Journal of Analytical Atomic Spectrometry最新文献

{"title":"A novel in situ methodology for U–Pb, (U–Th)/He, and fission track triple dating†","authors":"Jie Hu, Zhiwu Li, Jinxi Li, Shugen Liu, Ganqing Xu, Chaoqun Yang, Kui Tong and Yin Li","doi":"10.1039/D4JA00257A","DOIUrl":"https://doi.org/10.1039/D4JA00257A","url":null,"abstract":"<p >In this study, we present a novel laser-based technique for <em>in situ</em> U–Pb, (U–Th)/He, and fission track (FT) triple dating for apatite and other U-rich accessory minerals. This approach allows for obtaining three ages with different closure temperatures on a single crystal, significantly enhancing spatial resolution and analytical productivity. Our new workflow employs an Autoscan System for FT analysis, a ResoChron system for He determination, and an LA-ICP-MS system for parent isotope and U–Pb age measurements. We describe the sample preparation, instrument parameters, and data reduction for apatite in detail. Using a sample–standard bracketing approach to determine the pairwise factor <em>κ</em>, we significantly improved reproducibility, particularly by replacing volume with depth in helium pit measurement. Additionally, we found that chemical etching in FT dating can reduce (U–Th)/He age by removing the surrounding He, necessitating a second polishing for samples with high track density. This <em>in situ</em> triple dating method has been successfully applied to five large apatite crystals, improving analytical efficiency and resolving grain-to-grain age discrepancy.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 11","pages":" 2856-2869"},"PeriodicalIF":3.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142540539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evaluation and calibration of matrix effects during SIMS silicon isotope analysis in silicate glasses†","authors":"Liu-Yang Chen, Yu Liu, Di Zhang, Guo-Qiang Tang and Qiu-Li Li","doi":"10.1039/D4JA00253A","DOIUrl":"https://doi.org/10.1039/D4JA00253A","url":null,"abstract":"<p >Silicon is one of the most abundant elements in rocks, and its isotopic composition can be traced back to various geological processes. <em>In situ</em> high-precision silicon isotope analysis requires matrix-matched standards as reference materials for mass fractionation calibration. However, finding completely matrix-matched standards is impractical for minerals or glasses with complex matrices or a wide range of chemical compositions. For instance, the major component variation in lunar glasses can reach 30%, making it impossible to find matrix-matched standards for each glass bead. In this study, SIMS silicon isotope analyses on eleven glass standards ranging from basaltic to rhyolitic compositions were conducted to evaluate the relationship between instrumental mass fractionation and the major components. We established a calibration model highly correlated with instrumental mass fractionation based on the contents of Si, Ca, Al and Mg (<em>R</em><small>²</small> = 0.997, SCAM model) in glass samples. This model can accurately calibrate the instrumental mass fractionation of silicon isotopes in glass samples within the compositional range covered by the standards, providing insights and methods for accurately determining various isotope compositions in glass samples with varying compositions.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 11","pages":" 2832-2840"},"PeriodicalIF":3.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142540538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Titanomagnetite, a new potential geochronometer for in situ U–Pb dating†","authors":"Yanwen Tang, Na Liu, Jianfeng Gao, Junjie Han, Zhongjie Bai and Tingguang Lan","doi":"10.1039/D4JA00254G","DOIUrl":"10.1039/D4JA00254G","url":null,"abstract":"<p >Titanomagnetite occurs commonly in igneous and metamorphic rocks, and various types of deposits, and serves as a valuable indicator. Recently, it has been identified as a new geochronometer for U–Pb dating. However, no reference material is available currently. Thus, we used a titanomagnetite sample HG79c with a known age of 259.2 ± 2.8 Ma to evaluate potential primary standards and establish an accurate calibration method for widespread application. In our <em>in situ</em> U–Pb dating experiments, different ablation settings were optimized, <em>i.e.</em>, spot sizes of 44 and 60 μm, laser frequencies of 6, 8, and 10 Hz, and energy densities of 3, 4, and 8 J cm<small>⁻²</small>. 3 ml min<small>⁻¹</small> nitrogen was introduced to enhance sensitivity and reduce matrix effects. Five Concordia-intercept <small>²⁰⁶</small>Pb/<small>²³⁸</small>U ages were obtained for HG79c using cassiterite AY-4 as an external standard, and four are consistent with or slightly younger than the reference age within errors. Two accurate ages were obtained when HG79c was calibrated by zircon 91500 and garnet PL-57. All these age results and Pb/U fractionation confirm that cassiterite and zircon have a normalized Pb/U ratio consistent with titanomagnetite in some optimized ablation settings. We utilized cassiterite AY-4 as the primary standard, HG79c as quality control in an optimized ablation setting, <em>i.e.</em>, a spot size of 60 μm, energy density of 4 J cm<small>⁻²</small>, and laser frequency of 6 Hz, to date titanomagnetite LL22-137 from the Lala Fe–Cu deposit in the Kangdian IOCG metallogenic province, China. This titanomagnetite yielded a Concordia-intercept <small>²⁰⁶</small>Pb/<small>²³⁸</small>U age of 853.2 ± 9.9 Ma, which agrees well with the intergrown rutile U–Pb age of 850.8 ± 8.7 Ma and the published U–Pb ages for apatite and secondary allanite, and Re–Os age for molybdenite from the same deposit. This method offers a new tool for directly dating diagenesis and ore-forming processes related to Fe and Ti metals.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3017-3024"},"PeriodicalIF":3.1,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142247764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A simplified instrumental protocol for trace Nd and Hf isotope measurements (<10 ng) using a MC-ICP-MS and an Apex Omega de-solvating system†","authors":"Ting Zhou, Liang Qi, Sheng-hua Liu and Bo Zhou","doi":"10.1039/D4JA00276H","DOIUrl":"10.1039/D4JA00276H","url":null,"abstract":"<p >We reported a simple technique allowing accurate and precise Nd and Hf isotope measurements of samples with low contents using a Neptune Plus MC-ICP-MS and an Apex Omega membrane de-solvating system. By employing a highly sensitive jet sample cone and X skimmer cone, our protocol achieved a low oxide level (&lt;0.05%) at high ion transmission (∼880 V ppm<small>⁻¹</small> for Nd and 850 V ppm<small>⁻¹</small> for Hf) and was found to have little effect on the mass fractionation of Nd and Hf. This was accomplished by simple adjustments of the sweep gas of the membrane de-solvating system and the sample gas of the nebulizer. Instrumental sensitivities were enhanced by a factor exceeding tenfold, in comparison to those of standard measurements with wet plasma. Long term measurements of 1 ng Nd solution standards yielded <small>¹⁴³</small>Nd/<small>¹⁴⁴</small>Nd ratios of 0.512117 ± 0.000032 (2SD, <em>n</em> = 24) and 0.512227 ± 0.000036 (2SD, <em>n</em> = 42) for Jndi-1 and JMC-Nd solutions, respectively, while analysis of 1 ng JMC475 Hf gave <small>¹⁷⁶</small>Hf/<small>¹⁷⁷</small>Hf ratios of 0.282163 ± 0.000027 (2SD, <em>n</em> = 21). These results are in agreements with their reference values. Potential interfering elements Ce and Sm are found to have an insignificant influence on <small>¹⁴³</small>Nd/<small>¹⁴⁴</small>Nd ratios. Lu and Yb have a remarkable effect on <small>¹⁷⁶</small>Hf/<small>¹⁷⁷</small>Hf ratios. Improved correction performance can be achieved by using Lu and Yb ratios obtained by analyzing pure Lu and Yb solutions. Five chemically purified rock reference materials are measured with the presented method and the results are consistent with their recommended values. Relative to other approaches, this protocol is rapid and accurate and can be widely applied in Nd and Hf isotope analysis of samples with trace amounts of Nd and Hf (&lt;10 ng).</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 11","pages":" 2694-2702"},"PeriodicalIF":3.1,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142247726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simultaneous determination of the oxygen isotope ratio and volatile composition of apatite with high lateral resolution via nano-secondary-ion mass spectrometry†","authors":"Youwei Chen, Jianfeng Gao, Xianwu Bi, Shaohua Dong, Quanliang Lei and Ruizhong Hu","doi":"10.1039/D4JA00183D","DOIUrl":"10.1039/D4JA00183D","url":null,"abstract":"<p >Apatite is commonly used as a tracer in Earth and planetary sciences by leveraging its oxygen isotopes and volatile compositions to elucidate the derivation and evolution of magma and geological fluids. While secondary-ion mass spectrometry has proven effective in determining these compositions in apatite, the challenge lies in its relatively large spot size (&gt;20 μm), and obtaining O isotope and volatile data from different grains or domains by the current method. In addition, the sequential analysis of volatiles is both time-consuming and constrained by limited data, leading to increased uncertainties in subsequent elemental analysis. This hinders robust interpretations of geological events and the determination of smaller-grained apatite. In this study, we propose a high lateral resolution (∼7 μm) method for the simultaneous analysis of the O isotope ratio and volatile (OH, F, Cl, and S) composition of apatite. The analysis of the eight apatite standards using this method yields results that are consistent with literature values, demonstrating its reliability and robustness. This innovative approach stands out not only for its high lateral resolution and time efficiency but also for its enhanced data robustness, laying a solid foundation for further scientific investigation and analysis.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3000-3009"},"PeriodicalIF":3.1,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142247766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development and application of reference and routine analytical methods providing SI-traceable results for the determination of technology-critical elements in PCB from WEEE†","authors":"Giancarlo D'Agostino, Marcus Oelze, Jochen Vogl, Jean-Philippe Ghestem, Nicolas Lafaurie, Ole Klein, Daniel Pröfrock, Marco Di Luzio, Luigi Bergamaschi, Radojko Jaćimović, Caroline Oster, Johanna Irrgeher, Shaun T. Lancaster, Anna Walch, Anita Röthke, Lena Michaliszyn, Axel Pramann, Olaf Rienitz, Timo Sara-Aho, Oktay Cankur, Derya Kutan and Johanna Noireaux","doi":"10.1039/D4JA00235K","DOIUrl":"10.1039/D4JA00235K","url":null,"abstract":"<p >The recovery and reprocessing of technology-critical elements (TCE) present in printed circuit boards (PCB) from electrical and electronic waste is essential both for recycling valuable materials subject to supply risk and for reducing the environmental impact. Although the quantitative knowledge of TCE amounts in end-of-life PCB plays a key role, there are neither matrix certified reference materials nor harmonized analytical methods available to establish the traceability of the results to the International System of Units. To fill these gaps, we developed and applied five reference analytical methods based on ICP-MS standard addition calibrations and INAA <em>k</em><small>₀</small>- and relative calibrations suitable to certify reference materials. In addition, we developed and tested six analytical methods based on more commonly used ICP-MS external standard calibrations to provide industry with routine analysis methods. Twenty TCE (Ag, Au, Co, Cu, Dy, Ga, Gd, Ge, In, La, Li, Nd, Ni, Pd, Pr, Pt, Rh, Sm, Ta and Ti) were selected as target analytes and a batch of powdered PCB was used as measurement material. An overall mutual agreement was observed among data collected by reference methods at a few percent relative uncertainty levels. Moreover, all but one of the methods developed for routine analysis demonstrated their suitability in industrial applications by producing data within ± 20% of the values established with reference methods.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 11","pages":" 2809-2823"},"PeriodicalIF":3.1,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ja/d4ja00235k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142247769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Packing thickness dependent plasma emission induced by laser ablating thin-layer microgranular materials","authors":"Kou Zhao, Qiang Zeng, Yaju Li, Shu Hang Gong, Yifan Wu, Xiangyu Shi, Jinrui Ye, Xueqi Liu, Xinwei Wang, Dongbin Qian, Liangwen Chen, Shaofeng Zhang, Lei Yang and Xinwen Ma","doi":"10.1039/D4JA00213J","DOIUrl":"10.1039/D4JA00213J","url":null,"abstract":"<p >An experimental study on the packing thickness (PT) dependent plasma emission caused by laser ablating thin-layer microgranular samples in air was conducted using three sets of size-selected copper grains (median size <em>d</em><small>₅₀</small> = 53 μm, 72 μm, and 100 μm, respectively). For each size-selected case, the PT parameter was tuned from 0.15 to 1.00 mm through varying the amount of grains packed into a vessel with a steel bottom wall and the emission spectra of laser-induced plasma were measured at various PT. It is found that there is a striking threshold phenomenon in the measured behavior of PT-dependent plasma emission. Specifically, when PT is less than a threshold PT<small>_th</small>, the emission intensity exhibits an exponential decreasing with incremental thickness; however, when it exceeds PT<small>_th</small>, the emission intensity becomes almost constant. It is also found that the PT<small>_th</small> slightly depends on grain size but the ratio of PT<small>_th</small> to <em>d</em><small>₅₀</small> seems to be size independent. Combining the mechanical fundamentals of granular materials, we interpreted the findings by considering a PT-dependent effect of the vessel's bottom on the formation circumstance of a laser-induced plasma. This work has practical significance in assessing a threshold thickness above which laser-induced breakdown spectroscopy, as an analytical technique to quantify elements embedded in microgranular materials, is viable regardless of PT difference.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2374-2381"},"PeriodicalIF":3.1,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bimodal data fusion of LIBS spectroscopy and plasma acoustic emission signals: improving the accuracy of machining process identification for low roughness samples","authors":"Shilei Xiong, Minchao Cui, Nan Yang, Guangyuan Shi, Yuxin Pi, Yuyang Mu, Yuntao Zhang and Yue Zhao","doi":"10.1039/D4JA00225C","DOIUrl":"10.1039/D4JA00225C","url":null,"abstract":"<p >The identification of machining processes for low roughness samples is extremely challenging, and a reasonably quick identification of machining processes for low roughness parts is critical for ensuring that the samples are employed under the appropriate conditions and improving work efficiency. In this work, a new identification method of fusion of LIBS spectra and plasma acoustic emission signals (PAESs) with bimodal information is proposed, and the LIBS spectral data and PAES data of nine types of low roughness samples processed by three machining processes, namely horizontal milling, plain grinding, and vertical milling, are recorded and analyzed. The spectral intensities of the primary element Fe and trace element Mn are compared and analyzed. The spectrum intensities of the primary element Fe and trace element Mn, as well as the PAES maximum peak, are compared and examined. Using the PCA-SVM machine learning technique, the three recognition impacts of single LIBS data, single PAES data, and LIBS-PAES bimodal data fusion are examined and compared. At <em>R</em><small>_a</small> = 0.4 μm and 0.8 μm, vertical milling produces significantly higher spectral intensities than plain grinding and horizontal milling, while horizontal milling produces significantly higher intensities than plain grinding. When the surface roughness of the samples is the same, variations in the machining process cause changes in the PAES. The recognition accuracy was 86.67% for the test set of single LIBS spectral data, 78.89% for the test set of single PAES data, and 97.11% for the training set, and 91.11% for the test set of LIBS-PAES bimodal data fusion, respectively. When compared to single-modal data recognition, bimodal data fusion greatly improves recognition ability, fully reflecting the benefits of bimodal data fusion. Based on the results of this study, it can be preliminarily concluded that the fusion of spectral and acoustic information in laser-induced breakdown spectroscopy detection is very promising for recognizing the surface state of parts in the machining field.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 11","pages":" 2737-2747"},"PeriodicalIF":3.1,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid and accurate determination of chlorine isotopic ratios with ICP-MS/MS using O2 reaction gas†","authors":"Tyler D. Schlieder, Nicole D. Rocco, Maria Laura di Vacri, Isaac J. Arnquist, Danny Bottenus, Zachary Huber and Bruce McNamara","doi":"10.1039/D4JA00191E","DOIUrl":"10.1039/D4JA00191E","url":null,"abstract":"<p >Chlorine isotopic ratio measurements are useful for stable isotope tracing, isotopic abundance measurements in nuclear chemistry, and accurate determination of concentrations using isotope dilution methods. Accurate and precise determination of Cl isotopic ratios using inductively coupled plasma mass spectrometry (ICP-MS) methods is challenging due to major polyatomic interferences of <small>¹⁶</small>O<small>¹⁸</small>O<small>¹</small>H<small>⁺</small> and <small>³⁶</small>Ar<small>¹</small>H<small>⁺</small> on <small>³⁵</small>Cl<small>⁺</small> and <small>³⁷</small>Cl<small>⁺</small>, respectively. Previous work has demonstrated that using tandem mass spectrometry (ICP-MS/MS) with either H<small>₂</small> or O<small>₂</small> gas in the collision/reaction cell can significantly improve the precision, but not necessarily the accuracy, of chlorine isotopic measurements over single-quadrupole techniques. In this work, we further investigate ICP-MS/MS, using O<small>₂</small> as a reaction gas, as a technique for accurate determination of Cl isotopic ratios. Using the methodology developed herein we measure both natural and enriched chlorine isotopic ratios in diverse samples matrices, targeting <small>³⁷</small>Cl isotope enrichment efforts, without the need for complex front-end chemistry (<em>i.e.</em>, ion exchange chromatography), while maintaining a typical accuracy and precision better than ∼1%. The reduced need for time-consuming sample processing afforded by this method results in higher sample throughput (&gt;80 measurements/day) relative to other analytical techniques (<em>e.g.</em>, thermal ionization mass spectrometry, accelerator mass spectrometry, <em>etc.</em>). This work demonstrates that ICP-MS/MS with O<small>₂</small> as a reaction gas can be a useful tool for making rapid and accurate chlorine isotopic ratio measurements.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2502-2507"},"PeriodicalIF":3.1,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ja/d4ja00191e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-precision low-level Cd isotopic analysis using MC-ICP-MS and its application to marine samples from Terra Nova Bay (Antarctica)†","authors":"Maria Alessia Vecchio, Lana Abou-Zeid, Marco Grotti and Frank Vanhaecke","doi":"10.1039/D4JA00214H","DOIUrl":"10.1039/D4JA00214H","url":null,"abstract":"<p >This study presents the development, validation and use of an approach for precise and accurate cadmium (Cd) isotopic analysis at low concentration levels using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The MC-ICP-MS unit used was equipped with a standard sample introduction system, thus using an ICP operated under wet plasma conditions, and Faraday cup amplifiers equipped with a 10<small>¹³</small> Ω resistor. One-column anion exchange chromatography allowed isolation of Cd with 80–99% recovery and absence of an effect of potential on-column fractionation on the isotope ratio results was demonstrated. Use of both an internal (using Ag) and an external (measured in a sample-standard bracketing sequence) standard was relied on for correction of the bias introduced by instrumental mass discrimination. A long-term precision of 0.09‰ (2SD) for <em>δ</em><small>^114/110</small>Cd was achieved at a Cd concentration of 10 ng mL<small>⁻¹</small>. The method developed was validated by analysing NIST SRM 2711a (Montana soil) and NRC TORT-3 (Lobster hepatopancreas) reference materials, yielding results consistent with literature values. Subsequently, the method was applied to two Antarctic marine organisms <em>Adamussium colbecki</em> and <em>Trematomus bernacchii</em>, collected during both the 1990s and 2020s, to investigate its potential for identifying changes in the biogeochemical cycle of Cd over time and reveal natural or anthropogenic sources. A preferential uptake of the lighter Cd isotopes in both species was observed, indicated by negative <em>δ</em><small>^114/110</small>Cd values ranging between −0.24 and −0.09‰. This finding is consistent with previous studies that have reported Cd fractionation during its uptake by marine organisms, with a preference for the lighter isotopes. No significant differences in <em>δ</em><small>^114/110</small>Cd values were observed between organs of the same species or between the same species collected in the different decades, suggesting minimal Cd isotope fractionation during internal transfer and consistent Cd sources over time. Comparison with literature data suggests that the Cd source in Antarctic biota may be predominantly of natural origin, with <em>δ</em><small>^114/110</small>Cd values indicating isotopically heavier Cd than that found in Cd-polluted areas. However, further Cd isotope ratio data from various Antarctic sample types are necessary to further evaluate the Cd sources in marine samples.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 10","pages":" 2591-2603"},"PeriodicalIF":3.1,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ja/d4ja00214h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142207148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}