Editor in Chief:
Prof. Xian-Hua Li

Executive Editor:
Prof. Wei Guo

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

Print ISSN:0195-5373
Online ISSN: 2708-521X
2023 SCIE IF: 3.4 (JCR, Q1)

The ATOMIC SPECTROSCOPY is a peer-reviewed journal started in 1962 for PerkinElmer by Dr. Walter Slavin and now is published by Atomic Spectroscopy Press Limited (ASPL), Hongkong, P.R. China. It is intended for the rapid publication of both original paper and reviews in the fields of AAS, AFS, XRF, LIBS, ICP-OES, ICP-MS, GD-MS, TIMS, SIMS, AMS, electron microscopy and energy spectroscopy related microbeam analysis techniques, and Synchrotron radiation related technology,etc. Manuscripts dealing with (i) fundamentals & instrumentation development, (ii) novel methodology development & applications, (iii) sample preparation related technology, and (iv) standard reference materials development, can be submitted for publication. All published papers can be downloaded freely from the journal official website (www.at-spectrosc.com), and authors are not required to pay any publication fees (or APC).

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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*

DOI: 10.46770/AS.2025.157

[Abstract] (0) [PDF 4.01 M] (0) [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.

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] (5) [PDF 769.71 K] (23) [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‰.

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

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

DOI: 10.46770/AS.2025.202

[Abstract] (2) [PDF 1.01 M] (19) [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.

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

Pavel Coufalík*, Ond?ej Zvě?ina

DOI: 10.46770/AS.2025.201

[Abstract] (10) [PDF 4.17 M] (32) [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.

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

DOI: 10.46770/AS.2025.112

[Abstract] (7) [PDF 2.80 M] (35)

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.

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] (6) [PDF 9.16 M] (38) [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.

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

DOI: 10.46770/AS.2025.151

[Abstract] (8) [PDF 4.08 M] (44) [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.

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] (11) [PDF 8.28 M] (174) [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] (12) [PDF 3.92 M] (203) [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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Review

Review: Direct Analysis of Metal Constituents in Complex Samples by Mass Spectrometry

Lili Song, Wu Zhang, Luyao Zhong, Chun Wan, Hui Li, Xinglei Zhang*, Jiaquan Xu*

2025,46(5),457-474,

DOI: 10.46770/AS.2025.150

[Abstract] (11) [PDF 4.26 M] (287)

Abstract:
The information of metal constituents in complex samples is crucial for understanding the physicochemical properties and formation mechanisms of samples. Moreover, direct analysis of metal constituents in such samples without sample pretreatment not only enhances analytical efficiency but also facilitates the elucidation of physical and chemical relationships among the components, which has attracted wide spread attention. Mass spectrometry possesses remarkable advantages in both qualitative and quantitative analyses of metal constituents. This review systematically summarizes recent advances in mass spectrometry-based methods for the direct analysis of metal constituents over the past decade. Unlike existing reviews, this work offers a overview of both hard ionization and soft ionization mass spectrometry techniques applied to the direct analysis of metallic elements. In this review, we present the fundamental principles of mass spectrometry relevant to this application, highlight representative applications across diverse fields such as environmental science, geology, and materials science, and critically discuss the advantages and limitations of each approach. Finally, we outline future research directions for advancing mass spectrometry in the direct analysis of metal constituents. This review provides valuable insights for the development of high-performance analytical methods for metal constituent analysis.

Article

Molecular LIBS for Sorting and Analysis of Rare Earth Elements – Evaluation of Potential Applications

Michael Gaft*

2025,46(5),475-483,

DOI: 10.46770/AS.2025.149

[Abstract] (15) [PDF 942.91 K] (237) [Supporting Information]

Abstract:
The main purpose of this article is to attract attention to the molecular emission of rare earth elements (REEs) in laser-induced plasma (LIP) as a potential opportunity in addition to traditional atomic and ionic LIBS. This is relevant for analyzing REE-bearing materials of various types during exploration, mining, and processing. The first potential application is preliminary radiometric sorting, which enables the removal of a substantial portion of the waste rock from the entire technological process, making the development of even relatively low-grade deposits profitable. Additionally, products may be derived from the old waste, resulting in a positive ecological impact. Promising directions include electronic waste sorting, quantification of REE in Nd–Pr–Fe-B and Sm-Co super magnets, remote detection in nuclear-related applications, and the analysis of a small amount of a specific REE in the presence of a higher level of another one.

Raman-based Characterization of Chang’e-6 Farside Lunar Soil: Insights into Non-mare Ejecta Composition and Lithological Diversity

Shuang Shi, Xinyi Wang, Kenan Cao, Zhenbing She*, Zaicong Wang*, Qi He, Tianyang Li, Yiheng Li, Jiaqi Zheng, Xu Chen, Long Xiao, Biji Luo, Keqing Zong, Zhaochu Hu, Xiang Wu

2025,46(5),484-492,

DOI: 10.46770/AS.2025.147

[Abstract] (14) [PDF 1.11 M] (344) [Supporting Information]

Abstract:
The Chang’e-6 (CE-6) mission returned the first farside lunar soil samples which are of great importance to understand the geological diversity and evolutionary history of the Moon. In this study, we employed a Raman-based automated particle analysis system to investigate the grain size and mineral composition of the CE-6 soil, which are compared with results of the nearside Chang’e-5 (CE-5) soil. Our analyses reveal that the CE-6 soil exhibit small grain size (mean = 4.4 μm) as the CE-5 soil, but markedly higher glass content (37.8 vs. 8.3 vol%), slightly higher plagioclase abundance (39.0 vs. 37.5 vol%), and lower pyroxene (18.4 vs. 39.4 vol%) and olivine (2.3 vs. 9.8 vol%) content. Raman spectroscopic analysis further reveals a marked magnesium enrichment in CE-6 olivines (most grains with Fo of 40-90) compared to their CE-5 counterparts (most Fo < 60). Notably, evident compositional zonation in olivine (Fo of 66 to 47) is observed for a CE-6 lithic clast, which likely represents ejected crustal material with complex magmatic interactions. These findings support that the CE-6 scooped soil contains substantial non-mare components that is limited in the CE-5 sample. Given very low olivine abundance in the CE-6 landing site basalt, the wide range of olivine Fo in CE-6 soil reflects the contribution of olivine-bearing, mafic crustal lithologies such as magnesian-suite and ferroan anorthosite or even of material from the lunar mantle. This study highlights the capability of non-destructive, rapid and simultaneous determination of particle size and mineral composition with Raman-based analytical techniques, which enables direct analyses of complex soil samples and provides new insights into the mineral compositions of landing site basalts and also non-mare ejecta of the near and far sides of the Moon.

In-situ Trapping of Cd and Se in a Dielectric Barrier Discharge Atomizer after Volatile Species Generation: Optimization of the Preconcentration Step for Atomic Absorption Spectrometry

Linda Sagapova*, Milan Svoboda, Jan Kratzer*

2025,46(5),493-504,

DOI: 10.46770/AS.2025.146

[Abstract] (25) [PDF 1005.96 K] (245) [Supporting Information]

Abstract:
In-situ preconcentration of volatile Se and Cd species in the dielectric barrier discharge (DBD) atomizer for subsequent analyte detection by atomic absorption spectrometry (AAS) was investigated. Quantitative trapping of selenium hydride in the DBD atomizer, followed by incomplete volatilization of trapped analyte species, was previously described in the simplest apparatus arrangement. In this work, two advanced constructions of both the DBD atomizer and its high voltage power supply source were tested to improve the preconcentration efficiency by increasing the volatilization efficiency of trapped Se species. Unfortunately, no significant improvement was found. The overall preconcentration efficiency ranged between 60 and 70% regardless of the apparatus set-up. In contrast to Se, in-situ trapping of volatile Cd species in the DBD atomizer for AAS was optimized for the first time in this work. Quantitative Cd trapping was observed at 17.5 kV with 3.5 mL min-1 O2 admixed to 300 mL min-1 Ar, while complete analyte release was achieved at 25.2 kV with 75 mL min-1 Ar. The preconcentration efficiency was quantified to 98 ± 7%. The sample loop volume was optimized to 0.15 mL, as higher sample volumes unfortunately led to a significant decrease in preconcentration efficiency due to analyte loss during the prolonged trapping step.

Contribution of Planetary Ball Milling to the Homogeneity of Pyrrhotite Reference Material for LA-ICP-MS

A. O. Klimov, A. Bakhadur, V. D. Abramova, L. V. Ragozin, K. A. Kokh*

2025,46(5),505-511,

DOI: 10.46770/AS.2025.145

[Abstract] (25) [PDF 4.98 M] (249)

Abstract:
The present study optimized the planetary ball milling of synthetic pyrrhotite doped with trace metals in order to enhance homogeneity. It has been demonstrated that milling at 400 rpm with acetone is an effective method of reducing particle size, whilst also preventing oxidation and secondary phase formation, in contrast to the process of dry grinding. Annealed samples demonstrated excellent trace element uniformity (RSD ~2-3%) by LA-ICP-MS, comparable to or superior to existing standards. The work underlines the pivotal role of milling conditions in the production of reliable sulfide standards, which are essential for accurate analysis in geochemistry and materials science.

On-site Rapid Analysis of Metal Ions and Nanoparticles Based on the Preconcentration and Separation with Stereoscopic Amphiphiles

Yun Liu*, Weipeng Yao, Shengjie Chen, Yanhua Li, Fang Chen, Lin Gao

2025,46(5),512-519,

DOI: 10.46770/AS.2025.128

[Abstract] (15) [PDF 910.91 K] (224) [Supporting Information]

Abstract:
A novel on-site analytical approach for the determination of trace metal ions and nanoparticles in environmental water is presented, utilizing a self-developed amphiphilic material that enables rapid enrichment and precipitation of analytes. This material, consisting of a hydrophobic polyhedral oligomeric silsesquioxane (POSS) core covalently linked to functional hydrophilic ligands, spontaneously self-assembles in aqueous solutions to form micron-scale aggregates, thereby facilitating efficient extraction and phase separation without heating, pH adjustment, or auxiliary agents. After enrichment, the precipitate was readily redispersed and subjected to rapid spectrophotometric analysis directly in the field. The method achieved outstanding enrichment factors (up to 495 for metal ions and 475 for nanoparticles), high extraction efficiencies (95–99%), and excellent selectivity for analytes such as Cu2?, Pb2?, Ag nanoparticles, and ZnO nanoparticles. Notably, the detection limits and analytical performance of the on-site spectrophotometric method after preconcentration were significantly improved and comparable to those of laboratory-based atomic absorption spectrometry (AAS). For example, the limit of detection for Cu2? was reduced to 0.63 μg/L (24-fold improvement), for Pb2? to 11.25 μg/L (10-fold improvement), for Ag nanoparticles to 0.056 μg/mL, and for ZnO nanoparticles to 0.065 μg/mL, all with substantial increases in sensitivity after enrichment. The method also demonstrated high precision and accuracy with recoveries ranging from 91% to 108% and relative standard deviations below 5% for real water samples. The results obtained using this approach were in excellent agreement with those obtained using AAS, confirming its reliability. This study established a simple, rapid, and environmentally friendly platform for on-site spectrometric analysis of both metal ions and nanoparticles, providing a practical alternative to conventional laboratory instrumentation for environmental monitoring and analytical chemistry.

Online Acid Extraction Coupled with ICP–MS for Iodine-to-Calcium Ratio Measurements in Marine Carbonate Rock

Mingying Liu, Yan Wu, Xin Lan, Wei Guo*, Lanlan Jin, Shenghong Hu

2025,46(5),520-525,

DOI: 10.46770/AS.2025.160

[Abstract] (5) [PDF 2.12 M] (142) [Supporting Information]

Abstract:
The iodine-to-calcium (I/Ca) ratio in marine carbonates can indicate changes in seawater redox. The use of inductively coupled plasma mass spectrometry (ICP–MS) to determine the I/Ca ratio in carbonates is challenging owing to low iodine content, volatility, and significant Ca matrix effects. In this study, an online extraction device was designed to evaluate the influence of extraction time on the detection of iodine signals. The intensity of I signal increased from 0 to 3 min after the addition of 2% HNO3, and a stable I signal was obtained from 3 to 8 min. After 8 min, the analytical signal decreased owing to the volatilization of iodine. Experimental results revealed a linear relationship between the intensity of I/Ca ratio and the concentration of I/Ca ratio, indicating that Ca can serve as an excellent internal standard (I/Ca ratio) to correct the attenuation of the I signal caused by Ca matrix effects. Therefore, a novel online acid extraction method coupled with ICP–MS was developed by strictly controlling extraction time (3–5 min) and using the I/Ca ratio for direct correction to obtain the final I/Ca ratio, with a detection limit of 0.02 μmol/mol and relative standard deviation ranging from 1.5% to 10.3%. The proposed method was applied to determine the I/Ca ratio in carbonate reference materials. The measured I/Ca ratios were consistent with the reference values.

Low-damage Femtosecond Laser-induced Plasma Spectroscopy for Rapid Differentiation of the Surface Hardness of Steel

Lukas Retterath, Peter Kohns, Georg Ankerhold*

2025,46(5),526-535,

DOI: 10.46770/AS.2025.156

[Abstract] (8) [PDF 4.66 M] (152)

Abstract:
This proof-of-concept study investigates the application of femtosecond laser-induced breakdown spectroscopy (fs-LIBS) for a rapid, almost non-destructive assessment of surface hardness of 80CrV2 steel samples subjected to thermal treatment. Conventional hardness testing methods, such as Vickers and Rockwell, often necessitate extensive sample preparation, geometric requirements and can alter the material's surface, limiting their effectiveness for rapid assessments. In contrast, LIBS offers a contactless approach that minimizes surface damage while providing high spatial resolution. In previous work, we have already shown that nanosecond laser-induced breakdown spectroscopy (ns-LIBS) leads to melt and material redeposition around craters, consequently reducing the achievable effective spatial resolution. To circumvent these problems, we used femtosecond laser pulses to generate reproducible plasmas on 80CrV2 steel samples with varying degrees of hardness. By maintaining consistent parameters such as laser energy, surface roughness, and planarity, this method facilitates the analysis of spectral changes associated with mechanical properties. Our results identify a correlation between the intensity ratios of iron emission lines and material hardness, underscoring the method's sensitivity to microstructural material changes. As expected, the femtosecond laser-induced breakdown spectroscopy technique (fs-LIBS) produced significantly smaller ablation craters than ns-LIBS. When accounting for the fluence changes resulting from crater formation and making the necessary adjustments, repeated measurements at the same locations could become feasible in the future. A method using fs-LIBS could be a compelling alternative for hardness testing of finely structured or heat-sensitive components.

Evaluate Qinghu and Other Known Apatite Samples as the Reference Materials for In-situ U-Pb Dating

Jia-Ming Xia, Jian-Feng Gao, Yan-Wen Tang*, Kai Cui, Ting-Guang Lan*, Jun-Jie Han

2025,46(5),536-548,

DOI: 10.46770/AS.2025.096

[Abstract] (19) [PDF 5.03 M] (365) [Supporting Information]

Abstract:
Apatite has been widely applied as a reliable chronometer and geochemical tool for studies on genesis and provenance. Due to small quantity, most apatite standards for laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U?Pb dating were exhausted. Therefore, apatite reference materials with homogeneous age and abundant reserves are still necessary. The famous Qinghu (QH) monzonite in the western Nanling region, South of China was dated well at 159.5 ± 0.2 Ma (Isotope Dilution Thermal Ionization Mass Spectrometry (ID-TIMS) zircon U-Pb method) and 159.5 ± 0.7 Ma (Secondary Ion Mass Spectrometry (SIMS) zircon U?Pb method). The QH apatite grains selected from this monzonite are characterized by abundant reserves, euhedral crystals with sizes up to 1mm, high U and Pb contents of 137.30 and 7.82 μg/g, respectively, and a small Th/U value of 2.6. The QH apatite were analyzed as a quality control over five years in the SKLCMRE lab and yielded an accurate U?Pb age at 161.3 ± 0.8 Ma (N=110, MSWD= 1.1, calibrated by OD306), which agrees well with the published U?Pb ages within uncertainties. In combination of these age results and microscopic observations on cogenetic minerals in this rock, the zircon ID-TIMS U?Pb age of 159.5 Ma was accepted as a reference age for QH apatite. Up to now, it is the most suitable reference material for apatite samples from the Jurassic to Cretaceous periods owing to its high U and Pb content and formation age. An initial 207Pb/206Pb ratio of 0.837 ± 0.008, which was derived from LA-SF-ICP-MS analyses on intergrown feldspars, is consistent with the calculated value (0.836) in Stacey and Kramers (1975). One hundred and sixty analyses on QH apatite grains have a common lead percentage (f206) value ranging from 4.2% to 38.4% and form a good linear trend on the Tera–Wasserburg diagram. Using QH apatite as a primary standard in a two-stage calibration method, four known apatite standards, including OD306, 401, MAD1, and MM, have been accurately determined with age offsets of -0.7% to 1.2% by LA-ICP-MS. These age results are the same as those calibrated by apatite OD306 (-1.1% - 0.1%), MAD1 (-1.2% - -0.1%), and MM (-1.1% - 0.1%), and much improved than those calibrated by apatite 401 (0.3% - 1.4%) and Otter Lake (-3.4% - -2.2%). Moreover, in a method application, MRC-1 apatite yielded a lower intercept 206Pb/238U ages of 154.1 ± 5.3 Ma, which agrees well with the published ID-TIMS U?Pb age of 153.3 ± 0.2 Ma within uncertainty.

Thiol-functionalized Fe3O4-modified Membrane for Selective Preconcentration and Sensitive Detection of Metallic Copper Nanoparticles in Environmental Waters

Xinyuan Huang, Jia Lv, Siyuan Wang, Wanying Li, Ke Huang*

2025,46(5),549-556,

DOI: 10.46770/AS.2025.158

[Abstract] (6) [PDF 808.39 K] (124) [Supporting Information]

Abstract:
Membrane filtration is an efficient technique for rapid and precise separation, yet challenges persist in distinguishing and selectively separating nanoparticles with identical elemental compositions, especially copper-based nanomaterials. Here, we report for the first time the immobilization of thiol-functionalized Fe3O4 nanoparticles (Fe3O4 RSH NPs) onto mixed cellulose ester membranes for the selective separation and preconcentration of copper nanoparticles (Cu NPs). The Fe3O4–RSH NPs–modified membrane demonstrated significantly greater retention of Cu NPs than CuS and CuO NPs of comparable size. The functionalized membrane exhibits exceptional separation performance, achieving over 90% retention of Cu NPs and an enrichment factor of ~23, as verified by inductively coupled plasma mass spectrometry (ICP-MS). Notably, the retention rate of Cu NPs remained unaffected by other copper species, demonstrating the excellent selectivity of the modified membrane toward Cu NPs. Under optimized conditions, the method reached a limit of detection (LOD) of 2.2 pg mL?1 for Cu NPs. Furthermore, the approach enabled successful detection of Cu NPs in river water samples from Chengdu. This strategy provides a rapid, reliable, and cost-effective pretreatment method for trace nanoparticle analysis in environmental samples and offers a promising platform for the development of low-cost, on-site nanoparticle monitoring technologies.

Investigating Occurrence State of Rhenium in Limestone Using In Situ Microbeam Techniques

Yu Huang, Hong Zhao*, Shihua Zhong, Chao Li, Jiujiang Zhao, Limin Zhou, Xinwei Li

2025,46(5),557-564,

DOI: 10.46770/AS.2025.108

[Abstract] (10) [PDF 5.33 M] (198) [Supporting Information]

Abstract:
The rhenium–osmium (Re–Os) isotopic dating technique has been extensively applied for the precise geochronological determination of black shale formations, effectively overcoming difficulties in dating chronologically challenging strata. Recent advancements have extended this methodology to limestone systems with substantially lower Re and Os concentration, thereby providing novel technical approaches for dating carbonate sequences. Clarifying the Re distribution in limestone is critical for optimizing experimental protocols and enhancing the accuracy and precision of dating results. However, carriers of Re and Os in carbonate rocks, particularly the radioactive parent element Re, remain poorly constrained. This study investigated Permian limestone samples from Guangde, Anhui Province, via integrated mineralogical characterization using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and femtosecond laser ablation-inductively coupled plasma mass spectrometry (fs-LA-ICP-MS). The analytical results indicated that Re is predominantly hosted in authigenic phases such as organic matter (OM) and pyrite. Terrigenous quartz contains little to no Re, while calcite does not host Re. These findings emphasize that Re-Os pretreatment protocols should prioritize the complete dissolution of OM and pyrite, while avoiding the dissolution of silica phases.

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] (473) [PDF 146.88 K] (3647)

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] (435) [PDF 86.02 K] (3517)

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] (419) [PDF 99.16 K] (3834)

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] (433) [PDF 154.90 K] (3662)

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] (563) [PDF 135.56 K] (4090)

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] (360) [PDF 167.98 K] (3415)

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] (351) [PDF 116.38 K] (3286)

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] (478) [PDF 283.26 K] (3736)

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] (385) [PDF 0.00 Byte] (0)

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