Journal of Analytical Atomic Spectrometry最新文献

{"title":"Investigation of direct simultaneous uranium isotopic determination and age dating of micrometer-sized uranium particles by laser ablation – multi-collector ICPMS†","authors":"Anne-Claire Humbert, Fabien Pointurier and Amélie Hubert","doi":"10.1039/D4JA00280F","DOIUrl":"https://doi.org/10.1039/D4JA00280F","url":null,"abstract":"<p >In this study, we demonstrate that it is possible to simultaneously determine accurate uranium <small>²³⁴</small>U and <small>²³⁵</small>U abundances and the date of purification (or “age”) of uranium oxide materials at the particle scale using laser ablation – multi-collector ICPMS coupling. The method was successfully applied to microparticles of uranium materials enriched at 5%, 85% and 90% and purified 70 years ago. The deviations from the reference age are, at most, respectively 6 years, 2 years and 1 month which is comparable to what can be obtained using the reference technique LG-SIMS. The precision of <small>²³⁵</small>U abundances and <small>²³⁴</small>U abundances, at the particle scale, was respectively between 0.11% and 1.95% and between 0.4% and 5% which is equivalent to or better than what was previously published for the analyses of depleted to moderately enriched materials by LA-ICPMS, showing that adding <small>²³⁰</small>Th determination doesn't degrade the determination of <small>²³⁴</small>U and <small>²³⁵</small>U abundances. Due to the small amount of material introduced into the ICPMS, μm-sized particle analysis by LA-ICPMS has the advantage of being less subject to laser-induced fractionation than bulk material analyses by LA-ICPMS. In contrast to the latter, a correction for uranium <em>versus</em> thorium fractionation can be applied based on the measurement of their relative sensitivities in standard solutions.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3180-3189"},"PeriodicalIF":3.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714070","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":"Applying standard addition to determine antimony isotopes in low-Sb samples using HG-MC-ICP-MS†","authors":"Honggang Zhu, Jian-Ming Zhu, Decan Tan, Zhuo Lu, Hongfei Liao and Yiwei Ma","doi":"10.1039/D4JA00333K","DOIUrl":"https://doi.org/10.1039/D4JA00333K","url":null,"abstract":"<p >The standard addition (SA) method has been successfully employed in measuring metal-stable isotopes in recent years. Here, utilizing hydride generator (HG)-multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS, Nu Plasma II and Neptune Plus), we evaluated the method's robustness through achieving high-precision <em>δ</em><small>¹²³</small>Sb(antimony) values (relative to NIST 3102a) in samples with more complex matrices and low-Sb concentrations. By using element doping (<small>^113/111</small>cadmium) coupled with sample-standard bracketing (SSB), a mass discrimination correction model was presented. The Sb isotope ratios of 30 geological reference materials (GRMs) were reported, in which the values of selected GRMs agreed well with previously published values. The SA method was then used to determine four of these with low-Sb samples. The analytical precision (2 standard deviations: 2SD) was found to mainly depend on the sample fraction (<em>f</em><small>_spl</small>) in the mixture, with the ideal mixing range recommended to be <em>f</em><small>_spl</small> ≥ 0.50 for single- and ≥ 0.45 for double SA when expected precision is ≤0.09‰ (2SD). The <em>δ</em><small>¹²³</small>Sb ratio calculated for basalt BCR-2 (Sb = 0.30 μg g<small>⁻¹</small>) was 0.28 ± 0.09‰, and together with the other four GRMs, it confirmed that accurate and precise Sb isotopes can be analyzed for samples with low-Sb using SA. Validating the measurement of Sb isotope composition in low-Sb samples with complex matrices by SA will expand the application of Sb isotopes in environmental, agricultural, life, Earth, and planetary sciences.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3082-3093"},"PeriodicalIF":3.1,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714050","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":"Automated detection of element-specific features in LIBS spectra","authors":"Zuzana Gajarska, Anna Faruzelová, Erik Képeš, David Prochazka, Pavel Pořízka, Jozef Kaiser, Hans Lohninger and Andreas Limbeck","doi":"10.1039/D4JA00247D","DOIUrl":"https://doi.org/10.1039/D4JA00247D","url":null,"abstract":"<p >This work introduces a novel semi-automatic approach to identify elemental lines in spectra obtained <em>via</em> laser-induced breakdown spectroscopy (LIBS). The algorithm is based on unique spectral fingerprints of individual elements that are configured into comb-like filters. The element-specific filters are then correlated with measured spectra for semi-supervised qualitative analysis of samples. Spectral variations are accommodated by adjusting the micro-parameters of the comb filter. This step ensures accurate results despite minor deviations from the instrument's ideal calibration due to instrumental fluctuations, <em>e.g.</em>, drift in spectral calibration or line broadening. Additionally, the algorithm can autonomously detect spectral interference regions, aiding the analyst in verifying spectral lines where such interference may occur. The paper presents a comprehensive overview of the algorithm and discusses the main concepts, parameters, optimization steps, and limitations using Echelle spectra of two standard reference materials with different complexity: borosilicate glass (NIST 1411) and low-alloyed steel (SUS1R). Furthermore, the transferability of the approach to different scenarios and real-life applications is demonstrated using a single-channel Czerny–Turner spectrum of an amalgam filling extracted from a hyperspectral image of a human tooth. A demo of the algorithm is publicly available for non-commercial purposes.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3151-3161"},"PeriodicalIF":3.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ja/d4ja00247d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714081","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":"Determination of boron isotopic compositions in five fractions of soil boron: traces of the environmental behavior of boron in soil†","authors":"Xuejun Chen, Qingcai Xu, Li Yan, Xiaodong Hao, Xiaochen Guan, Xiaopeng Han, Aide Sun, Zhiqun Chen, Lihua Liu and Zihao Zhu","doi":"10.1039/D4JA00286E","DOIUrl":"https://doi.org/10.1039/D4JA00286E","url":null,"abstract":"<p >Boron in soil can be divided into five fractions: readily soluble, carbonate-adsorbed, organically bound, adsorbed-bound and residual boron. Regarding differences in physicochemical properties, the fractions of soil boron affect the distribution and processes of boron and its isotopes in soil. A stepwise extraction for five fractions of soil boron was successfully established to reveal the isotopic behavior of boron in soils, which was performed to eliminate the isotope interference of neighboring forms in soil boron as much as possible. Ten soil samples were used to evaluate the proposed method. A large difference of 57‰ (−31.9‰ to +25.8‰) in the <em>δ</em><small>¹¹</small>B values occurred among the five fractions of soil boron. Residual boron had the highest content, which was hundreds of times greater than that in the other forms, and the lowest <em>δ</em><small>¹¹</small>B values, ranging from −31.9‰ to −24.5‰. Among the other four fractions, readily soluble boron had a relatively low content and the most positive <em>δ</em><small>¹¹</small>B values, adsorbed-bound boron had a relatively high content and less negative <em>δ</em><small>¹¹</small>B values, and carbonate-adsorbed boron had the lowest content. The relationship between the content and <em>δ</em><small>¹¹</small>B values revealed the scope of each fraction of soil boron, which may have resulted from the different processes of adsorption, transportation and weathering and the input of various provenances in the open soil medium. Further studies on the different types of soil influenced by different climates are expected to make important contributions to further knowledge of boron recycling in plant–soil systems with the proposed extraction method.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3162-3170"},"PeriodicalIF":3.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714064","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 single-stage purification method for the precise determination of zirconium isotopic composition in geological samples by double spike MC-ICP-MS†","authors":"Lanping Feng, Chen Wang, Yan Han, Wen Zhang, Jing-Liang Guo, Lian Zhou and Zhaochu Hu","doi":"10.1039/D4JA00332B","DOIUrl":"https://doi.org/10.1039/D4JA00332B","url":null,"abstract":"<p >Interest in studying zirconium (Zr) stable isotopic fractionation in both low and high-temperature environments has increased significantly in recent years. Multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) is the preferred technique for stable Zr isotope analysis due to its low sample consumption and high precision. However, the multi-column separation steps required to remove interferences and meet the stringent matrix requirements for Zr isotopes during MC-ICP-MS testing typically make the sample preparation process time-consuming. Here, we present a new, simple, and efficient single-pass chromatographic exchange technique for the chemical isolation of Zr from complex sample matrices. This new separation protocol is based on DGA resin and consists of only three elution steps and two types of acid eluents (15 mL 7 mol L<small>⁻¹</small> HNO<small>₃</small> and 5 mL 3 mol L<small>⁻¹</small> HNO<small>₃</small> + 0.1 mol L<small>⁻¹</small> HF), which afford straightforward separation of Zr with high yield, good purity, and low blank levels. Zr isotope ratios were measured using Neptune Plus MC-ICP-MS with the <small>⁹¹</small>Zr–<small>⁹⁶</small>Zr double spike in combination with standard–sample bracketing for mass bias correction. The validity of the proposed method is demonstrated by analyzing eight geological reference materials (including BCR-2, which has an extremely high Mo content of ∼248 μg g<small>⁻¹</small>) with satisfactory results that are in good agreement with published values. Based on repeated analyses of pure standard solutions and geological reference materials, the long-term measurement reproducibility is better than ±0.048‰ for <em>δ</em><small>⁹⁴</small>Zr. Therefore, the proposed method can be used for the rapid and efficient determination of stable Zr isotope ratios in geological samples.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3035-3047"},"PeriodicalIF":3.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714103","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":"Chemical analysis of Chang'e-5 lunar soil using LA-ICP-MS in highly diluted fused glass discs †","authors":"Shitou Wu, Dingshuai Xue, Yueheng Yang, Hao Wang, Chunlai Li and Fuyuan Wu","doi":"10.1039/D4JA00329B","DOIUrl":"https://doi.org/10.1039/D4JA00329B","url":null,"abstract":"<p >The bulk chemical compositions of extraterrestrial materials can provide critical information on the evolution and magmatism of planetary bodies. However, accurate measurements are challenging because these samples, particularly returned samples, are extremely limited and valuable. We demonstrate the practicality of chemical analysis using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) on highly diluted fused glass discs (lithium borate flux : sample = 100 : 1). Only 30 mg of sample is required to produce a lithium borate disc, which is one magnitude lower than previously used (&gt;300 mg). We proposed a modified Jet sample cone (the orifice diameter enlarging from 1.1 mm to 1.2 mm) to improve the sensitivity by a factor of ∼4.5 compared to that of standard sample cone. The interferences from the lithium borate discs were evaluated systemically, and corrections are necessary for some elements (<em>e.g.</em>, Si, Ca, Pb). The limits of detection for most elements are in the range of 0.1–1.0 μg g<small>⁻¹</small>. The analytical precision is better than 30% (relative standard deviation) for elements with concentrations of &gt;0.5 μg g<small>⁻¹</small>. The accuracy is better than 15% (relative deviation), as demonstrated by analyses of BCR-2 and BHVO-1 rock powder reference materials. This innovative technique was applied to lunar samples collected by Chang'e-5 (CE-5) mission, and an independent dataset of 38 major and trace elements was obtained. We report the average chemical composition of the CE-5 lunar soil samples, which will be an important reference for future study. This method will be useful for other precious extraterrestrial samples (<em>e.g.</em>, CE-6 lunar samples).</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 1","pages":" 98-103"},"PeriodicalIF":3.1,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912626","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 simple method for elemental analysis of liquids in sprayed microdroplets by laser-induced breakdown spectroscopy","authors":"Jun Feng, Yihui Yan, Yuzhu Liu and Jozef Lengyel","doi":"10.1039/D4JA00192C","DOIUrl":"https://doi.org/10.1039/D4JA00192C","url":null,"abstract":"<p >The combination of paper spray with laser-induced breakdown spectroscopy (PS-LIBS) was used to analyze trace elements in aqueous solutions. The analysis of sprayed charged microdroplets eliminates the experimental challenges of bulk liquid analysis, such as splashing and surface ripples, which often affect LIBS sensitivity. In contrast to other electrospray techniques, PS is a simple and robust method that allows for the direct loading of liquid samples onto paper. Its performance is largely dependent on the quality of the spray plume, influenced by factors like paper shape, tip angle, spray voltage, and solvent composition. The cut angle of the paper tip significantly influences the spray plume and total ion current, with sharper tips being more efficient at generating sprayed microdroplets. The detection limits for Na, K, and Cr – 11.1 mg L<small>⁻¹</small>, 28.9 mg L<small>⁻¹</small>, and 67.9 mg L<small>⁻¹</small>, respectively, – are in line with typical values from other LIBS experiments on liquid samples. These experimental results indicate that PS-LIBS is a promising technique for the <em>in situ</em> analysis of trace elements in liquid samples.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 1","pages":" 114-121"},"PeriodicalIF":3.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912687","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":"Hydrophobicity induced graphene oxide based dispersive micro solid phase extraction of strontium from seawater and groundwater prior to GFAAS determination","authors":"M. Sebastian, D. Saikrishna, S. K. Jayabun, N. N. Meeravali, R. Shekhar and A. C. Sahayam","doi":"10.1039/D3JA00445G","DOIUrl":"https://doi.org/10.1039/D3JA00445G","url":null,"abstract":"<p >A novel graphene oxide (GO) mediated dispersive micro solid phase extraction method (Dμ-SPE) is developed for the extraction of strontium (Sr) from seawater and groundwater. This method involves the quantitative sorption of Sr<small>²⁺</small> ions from seawater onto the negatively charged surface of GO through electrostatic interactions. Notably, Sr was extracted directly from seawater without altering the inherent composition of the sample. After the sorption of Sr, the excess charge on GO was neutralized by the addition of an electrolyte, KCl. Following charge neutralization, attractive forces between discrete π-electron networks of GO nano-sheets dominate and induce coagulation of GO, forming bulky GO aggregates with partial hydrophobicity. These aggregates were easily extracted into a small organic phase, CCl<small>₄</small>, resulting in the separation and pre-concentration of Sr. The Sr present in the organic phase was back-extracted into dilute nitric acid and quantified using graphite furnace atomic absorption spectrometry (GFAAS). Under optimized conditions, a pre-concentration factor of 100, a limit of detection of 0.004 ng mL<small>⁻¹</small> for 50 mL seawater and recoveries ranging from 88% to 100% at concentrations of 0.2–2 ng mL<small>⁻¹</small> were achieved. The developed method was successfully applied to tap water, groundwater and seawater matrices.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3190-3197"},"PeriodicalIF":3.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714071","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 new concept for correction of instrumental isotopic fractionation in MC-ICP-MS using a pair of monoisotopic elements: a critical evaluation†","authors":"Andrii Tupys, Klaudia Tetfejer, Ludwik Halicz, Ewa Bulska and Jakub Karasiński","doi":"10.1039/D4JA00117F","DOIUrl":"https://doi.org/10.1039/D4JA00117F","url":null,"abstract":"&lt;p &gt;In this research work, we investigated the possibility of using mixtures of monoisotopic elements (&lt;small&gt;&lt;sup&gt;93&lt;/sup&gt;&lt;/small&gt;Nb/&lt;small&gt;&lt;sup&gt;89&lt;/sup&gt;&lt;/small&gt;Y, &lt;small&gt;&lt;sup&gt;165&lt;/sup&gt;&lt;/small&gt;Ho/&lt;small&gt;&lt;sup&gt;159&lt;/sup&gt;&lt;/small&gt;Tb and &lt;small&gt;&lt;sup&gt;209&lt;/sup&gt;&lt;/small&gt;Bi/&lt;small&gt;&lt;sup&gt;197&lt;/sup&gt;&lt;/small&gt;Au) as calibrators for accurate determination of isotope ratios by multicollector mass spectrometry (MC-ICP-MS). The potential advantage of using monoisotopic elements for calibration lies in their significantly lower uncertainty in atomic masses. This would certainly affect the uncertainty of a measured isotope ratio after data processing, particularly if absolute isotope ratios are being evaluated. Model isotopic systems (&lt;small&gt;&lt;sup&gt;87&lt;/sup&gt;&lt;/small&gt;Sr/&lt;small&gt;&lt;sup&gt;86&lt;/sup&gt;&lt;/small&gt;Sr–&lt;small&gt;&lt;sup&gt;93&lt;/sup&gt;&lt;/small&gt;Nb/&lt;small&gt;&lt;sup&gt;89&lt;/sup&gt;&lt;/small&gt;Y, &lt;small&gt;&lt;sup&gt;92&lt;/sup&gt;&lt;/small&gt;Zr/&lt;small&gt;&lt;sup&gt;90&lt;/sup&gt;&lt;/small&gt;Zr–&lt;small&gt;&lt;sup&gt;93&lt;/sup&gt;&lt;/small&gt;Nb/&lt;small&gt;&lt;sup&gt;89&lt;/sup&gt;&lt;/small&gt;Y, &lt;small&gt;&lt;sup&gt;208&lt;/sup&gt;&lt;/small&gt;Pb/&lt;small&gt;&lt;sup&gt;207&lt;/sup&gt;&lt;/small&gt;Pb–&lt;small&gt;&lt;sup&gt;209&lt;/sup&gt;&lt;/small&gt;Bi/&lt;small&gt;&lt;sup&gt;197&lt;/sup&gt;&lt;/small&gt;Au and &lt;small&gt;&lt;sup&gt;167&lt;/sup&gt;&lt;/small&gt;Er/&lt;small&gt;&lt;sup&gt;166&lt;/sup&gt;&lt;/small&gt;Er–&lt;small&gt;&lt;sup&gt;165&lt;/sup&gt;&lt;/small&gt;Ho/&lt;small&gt;&lt;sup&gt;159&lt;/sup&gt;&lt;/small&gt;Tb) were selected and the Internal Standard method (Russell's law) and optimized regression model (ORM) for isotope measurements, using the mentioned mixtures of monoisotopic elements as calibrators, were applied. The precision and trueness of the obtained results were assessed. For example, the &lt;small&gt;&lt;sup&gt;167&lt;/sup&gt;&lt;/small&gt;Er/&lt;small&gt;&lt;sup&gt;166&lt;/sup&gt;&lt;/small&gt;Er isotope ratio in a certified reference material of erbium was measured using a gravimetric mixture of Ho and Tb as well as a &lt;small&gt;&lt;sup&gt;160&lt;/sup&gt;&lt;/small&gt;Gd/&lt;small&gt;&lt;sup&gt;158&lt;/sup&gt;&lt;/small&gt;Gd pair (NRC GADS-1) as instrumental isotopic fractionation (IIF) calibrators in ORM. Although the average result for both approaches was in the range of instrumental error (0.68223 ± 0.00351 with &lt;small&gt;&lt;sup&gt;165&lt;/sup&gt;&lt;/small&gt;Ho/&lt;small&gt;&lt;sup&gt;159&lt;/sup&gt;&lt;/small&gt;Tb and 0.68236 ± 0.00034 with &lt;small&gt;&lt;sup&gt;160&lt;/sup&gt;&lt;/small&gt;Gd/&lt;small&gt;&lt;sup&gt;158&lt;/sup&gt;&lt;/small&gt;Gd), the precision was ten times lower when a mixture of monoisotopic elements was used for correction. Based on the results obtained, it was assessed that Russell's law does not provide a correct description for systems with a mixture of two monoisotopic elements, probably due to the assumption of equal IIF for the analyte and internal calibrator. In our opinion, such an assumption is not true in a system when the internal calibrator is a pair of two different elements. A new mathematical description of such a system could enable the introduction of a suitable correction. The ORM method is free from assumptions about the same IIF for individual chemical entities and for this reason it looks more encouraging and shows the potential to be useable even with a mixture of monoisotopic elements as calibrators. In this paper we present experimental results confirming thi","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 12","pages":" 3142-3150"},"PeriodicalIF":3.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ja/d4ja00117f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714080","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":"Insights into the role of transition and noble metals mediating photochemical vapor generation†","authors":"Ralph E. Sturgeon, Enea Pagliano, Gisele S. Lopes, Renato S. A. Neto and Jane K. S. Brito","doi":"10.1039/D4JA00261J","DOIUrl":"https://doi.org/10.1039/D4JA00261J","url":null,"abstract":"<p >The recent expansion of the suite of elements amenable to photochemical vapor generation (PVG) is primarily linked to the addition of mg L<small>⁻¹</small> concentrations of selected transition metals (TMs) to the photolysis medium, principally Fe, Cd, Co, Ni and Cu. Their presence enhances synthesis yields of several analytical targets, particularly carbonylated species, in some cases by orders of magnitude. A consideration of curated analytical PVG literature reveals substantial inconsistencies with the current use of generalized ligand-to-metal charge transfer processes to mechanistically account for these so-called TM “sensitizer” effects <em>via</em> their enhancement in free radical populations participating in the PVG synthesis routes. In this study, a novel approach utilizes an independent window for evaluation of the effects of added TMs on radical production based on an examination of the altered concentration profiles of H<small>₂</small>, CO, CH<small>₄</small> and CO<small>₂</small> generated in formic and acetic acid media, whose origins lie with the precursor free radicals responsible for the analytical PVG process. A photocatalytic mechanism induced by homogeneous co-generation of TM nanoparticles is proposed which more reasonably accounts for both the altered gas profiles and their notable selectivity evident with improved PVG efficiencies of specific analytes. A tutorial approach to the topic has been adopted in an effort to provide a balanced framework within which the various processes are comprehensively discussed with relevance to state-of-the-art PVG techniques and current literature.</p>","PeriodicalId":81,"journal":{"name":"Journal of Analytical Atomic Spectrometry","volume":" 1","pages":" 70-97"},"PeriodicalIF":3.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ja/d4ja00261j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912625","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}