Nikolai V. Alov, Dmitry V. Danilov, Pavel Yu. Sharanov, Valentin G. Semenov, Vitaly V. Panchuk, Sergey S. Savinov, Maria M. Khaydukova
Abstract The main purpose of this study was the comparison of the results of quantification obtained via different sample preparation approaches such as microwave‐assisted wet digestion (MAWD) and suspension preparation. Two total reflection x‐ray fluorescence (TXRF) spectrometers equipped with Mo x‐ray tubes were used to compare results obtained via two different paths of sample preparations which would further be compared to the conventional way of analysis by inductively coupled plasma optical emission spectrometry (ICP‐OES) including MAWD. Three dietary supplement samples with different sets and concentrations of elements were analyzed. The benefits and limitations of the simplified path of sample preparation were highlighted. A round‐robin test between TXRF and ICP‐OES was discussed. Accuracy as the percentage of recovery in all measurements ranged from 80 to 120. Precision for all results did not exceed 8% for TXRF and 5% for ICP‐OES. Limits of quantification by TXRF are ranged from 1 to 0.01 mg/pill for different elements. It was shown that suspension preparation of samples might be a useful response to increasing demand for quality control of dietary supplements since it is less time consuming and cost efficient.
{"title":"Quantification of elements in dietary supplements by total reflection x‐ray fluorescence and inductively coupled plasma optical emission spectrometry","authors":"Nikolai V. Alov, Dmitry V. Danilov, Pavel Yu. Sharanov, Valentin G. Semenov, Vitaly V. Panchuk, Sergey S. Savinov, Maria M. Khaydukova","doi":"10.1002/xrs.3402","DOIUrl":"https://doi.org/10.1002/xrs.3402","url":null,"abstract":"Abstract The main purpose of this study was the comparison of the results of quantification obtained via different sample preparation approaches such as microwave‐assisted wet digestion (MAWD) and suspension preparation. Two total reflection x‐ray fluorescence (TXRF) spectrometers equipped with Mo x‐ray tubes were used to compare results obtained via two different paths of sample preparations which would further be compared to the conventional way of analysis by inductively coupled plasma optical emission spectrometry (ICP‐OES) including MAWD. Three dietary supplement samples with different sets and concentrations of elements were analyzed. The benefits and limitations of the simplified path of sample preparation were highlighted. A round‐robin test between TXRF and ICP‐OES was discussed. Accuracy as the percentage of recovery in all measurements ranged from 80 to 120. Precision for all results did not exceed 8% for TXRF and 5% for ICP‐OES. Limits of quantification by TXRF are ranged from 1 to 0.01 mg/pill for different elements. It was shown that suspension preparation of samples might be a useful response to increasing demand for quality control of dietary supplements since it is less time consuming and cost efficient.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":"23 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135396761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daichi Kohmoto, K. Miyazaki, Masahito Morita, K. Fukuda, Takeshi Abe
This study developed a method to detect and analyze deterioration in sections of a battery during charge–discharge tests in real time. This method is based on a time‐series analysis using x‐ray computed tomography, three‐dimensional reconstruction of the battery volume, and unsupervised machine learning. The developed method detects not only electrochemical changes in a battery through the conventional voltage‐capacity diagram but also physical changes such as the deterioration of the parts of a battery that cannot be found via human inspection directly from the sliced images of the three‐dimensional reconstructed volumes. Furthermore, the characteristics of these changes inside a battery can be captured through precise analysis using persistent homology, a mathematical machinery, at degrees 0 and 1. This demonstrates that our method can capture both continuous and discrete structural changes (e.g., a continuous deformation of active materials and compounds that are precipitated randomly in the electrolytes) within a battery. As a by‐product, the start of the venting system implemented near the anode of a battery can be detected using the method from a specific cycle during the charge–discharge tests.
{"title":"Detecting electrochemical changes in a nickel–zinc battery by operando x‐ray computed‐tomography analysis during charge–discharge tests","authors":"Daichi Kohmoto, K. Miyazaki, Masahito Morita, K. Fukuda, Takeshi Abe","doi":"10.1002/xrs.3400","DOIUrl":"https://doi.org/10.1002/xrs.3400","url":null,"abstract":"This study developed a method to detect and analyze deterioration in sections of a battery during charge–discharge tests in real time. This method is based on a time‐series analysis using x‐ray computed tomography, three‐dimensional reconstruction of the battery volume, and unsupervised machine learning. The developed method detects not only electrochemical changes in a battery through the conventional voltage‐capacity diagram but also physical changes such as the deterioration of the parts of a battery that cannot be found via human inspection directly from the sliced images of the three‐dimensional reconstructed volumes. Furthermore, the characteristics of these changes inside a battery can be captured through precise analysis using persistent homology, a mathematical machinery, at degrees 0 and 1. This demonstrates that our method can capture both continuous and discrete structural changes (e.g., a continuous deformation of active materials and compounds that are precipitated randomly in the electrolytes) within a battery. As a by‐product, the start of the venting system implemented near the anode of a battery can be detected using the method from a specific cycle during the charge–discharge tests.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45012517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
T. Matsuyama, Shota Sonoda, Tomoki Fuchita, Shinji Sakashita, Kouichi Tsuji
Steel plates have been widely used in bridges, vehicle bodies, guardrails, and so forth. Generally, to improve corrosion resistance, the surface of a steel plate is coated with a Zn layer. However, when the coated steel plate is scratched by external factors, the corrosion resistance decreases. Therefore, it is important to elucidate the elution processes of elements in coated layers and steel plates to develop new coated films and improve corrosion‐resistant techniques. During corrosion, an elution reaction between the coated metal and Fe (anodic reaction) and a reduction reaction of oxygen (cathodic reaction) occur. Confocal micro‐x‐ray fluorescence imaging was employed to visualize the elution processes at the anodic and cathodic steel plates. A Zn primer steel plate was scratched and then immersed in sodium chloride solution. The Zn elution process at the anodic side was observed when a constant current was applied to the two steel plates by a galvanostat. The Fe elution process did not occur, and we believe that the sacrificial protection of Zn inhibited the process. The elutions of Zn and Fe were not observed on the cathodic side of the steel plate. Using the proposed method, we successfully visualized the elemental distributions at the anodic and cathodic sides of the steel plates.
{"title":"In situ observation of electrochemical reaction of Zn primer steel plate in NaCl solution using confocal micro‐x‐ray fluorescence imaging","authors":"T. Matsuyama, Shota Sonoda, Tomoki Fuchita, Shinji Sakashita, Kouichi Tsuji","doi":"10.1002/xrs.3401","DOIUrl":"https://doi.org/10.1002/xrs.3401","url":null,"abstract":"Steel plates have been widely used in bridges, vehicle bodies, guardrails, and so forth. Generally, to improve corrosion resistance, the surface of a steel plate is coated with a Zn layer. However, when the coated steel plate is scratched by external factors, the corrosion resistance decreases. Therefore, it is important to elucidate the elution processes of elements in coated layers and steel plates to develop new coated films and improve corrosion‐resistant techniques. During corrosion, an elution reaction between the coated metal and Fe (anodic reaction) and a reduction reaction of oxygen (cathodic reaction) occur. Confocal micro‐x‐ray fluorescence imaging was employed to visualize the elution processes at the anodic and cathodic steel plates. A Zn primer steel plate was scratched and then immersed in sodium chloride solution. The Zn elution process at the anodic side was observed when a constant current was applied to the two steel plates by a galvanostat. The Fe elution process did not occur, and we believe that the sacrificial protection of Zn inhibited the process. The elutions of Zn and Fe were not observed on the cathodic side of the steel plate. Using the proposed method, we successfully visualized the elemental distributions at the anodic and cathodic sides of the steel plates.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42145899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review provides an overview and description of the results obtained from our coal studies conducted over the past two decades. It places specific emphasis on crucial parameters, including the ash content and calorific value of lignite, which is the main energy source in Mongolia. Through the research, we observed that the ash content of coal can be estimated by analyzing the concentrations of key chemical elements, including Ca, Fe, and Sr. The results of ash content obtained from the x‐ray fluorescence analysis are consistent with the outcomes of chemical analysis. Furthermore, we established an inverse linear correlation between the calorific value of coal and its ash content. Building upon this correlation, we have proposed a method that allows for the direct determination of coal calorific value without relying on calorimetric measurements.
{"title":"Brief overview of x‐ray fluorescence applications in Mongolian brown coal","authors":"Z. Damdinsuren, P. Zuzaan, B. Damdinsuren","doi":"10.1002/xrs.3399","DOIUrl":"https://doi.org/10.1002/xrs.3399","url":null,"abstract":"The review provides an overview and description of the results obtained from our coal studies conducted over the past two decades. It places specific emphasis on crucial parameters, including the ash content and calorific value of lignite, which is the main energy source in Mongolia. Through the research, we observed that the ash content of coal can be estimated by analyzing the concentrations of key chemical elements, including Ca, Fe, and Sr. The results of ash content obtained from the x‐ray fluorescence analysis are consistent with the outcomes of chemical analysis. Furthermore, we established an inverse linear correlation between the calorific value of coal and its ash content. Building upon this correlation, we have proposed a method that allows for the direct determination of coal calorific value without relying on calorimetric measurements.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46533768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chiara Ricci, Valeria Ponza, Francesco Paolo Romano, C. Caliri, Claudia Conti, A. Botteon, E. Possenti, Dominique Scalarone, M. Cardinali, Alessandra Bassi, Sara Abram, Luca Avataneo, Daniele Demonte, Federico Di Iorio, Melissa David, C. Miliani, Angela Fabrizia Previtali, A. Piccirillo
The study and conservation of a painting by Wasily Kandinsky, titled Spitz‐Rund and dated to 1925, was carried out at the Centro per la Conservazione ed il Restauro dei Beni Culturali “La Venaria Reale” 2018 and 2021. This work, owned by the Galleria d'Arte Moderna e Contemporanea of Bergamo (GAMeC), was created with oil paints on cardboard, and later glued onto a wooden support. A first phase of the project entailed a thorough scientific investigation of the artist's materials and techniques by means of a multi‐analytical approach, including both non‐invasive and micro‐invasive techniques. The present contribution discusses some of the most relevant results obtained from scientific analyses on Kandinsky's masterpiece. The painting stratigraphy and colour palette were investigated using multispectral imaging, spot XRF and in situ Raman analyses. Micro‐samples were also taken and analysed with FTIR spectroscopy, Py‐GC/MS, optical microscopy and SEM–EDX. Additional investigations using MA‐XRF provided further insight into the distribution of various chemical elements, proving essential to deepen our knowledge of the painting and to integrate the information obtained from other analytical techniques. The study highlighted several similarities between Spitz‐Rund and other Kandinsky's artworks and made it possible to gain a broader understanding of the artist's technique during the Bauhaus period (1922–1933).
{"title":"Exploring the colour palette of Wasily Kandinsky: The case study of Spitz‐Rund (1925)","authors":"Chiara Ricci, Valeria Ponza, Francesco Paolo Romano, C. Caliri, Claudia Conti, A. Botteon, E. Possenti, Dominique Scalarone, M. Cardinali, Alessandra Bassi, Sara Abram, Luca Avataneo, Daniele Demonte, Federico Di Iorio, Melissa David, C. Miliani, Angela Fabrizia Previtali, A. Piccirillo","doi":"10.1002/xrs.3397","DOIUrl":"https://doi.org/10.1002/xrs.3397","url":null,"abstract":"The study and conservation of a painting by Wasily Kandinsky, titled Spitz‐Rund and dated to 1925, was carried out at the Centro per la Conservazione ed il Restauro dei Beni Culturali “La Venaria Reale” 2018 and 2021. This work, owned by the Galleria d'Arte Moderna e Contemporanea of Bergamo (GAMeC), was created with oil paints on cardboard, and later glued onto a wooden support. A first phase of the project entailed a thorough scientific investigation of the artist's materials and techniques by means of a multi‐analytical approach, including both non‐invasive and micro‐invasive techniques. The present contribution discusses some of the most relevant results obtained from scientific analyses on Kandinsky's masterpiece. The painting stratigraphy and colour palette were investigated using multispectral imaging, spot XRF and in situ Raman analyses. Micro‐samples were also taken and analysed with FTIR spectroscopy, Py‐GC/MS, optical microscopy and SEM–EDX. Additional investigations using MA‐XRF provided further insight into the distribution of various chemical elements, proving essential to deepen our knowledge of the painting and to integrate the information obtained from other analytical techniques. The study highlighted several similarities between Spitz‐Rund and other Kandinsky's artworks and made it possible to gain a broader understanding of the artist's technique during the Bauhaus period (1922–1933).","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47546175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
G. Pashkova, A. Nikonova, S. D. Dylgerova, E. Chuparina, A. Maltsev, A. N. Zhilicheva, O. Belozerova, L. P. Paradina, O. Glyzina, I. Khanaev
Oxidative stress of Lake Baikal organisms can be caused by pollution of nearshore with anionic surfactants or heavy metals. Some specific heavy metals are essential for aquatic organisms. At present, there are no data concerning heavy metal content caused by anthropogenic pollution or chemotaxonomic features of Baikal sponges. Here, we consider the applicability of total reflection x‐ray fluorescence (TXRF) to analyze heavy metals in Lubomirskia baikalensis to fill this gap. It was shown that TXRF method can be successfully applied to the fast and reliable quantification of Cu, Zn, Fe, and Mn in this object. Evaluation of different sample treatment procedures showed that the acid digestion by HNO3/H2O2 mixture is an optimal procedure for the preparation of sponges compared with suspension preparation. It helps to improve sensitivity, eliminate the effects of particle size and specimen heterogeneity. The total uncertainty of the TXRF results associated with the sample preparation, taking, depositing, and measuring of the specimen was 6%–18% for Mn, 3%–5% for Cu, 5%–12% for Fe, and 4%–5% for Zn. To validate the developed method, the TXRF results were compared with the data obtained by wavelength dispersive x‐ray fluorescence spectrometry. A good agreement of results was achieved. TXRF data show the dominance of essential heavy metals in L. baikalensis (n = 14) among other heavy metals. Correlations between Cu/Zn contents (R2 = 0.515) as well as between Fe/Mn contents (R2 = 0.972) can be explained by the contribution of them to L. baikalensis antioxidant system.
{"title":"Applicability of total reflection x‐ray fluorescence for heavy metal analysis in Lake Baikal sponges","authors":"G. Pashkova, A. Nikonova, S. D. Dylgerova, E. Chuparina, A. Maltsev, A. N. Zhilicheva, O. Belozerova, L. P. Paradina, O. Glyzina, I. Khanaev","doi":"10.1002/xrs.3396","DOIUrl":"https://doi.org/10.1002/xrs.3396","url":null,"abstract":"Oxidative stress of Lake Baikal organisms can be caused by pollution of nearshore with anionic surfactants or heavy metals. Some specific heavy metals are essential for aquatic organisms. At present, there are no data concerning heavy metal content caused by anthropogenic pollution or chemotaxonomic features of Baikal sponges. Here, we consider the applicability of total reflection x‐ray fluorescence (TXRF) to analyze heavy metals in Lubomirskia baikalensis to fill this gap. It was shown that TXRF method can be successfully applied to the fast and reliable quantification of Cu, Zn, Fe, and Mn in this object. Evaluation of different sample treatment procedures showed that the acid digestion by HNO3/H2O2 mixture is an optimal procedure for the preparation of sponges compared with suspension preparation. It helps to improve sensitivity, eliminate the effects of particle size and specimen heterogeneity. The total uncertainty of the TXRF results associated with the sample preparation, taking, depositing, and measuring of the specimen was 6%–18% for Mn, 3%–5% for Cu, 5%–12% for Fe, and 4%–5% for Zn. To validate the developed method, the TXRF results were compared with the data obtained by wavelength dispersive x‐ray fluorescence spectrometry. A good agreement of results was achieved. TXRF data show the dominance of essential heavy metals in L. baikalensis (n = 14) among other heavy metals. Correlations between Cu/Zn contents (R2 = 0.515) as well as between Fe/Mn contents (R2 = 0.972) can be explained by the contribution of them to L. baikalensis antioxidant system.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48084050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marco Colombo, F. Muench, P. Hoffmann, Jochen Sander, W. Ensinger
Fe and/or Mn‐containing yellow ochre, red ochre, and umber earth pigments are omnipresent in 17th century paintings. Less common in the materials used in historical paintings of this period is the Fe and Mn‐rich earth pigment sienna. Different uses of historical pigments in one painting by Georg Flegel (1566–1638) and another version of the same painting but of disputed attribution were recently uncovered by means of macro‐x‐ray fluorescence (MA‐XRF) scanning and other non‐invasive analytical techniques. In this paper, an approach solely based upon the correlation of Fe and Mn MA‐XRF maps with the optical image of the painting is compared to the use of Mn/Fe correlation plots. The identification of clusters within a plot of the Fe counts vs. the Mn counts can aid to infer whether an area with a certain color matches with the use of the earth pigments found in the two paintings and to ultimately shed light on the different usage of these pigments. The analytical thresholds found in the Mn/Fe correlation plots allowed to identify clusters differing in composition, which matched an area of a certain color with the earth pigments used therein. This highlighted the differences and similarities between the two paintings, ultimately ascertaining the lower value of the painting of disputed attribution. The analysis of single‐pixel spectra allowed refining the interpretation of specific Mn/Fe correlation plots. The purpose of these data evaluation steps is presented and the limitations of the proposed methodology are also discussed.
{"title":"Scanning macro x‐ray fluorescence spectroscopy maps for matching 17th century paintings color areas to different earth pigments uses and for investigating attribution issues","authors":"Marco Colombo, F. Muench, P. Hoffmann, Jochen Sander, W. Ensinger","doi":"10.1002/xrs.3398","DOIUrl":"https://doi.org/10.1002/xrs.3398","url":null,"abstract":"Fe and/or Mn‐containing yellow ochre, red ochre, and umber earth pigments are omnipresent in 17th century paintings. Less common in the materials used in historical paintings of this period is the Fe and Mn‐rich earth pigment sienna. Different uses of historical pigments in one painting by Georg Flegel (1566–1638) and another version of the same painting but of disputed attribution were recently uncovered by means of macro‐x‐ray fluorescence (MA‐XRF) scanning and other non‐invasive analytical techniques. In this paper, an approach solely based upon the correlation of Fe and Mn MA‐XRF maps with the optical image of the painting is compared to the use of Mn/Fe correlation plots. The identification of clusters within a plot of the Fe counts vs. the Mn counts can aid to infer whether an area with a certain color matches with the use of the earth pigments found in the two paintings and to ultimately shed light on the different usage of these pigments. The analytical thresholds found in the Mn/Fe correlation plots allowed to identify clusters differing in composition, which matched an area of a certain color with the earth pigments used therein. This highlighted the differences and similarities between the two paintings, ultimately ascertaining the lower value of the painting of disputed attribution. The analysis of single‐pixel spectra allowed refining the interpretation of specific Mn/Fe correlation plots. The purpose of these data evaluation steps is presented and the limitations of the proposed methodology are also discussed.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41962355","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
At the Museo Campano (Capua, Italy), eight double‐relief silver coins belonging to southern Italian poleis and dated between the end of the 5th century and the beginning of the 3rd century BC were analysed. These coins are of great interest to historians and archaeologists because they provide extensive evidence on the monetary history and circulation of coins since the earliest times in the Campania region. Non‐invasive in situ analyses were performed using point XRF and MA‐XRF measurements and digital microscope photos. These coins were of high fineness. Data analysis methods using ROI imaging, deconvoluted maps, NMF (nonnegative matrix factorization), and k‐means were applied on the elemental maps to study the critical surface areas and to compare the effectiveness of different methods not commonly used for coins. These results combined with numismatic studies provided information on the historical context, the alloy used, and cases such as subaerati and restored coins. Important data were obtained on the currencies of the period under review, which will be useful to integrate with the analysis of further samples.
{"title":"MA‐XRF analysis of ancient silver coins minted in southern Italy","authors":"J. Brocchieri, R. Vitale, C. Sabbarese","doi":"10.1002/xrs.3395","DOIUrl":"https://doi.org/10.1002/xrs.3395","url":null,"abstract":"At the Museo Campano (Capua, Italy), eight double‐relief silver coins belonging to southern Italian poleis and dated between the end of the 5th century and the beginning of the 3rd century BC were analysed. These coins are of great interest to historians and archaeologists because they provide extensive evidence on the monetary history and circulation of coins since the earliest times in the Campania region. Non‐invasive in situ analyses were performed using point XRF and MA‐XRF measurements and digital microscope photos. These coins were of high fineness. Data analysis methods using ROI imaging, deconvoluted maps, NMF (nonnegative matrix factorization), and k‐means were applied on the elemental maps to study the critical surface areas and to compare the effectiveness of different methods not commonly used for coins. These results combined with numismatic studies provided information on the historical context, the alloy used, and cases such as subaerati and restored coins. Important data were obtained on the currencies of the period under review, which will be useful to integrate with the analysis of further samples.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46421418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luís Manuel de Almeida Nieto, F. Gabrieli, A. van Loon, Victor Gonzalez, J. Dik, R. Van de Plas, M. Alfeld
Macroscopic x‐ray fluorescence imaging spectroscopy (MA‐XRF) and reflectance imaging spectroscopy (RIS) are important tools in the analysis of cultural heritage objects, both for conservation and art historical research purposes. The elemental and molecular distributions provided by MA‐XRF and RIS respectively, are particularly useful for the identification and mapping of pigments in easel paintings. While MA‐XRF has relatively established data processing methods based on modeling of the underlying physics, RIS data cannot be modeled with sufficient precision and its processing has considerable room for improvements. This work seeks to improve RIS data processing workflows in the short wavelength infrared range (SWIR, 1000–2500 nm) with a novel method that fits Gaussian profiles to pigment‐specific absorption features, and we compare its performance to MA‐XRF for the task of semi‐quantitative pigment mapping, evaluating their limits of detection (LODs) and the matrix effects that affect their signals. Two pigments are considered in this work, lead white and blue verditer, which are mapped in SWIR RIS using the first overtone of OH stretching of their primary compounds, hydrocerussite (Pb3(CO3)2(OH)2) and azurite (Cu3(CO3)2(OH)2), at 1447 and 1497 nm respectively, and in MA‐XRF using the Pb‐L and Cu‐K fluorescence signals. The methods are evaluated using two sets of custom‐prepared paint samples, as well as a 16th‐century painting, discussing the identification, mapping, and semi‐quantitative analysis of the considered pigments. We found SWIR RIS to be a pigment‐specific method with a longer linear range but inferior LODs and penetration depth when compared to MA‐XRF, the latter is often not capable of discriminating between different pigments with identical elemental markers. We furthermore present a novel color scale that allows the simultaneous visualization of signals above and below a confidence limit.
{"title":"Comparison of macro x‐ray fluorescence and reflectance imaging spectroscopy for the semi‐quantitative analysis of pigments in easel paintings: A study on lead white and blue verditer","authors":"Luís Manuel de Almeida Nieto, F. Gabrieli, A. van Loon, Victor Gonzalez, J. Dik, R. Van de Plas, M. Alfeld","doi":"10.1002/xrs.3394","DOIUrl":"https://doi.org/10.1002/xrs.3394","url":null,"abstract":"Macroscopic x‐ray fluorescence imaging spectroscopy (MA‐XRF) and reflectance imaging spectroscopy (RIS) are important tools in the analysis of cultural heritage objects, both for conservation and art historical research purposes. The elemental and molecular distributions provided by MA‐XRF and RIS respectively, are particularly useful for the identification and mapping of pigments in easel paintings. While MA‐XRF has relatively established data processing methods based on modeling of the underlying physics, RIS data cannot be modeled with sufficient precision and its processing has considerable room for improvements. This work seeks to improve RIS data processing workflows in the short wavelength infrared range (SWIR, 1000–2500 nm) with a novel method that fits Gaussian profiles to pigment‐specific absorption features, and we compare its performance to MA‐XRF for the task of semi‐quantitative pigment mapping, evaluating their limits of detection (LODs) and the matrix effects that affect their signals. Two pigments are considered in this work, lead white and blue verditer, which are mapped in SWIR RIS using the first overtone of OH stretching of their primary compounds, hydrocerussite (Pb3(CO3)2(OH)2) and azurite (Cu3(CO3)2(OH)2), at 1447 and 1497 nm respectively, and in MA‐XRF using the Pb‐L and Cu‐K fluorescence signals. The methods are evaluated using two sets of custom‐prepared paint samples, as well as a 16th‐century painting, discussing the identification, mapping, and semi‐quantitative analysis of the considered pigments. We found SWIR RIS to be a pigment‐specific method with a longer linear range but inferior LODs and penetration depth when compared to MA‐XRF, the latter is often not capable of discriminating between different pigments with identical elemental markers. We furthermore present a novel color scale that allows the simultaneous visualization of signals above and below a confidence limit.","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":" ","pages":""},"PeriodicalIF":1.2,"publicationDate":"2023-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45138146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Detection of single atom using soft X-ray spectroscopy (May 31, 2023) A research group at Argonne National Laboratory's APS synchrotron radiation facility has reported the detection of single atoms using synchrotron radiation X-rays (Tolulope M. Ajayi, Nozomi Shirato, Tomas Rojas, Sarah Wieghold, Xinyue Cheng, Kyaw Zin Latt, Daniel J. Trainer, Naveen K. Dandu, Yiming Li, Sineth Premarathna, Sanjoy Sarkar, Daniel Rosenmann, Yuzi Liu, Nathalie Kyritsakas, Shaoze Wang, Eric Masson, Volker Rose, Xiaopeng Li, Anh T. Ngo and Saw-Wai Hla, “Characterization of just one atom using synchrotron X-rays,” Nature, 618, 69–73 (2023) https://doi.org/10.1038/s41586-023-06011-w). This research was performed at XTIP21, a beamline equipped with an STM probe in an ultrahigh vacuum chamber that can simultaneously perform STM imaging and soft X-ray spectroscopy experiments. The research sample is a supramolecular assembly with a ring structure consisting of seven terpyridine-metal-terpyridine bridges, with six ruthenium atoms and one iron atom on the metal. First, the sample was imaged by STM, and then, under the same conditions, the X-ray energy near the L2,3 absorption edge of iron was scanned with a monochromator, and the excitation current was measured by the probe. The electric current changed at the absorption edge, indicating that a single atom could be detected. Since the X-ray signal was detected only when the probe was placed extremely close to the atom, X-ray excitation resonance tunneling is dominant, confirming the detection of atom localization in the tunneling region. Another sample in this study, a terbium complex, was also measured. In this complex, the terbium is firmly anchored by three brominated pyridine-2,6-dicarboxamide ligands. As with the previous sample, STM imaging was performed and the synchrotron radiation energy was varied near the M4,5 absorption edge of terbium under the same conditions and a single atom was detected. Some readers may ask whether such a measurement can be achieved with X-ray fluorescence. It would depend on the sample conditions. The analysis of very small numbers of atoms by X-ray fluorescence spectroscopy is mainly limited by the background. If a sample has almost no background, in contrast to conventional X-ray analysis, it would theoretically be possible to detect a single atom. For example, if we have a sample in which only one atom is trapped in a fullerene, and the fullerene is placed in a carbon nanotube, it is possible to detect characteristic X-rays excited by electron beams with a semiconductor detector while observing the single atom with a transmission electron microscope. This was reported more than 10 years ago. For more details, see T. C. Lovejoy, Q. M. Ramasse, M. Falke, A. Kaeppel, R. Terborg, R. Zan, N. Dellby, and O. L. Krivanek, “Single atom identification by energy dispersive x- ray spectroscopy,” Appl. Phys. Lett. 100, 154101 (2012). https://doi.org/10.1063/1.3701598, and Kazu Suenaga, Toshiya Okaz
(2023年5月31日)美国阿贡国家实验室APS同步辐射设施的一个研究小组报道了使用同步辐射x射线探测单原子的研究成果(Tolulope M. Ajayi, Nozomi Shirato, Tomas Rojas, Sarah Wieghold, Xinyue Cheng, Kyaw Zin Latt, Daniel J. Trainer, Naveen K. Dandu, Yiming Li, Sineth Premarathna, Sanjoy Sarkar, Daniel Rosenmann, Yuzi Liu, Nathalie Kyritsakas, Shaoze Wang, Eric Masson, Volker Rose，李晓鹏，Anh T. Ngo和Saw-Wai Hla，“使用同步加速器x射线表征仅一个原子”，Nature, 618, 69-73 (2023) https://doi.org/10.1038/s41586-023-06011-w)。这项研究是在XTIP21上进行的，XTIP21是一个在超高真空室中配备STM探针的光束线，可以同时进行STM成像和软x射线光谱实验。该研究样品是一种由7个三吡啶-金属-三吡啶桥组成的环状结构的超分子组装体，金属上有6个钌原子和1个铁原子。首先对样品进行STM成像，然后在相同条件下，用单色仪扫描铁的L2,3吸收边附近的x射线能量，并用探针测量激发电流。电流在吸收边缘发生变化，表明可以检测到单个原子。由于只有当探针放置在离原子非常近的位置时，x射线信号才会被探测到，因此x射线激发共振隧穿占主导地位，证实了在隧穿区探测到原子的局域化。在这项研究中，还测量了另一种样品——铽络合物。在这个配合物中，铽被三个溴化吡啶-2,6-二羧基酰胺配体牢牢固定。与前一个样品一样，进行STM成像，在相同条件下，同步辐射能量在terbir的M4,5吸收边附近变化，并检测到单个原子。一些读者可能会问，这种测量是否可以用x射线荧光来实现。这取决于样品条件。x射线荧光光谱法对极少量原子的分析主要受到背景的限制。与传统的x射线分析不同，如果样品几乎没有背景，理论上就有可能检测到单个原子。例如，如果我们有一个样品，其中只有一个原子被困在富勒烯中，并且富勒烯被放置在碳纳米管中，那么在用透射电子显微镜观察单个原子的同时，用半导体探测器就有可能探测到电子束激发的特征x射线。这是十多年前的报道。更多细节，参见t.c. Lovejoy, Q. M. Ramasse, M. Falke, A. Kaeppel, R. Terborg, R. Zan, N. Dellby和O. L. Krivanek，“用能量色散x射线光谱学识别单原子”，苹果。理论物理。生物医学工程学报，2012,32(4):481 - 481。https://doi.org/10.1063/1.3701598，和Kazu Suenaga, Toshiya Okazaki, Eiji Okunishi和Syo Matsumura，“在能量色散x射线光谱中探测单个erm原子发射的光子，”Nature Photonics 6, 545-548(2012)。https://doi.org/10.1038/nphoton.2012.148。
{"title":"News Article","authors":"Kenji Sakurai","doi":"10.1002/xrs.3393","DOIUrl":"https://doi.org/10.1002/xrs.3393","url":null,"abstract":"Detection of single atom using soft X-ray spectroscopy (May 31, 2023) A research group at Argonne National Laboratory's APS synchrotron radiation facility has reported the detection of single atoms using synchrotron radiation X-rays (Tolulope M. Ajayi, Nozomi Shirato, Tomas Rojas, Sarah Wieghold, Xinyue Cheng, Kyaw Zin Latt, Daniel J. Trainer, Naveen K. Dandu, Yiming Li, Sineth Premarathna, Sanjoy Sarkar, Daniel Rosenmann, Yuzi Liu, Nathalie Kyritsakas, Shaoze Wang, Eric Masson, Volker Rose, Xiaopeng Li, Anh T. Ngo and Saw-Wai Hla, “Characterization of just one atom using synchrotron X-rays,” Nature, 618, 69–73 (2023) https://doi.org/10.1038/s41586-023-06011-w). This research was performed at XTIP21, a beamline equipped with an STM probe in an ultrahigh vacuum chamber that can simultaneously perform STM imaging and soft X-ray spectroscopy experiments. The research sample is a supramolecular assembly with a ring structure consisting of seven terpyridine-metal-terpyridine bridges, with six ruthenium atoms and one iron atom on the metal. First, the sample was imaged by STM, and then, under the same conditions, the X-ray energy near the L2,3 absorption edge of iron was scanned with a monochromator, and the excitation current was measured by the probe. The electric current changed at the absorption edge, indicating that a single atom could be detected. Since the X-ray signal was detected only when the probe was placed extremely close to the atom, X-ray excitation resonance tunneling is dominant, confirming the detection of atom localization in the tunneling region. Another sample in this study, a terbium complex, was also measured. In this complex, the terbium is firmly anchored by three brominated pyridine-2,6-dicarboxamide ligands. As with the previous sample, STM imaging was performed and the synchrotron radiation energy was varied near the M4,5 absorption edge of terbium under the same conditions and a single atom was detected. Some readers may ask whether such a measurement can be achieved with X-ray fluorescence. It would depend on the sample conditions. The analysis of very small numbers of atoms by X-ray fluorescence spectroscopy is mainly limited by the background. If a sample has almost no background, in contrast to conventional X-ray analysis, it would theoretically be possible to detect a single atom. For example, if we have a sample in which only one atom is trapped in a fullerene, and the fullerene is placed in a carbon nanotube, it is possible to detect characteristic X-rays excited by electron beams with a semiconductor detector while observing the single atom with a transmission electron microscope. This was reported more than 10 years ago. For more details, see T. C. Lovejoy, Q. M. Ramasse, M. Falke, A. Kaeppel, R. Terborg, R. Zan, N. Dellby, and O. L. Krivanek, “Single atom identification by energy dispersive x- ray spectroscopy,” Appl. Phys. Lett. 100, 154101 (2012). https://doi.org/10.1063/1.3701598, and Kazu Suenaga, Toshiya Okaz","PeriodicalId":23867,"journal":{"name":"X-Ray Spectrometry","volume":"18 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135835791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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