design, for Mo isotope measurements. We investigated how instrumental configurations—specifically cone combinations and plasma conditions—affect sensitivity and matrix tolerance, focusing on its potential to overcome existing analytical barriers. Compare to Neptune platform, the Neoma MS/MS exhibits markedly enhanced sensitivity, yielding a 2- to 5-fold improvement, under both dry and wet plasma conditions. Critically, a long-term external precision of 0.06‰ (2SD) at low concentrations, down to 10 ng g-1, was achieved via Neoma. Notably, the Jet/X cone interface simultaneously enhances signal intensity and mitigates matrix effect, successfully challenging the conventional trade-off between sensitivity and matrix effect. These results highlight the Neoma MS/MS as a significant advancement for high-precision Mo isotope analysis, offering unprecedented accuracy and resilience under demanding geological conditions, particularly for samples with extremely low Mo content.

Determination of Trace Copper in Biological Samples by On-line Chemical Vapor Generation-Atomic Fluorescence Spectrometry

Liang He, Xiaofan Zhu, Li Wu, Xiandeng Hou*

, DOI: 10.46770/AS.2008.03.004

[Abstract] (489) [PDF 146.88 K] (3677)

Abstract:
On-line chemical vapor generation atomic fluorescence spectrometry (CVG-AFS) was, for the first time, used to determine trace copper in biological samples by merging acidified sample solution with potassium tetrahydroborate aqueous solution in the presence of micro-amounts of 1,10-phenanthroline. Nitric acid, for both sample digestion and chemical vapor generation, was used as the acid medium. CVG conditions and instrumental parameters were optimized for the best CVG efficiency, good gas/liquid separation, and efficient atomization/excitation. Under the optimized conditions, a limit of detection of 4 ng mL(-1) was obtained for copper, with a linear dynamic range of over three orders of magnitude. The proposed method was successfully applied to the determination of copper in biological certified reference materials.

Rapid Determination of Chemical Oxygen Demand by Flame AAS Based on Flow Injection On-line Ultrasound- assisted Digestion and Manganese Speciation Separation

Zhi-Qi Zhang*, Hong-Tao Yan, Lin Yue

, DOI: 10.46770/AS.2004.04.006

[Abstract] (446) [PDF 86.02 K] (3560)

Abstract:
A rapid, sensitive, and cost-effective method was developed for the determination of trace mercury in water samples by on-line coupling of flow injection (FI) sorption preconcentration with oxidative elution to cold vapor atomic fluorescence spectrometry (CV-AFS). race Hg(II) in aqueous solution was preconcentrated by on-line formation of mercury diethyldithiocarbamate complex (Hg-DDTC) and adsorption of the resulting neutral complex on the inner walls of a PTFE knotted reactor (KR). A mixture of 16% (v/v) HCl and 10% (v/v) H2O2 was used as the eluent to remove the adsorbed Hg-DDTC from the KR, then convert on-line the Hg-DDTC into Hg(II) prior to its reduction to elemental mercury by KBH4 for subsequent on-line CV-AFS detection. The tolerable concentrations of Cd(II) As(Ill) Se(IV) Fe(III), Co(II), Ni(II), and Cu(II) and Cu(II) for the determination of 0.1 mug L-I Hg(II) were 0.1, 10, 0.1, 0.1, 0.7, 1, 0.3, and 0.2 mg L-1, respectively. With a sample loading flow rate of 3.1 mL, min(-1) for a 60-s preconcentration, a detection limit (3sigma) of 4.4 ng L-I was achieved at a sample throughput of 36 samples h(-1). The precision (RSD, n = 11) was 1.7% at the 1 0, 1-mug L-1 Hg (11) level. The method was successfully applied to the determination of mercury in a certified reference material, GBW(E) 080392, and a number of local natural water samples.

Determination of Cadmium at the Nanogram per Liter Level in Seawater by Graphite Furnace AAS Using Cloud Point Extraction

Chun-gang Yuan, Gui-bin Jiang*, Ya-qi Cai, Bin He, Jing-fu Liu

, DOI: 10.46770/AS.2004.04.003

[Abstract] (436) [PDF 99.16 K] (3868)

Abstract:
A method based on?cloud?point?extraction?was developed to determine?cadmium?at?the?nanogram?per?liter?level?in?sea-water?by?graphite?furnace?atomic absorption spectrometry. Diethyldithiocarbamate (DDTC) was used as?the?chelating reagent to form Cd-DDTC complex; Triton X-114 was added as?the?surfactant.?The?parameters affecting sensitivity and?extraction?efficiency (i.e., pH?of?the?solution, concentration?of?DDTC and Triton X-114, equilibration temperature, and centrifugation time) were evaluated and optimized. Under?the?optimum conditions, a preconcentration factor?of?51.6 was obtained for a 20-ml, water sample.?The?detection limit was as low as 2.0 ng L-1 and?the?analytical curve was linear?in?the?10.0-200.0 ng L-1 range with satisfactory precision (RSD < 4.7%).?The?proposed method was successfully applied to?the?trace?determination?of?cadmium?in?seawater.

Development and Validation Method for the Determination of Rare Earth Impurities in High Purity Neodymium Oxide by ICP-MS

Man He, Bin Hu*, Zucheng Jiang, Yan Zeng

, DOI: 10.46770/AS.2004.01.002

[Abstract] (456) [PDF 154.90 K] (3711)

Abstract:
The analytical procedure for the determination of trace rare earth impurities in high purity neodymium oxide (Nd2O3) by ICP-MS is described. The effect of ICP-MS operating parameters on the REO(H)(+)/RE+ production ratio was studied in detail, and the optimal ICP operating conditions were established. In this context, the relationship between REO(H)(+)/RE+ production ratio and the bond strength of the rare earth oxides is also discussed briefly. For the correction of the spectral interference induced by the matrix (neodymium), a simple correction equation was used for correcting the interferences of the polyatomic ions NdO+ and NdOH+ with Tb-159 and Ho-165. The proposed method was applied to the determination of trace rare earth impurities in high purity Nd2O3\, and the analytical results were in good agreement with the recommended reference values.

Multielement Analysis of Alkaline-Resistant Glass and Basalt Glass Fibers Using Laser Ablation ICP-MS: A Useful Tool in Technical Textile Quality Control

J. Su. Becker, C. Pickhardt, N. Hoffmann, H. H?cker, J. Sa. Becker*

, DOI: 10.46770/AS.2002.01.001

[Abstract] (578) [PDF 135.56 K] (4131)

Abstract:
A powerful multielement analytical technique using laser ablation Inductively coupled plasma source mass spectrometry (LA-ICP-MS) for the sensitive determination of trace impurities in thin glass filaments, used as reinforcing material in the construction industry, was developed. The trace analysis was carried out directly on very thin solid strands (without any sample preparation steps) by LA-ICP-MS whereby a bundle of thin glass fibers (with a filament diameter of about 10 - 20 mum) was fixed on a thin, special tape of a target holder. The fibers were ablated in the ablation chamber with the aid of a commercial laser ablation system using a Nd-YAG laser at a wavelength of 266 nm). In order to verify the trace analytical data, the ablated T-glass fibers were analyzed using a quadrupole (LA-ICP-QMS) and double-focusing sector field mass spectrometer (LA-ICP-SFMS). The detection limits of the trace elements in glass fibers using the LA-ICP-MS with a quadrupole analyzer were in the sub mug g(-1) range, whereas using a sector,field mass spectrometer (LA-ICP-SFMS) the detection limits could be Improved by 3-4 orders of magnitude down to the low and sub ng g(-1) range. The multielement trace analytical method, developed for high-purity glass fibers, was applied to the determination of chemical composition on thin alkati-resistant glass and basalt fibers with finishing additives used in fine concrete for the building industry. The analytical results were quantified using standard reference materials (SRMs) of glass matrix, such as the NIST 612 glass SRM and the basalt geological reference glasses, KL-2G and ML3B-G, for the trace analysis of basalt glass fibers. The experimentally determined relative sensitivity coefficients (RSC) in LA-ICP-MS for both SRMs varied between 0.2 and 3 for most of the elements. An increase of the relative sensitivity coefficients was observed with increasing mass. The relative standard deviation (RSD) of most elements (N = 3) was T between 2 and 10%. The results of the trace element concentrations by LA-ICP-MS using different instrumentation are in good agreement.

On-line Ion Exchange Preconcentration in a Sequential Injection Lab-on-valve Microsystem Incorporating a Renewable Column With ETAAS for the Trace Level Determination of Bismuth in Urine and River Sediment

Jianhua Wang, Elo Harald Hansen*

, DOI: 10.46770/AS.2001.03.003

[Abstract] (371) [PDF 167.98 K] (3450)

Abstract:
A?sequential?injection?system?for?on-line?ion exchange separation and?preconcentration?of trace level amounts of metal ions with ensuing detection by electrothermal atomic absorption spectrometry (ETAAS) is described. Based on the use of?a?renewable microcolumn incorporated within an integrated lab-on-valve microsystem, the?column?is initially loaded with?a?defined volume of beads of an SP Sephadex C-25 cation exchange resin. After having been exposed to?a?metered amount of sample solution, the loaded bead suspension is precisely manipulated within the valve to allow reproducible elution of the retained analyte by 30 muL nitric acid (1: 16,v/v) which, via air segmentation, are then transported into the graphite tube for quantification. The content of the used?column?is afterwards discarded and new?column?material is aspirated for the next run. The ETAAS determination is performed in parallel with the?preconcentration?process of the ensuing sample. The performance of the?system?is demonstrated for the determination of bismuth. With 2.4-mL sample loading, an enrichment factor of 33.4,?a?detection limit of 27 ng 1:1, along with?a?sampling frequency of 10 h(-1) was obtained. The relative standard deviation was 2.3% for the determination of 2.0 mg 1:1 Bi (n = 7). The procedure was validated by determination of bismuth in?a?certified reference material CRM 320 (river sediment) and by bismuth spike recoveries in two human urine samples.

A Sequential Injection On-Line Column Preconcentration System for Electrothermal AAS Determination of Thallium in Geochemical Samples

Zhang-Run Xu, Shu-Kun Xu, Zhao-Lun Fang*

, DOI: 10.46770/AS.2000.01.004

[Abstract] (361) [PDF 116.38 K] (3322)

Abstract:
A?sequential?injection?system?for?on-line?sorbent extraction?preconcentration?in electrothermal atomic absorption spectroscopy was developed for the determination of trace thallium in geochemical samples. The TlBr4-1 complex was adsorbed on?a?20-mu L micro-column?(located at the tip of the furnace sampling probe) packed with XAD-8 resin. After sequentially aspirating separate zones of acetone, rinsing acid, and sample (pretreated with bromine) into?a?2.5-m long, 1-mm i.d. holding coil, the flow was reversed and directed to the?column. Sample loading, analyte adsorption,?column?rinsing and analyte elution were achieved within?a?single reversed syringe stroke. The adsorbed analyte was eluted into the furnace with 50 mu L acetone. Mutual mixing between sample, rinsing acid, and eluent were prevented by separating the zones with small air segments during metering. Tightening of?column?packing was avoided by?a?slight back-suction through the?column?after each operational cycle. With 1-mL sample loading, an enrichment factor of 15 was obtained with?a?detection limit of 18 ng/L thallium (3 sigma).?A?precision of 2.4% RSD (n=11, 4 μ g/L) and?a?sampling frequency of 11/hour were achieved. The method was applied to the analysis of geochemical samples. The results were in good agreement with the certified values of standard reference geochemical materials.

Trace Metals in Traditional Chinese Medicine: A Preliminary Study Using ICP-MS for Metal Determination and As Speciation

Xiaoru Wang, Zhixia Zhuang, Dahai Sun, Jiangxing Hong, Xihong Wu

, DOI: 10.46770/AS.1999.03.002

[Abstract] (509) [PDF 283.26 K] (3777)

Abstract:
The metal content in several TCM drugs was determined by ICP-MS. The efficiencies of different sample digestion methods were compared. Since one of the products studied is known to contain arsenic sulfides as a main ingredient, a solvent fractionation scheme was developed and applied to speciate As in the product. The metal content in the same TCM drug produced by different manufacturers was compared. The concentration of some metals such as Pb and Cd differs widely with different manufacturers, suggesting that their origin is primarily from external contamination. The high sensitivity and precision of the ICP-MS technique offers considerable advantages over conventional ICP-OES techniques for the analysis of complex samples such as TCM materials. Standardized analytic protocols based on ICP-MS are being developed fur the determination and characterization of metals and trace elements in TCM materials for product quality assessment.

Theory, design, and operation of a dynamic reaction cell for ICP-MS

Tanner S.D.* Baranov V.I.

, DOI: 10.46770/AS.1999.02.001

[Abstract] (423) [PDF 0.00 Byte] (0)

Abstract:
Theory, design, and operation of a dynamic reaction cell for ICP-MS

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