Lead isotope analysis of lead white as a tool for the dating Józef Szermentowski’s paintings

Lead isotope analysis of lead white as a tool for the dating Józef Szermentowski’s paintings | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Lead isotope analysis of lead white as a tool for the dating Józef Szermentowski’s paintings Ewa Doleżyńska-Sewerniak, Jakub Karasiński, Piotr Radziński This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8584692/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 9 You are reading this latest preprint version Abstract This paper presents the results of lead isotope composition analyses of lead white samples taken from paintings by Józef Szermentowski, a Polish painter. The examination of works by the artist revealed changes in the source of lead in the white paint samples that were associated with his activity in various artistic centres. This indicates that while working in Poland as well as in various regions of France, Szermentowski used lead white derived from a variety of geological deposits. Differences in the lead isotope composition may be a potential for broader future applications of this method in determining the date and place of execution of works whose precise provenance has not yet been established. The results also provide information on the availability of specific types of lead white in certain geographical areas, making a comparative reference framework for other paintings from this period and for the nineteenth-century lead white trade networks. Figures Figure 1 Figure 2 1. Introduction Lead isotope composition analysis enables the description of the geological origin of lead and has been widely employed in e.g., forensic science, environmental studies, and geochemistry [ 1 , 2 , 3 , 4 ]. This method has also been applied in archaeology and geology for the dating of minerals and artefacts [ 2 , 5 , 6 ]. The field literature, although less frequently, also offers examples of this method’s applications to the study of painting. The objectives of previous analyses have included, e.g., the identification of the origin of lead white used in specific works [ 7 , 8 , 9 , 10 , 11 , 12 ], the characterisation of this pigment in individual paintings [ 13 , 14 , 15 ], the authentication of attribution and provenance of paintings [ 15 , 16 ], and dating studies [ 10 , 11 ]. Researchers have demonstrated that variability in lead isotope ratios can be used to establish the provenance of artefacts. Analyses of types of lead white within specific chronological ranges and geographical regions provide information on the availability of this pigment in various artistic centres and on its trade [ 8 , 9 , 10 , 12 , 15 ]. This approach may, at times, enable the identification of the place of execution of a painting and the artistic group that employed characteristic types of lead white. Isotopic analysis may also be a complementary tool for confirming attribution and dating of paintings of disputed dating [ 15 , 16 ], as well as for reconstructing the workshop practice of an individual artist or artistic groups [ 8 , 9 , 10 , 11 ]. The trade and distribution networks of lead white in Europe were complex and often correlated with various historical events [ 10 ]. The interpretation of analytical results may thus be challenging due to the absence of systematic studies on this issue and the limited availability of databases on the lead isotope composition of all major, or most frequently exploited, deposits. Until detailed data on the mining sources of lead used for artistic purposes and its trade routes are established, the difficulties associated with determining the provenance of artefacts must be acknowledged. This issue is particularly complex in the case of industrially manufactured lead whites from the nineteenth century onwards. At that time, there were some large enterprises whose core activity was paint production; their products were exported over long distances, which was also facilitated by the development of steam railways and maritime transport. The key research objective of this study was to determine the lead isotope composition of representative lead white samples taken from paintings by the Polish painter Józef Szermentowski, who was active in the third quarter of the nineteenth century. Szermentowski was a pioneer and leading figure of realist landscape painting in Poland. His artistic formation was rooted in the Warsaw milieu of the 1850s. After 1860, he relocated to France, where he initially worked in the vicinity of Fontainebleau and Bourron-Marlotte—centres associated with the Barbizon School and artists from all over the world—before settling permanently in Paris, where he died [ 17 ]. It was essential to verify whether any measurable differences in the lead isotope composition of lead white can be identified in the artist’s works executed in geographically distant artistic centres, namely in Poland (Warsaw and the Kielce region) and in France (Bourron-Marlotte, Fontainebleau and Paris). We sought to determine whether, when working in Poland and abroad, the artist used lead whites derived from the same sources, for example acquired from the same manufacturers. We also wanted to assess whether lead isotope analyses could corroborate the already existing dating of unsigned works, and to investigate whether, in the second half of the nineteenth century, lead whites produced from lead ores originating from specific ore mining regions were prevalent on the artistic markets in the regions where the artist was active, as well as to establish the possible range of their distribution. Lead isotope ratios were determined using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) with an internal standardisation approach. To date, this method has been applied primarily to the analysis of lead whites used by early modern artists. An additional objective of this study was therefore to evaluate its usefulness for the analysis of lead whites, used by artists active years later, in a period when industrially manufactured white pigments—often mixtures of different white pigments and extenders—had become commonly used by artists. 2. Methods 2.1. Lead white White pigment is the fundamental pigment that has been used in painting of the past and the present. Lead white occupies a prominent position among the variety of whites, primarily due to its long-term presence in painting materials [ 18 ]. It was used from the earliest times and only began to lose its dominant status in the second half of the nineteenth century [ 18 , 19 ]. Lead white is also one of the oldest synthetic pigments. It has a number of advantages: high opacity, good lightfastness, and good drying properties in drying oils [ 18 , 19 ]. These distinctive properties set it apart from other white pigments. Yet, it also has its major drawbacks: it blackens upon exposure to hydrogen sulphide and is highly toxic [ 18 , 19 , 20 ]. The latter property resulted in its replacement by other pigments, one of which was zinc white, which gained popularity in painting in the nineteenth century [ 20 , 21 ] and which was widely used in oil paints from around 1850. It has lower opacity in oil than lead white, does not act as a siccative, and has a tendency to form cracks when applied in thicker layers. Consequently, in the second half of the nineteenth century, lead white still remained the dominant white pigment that was frequently employed, especially towards the end of the century, in mixtures with other white pigments and extenders. This dominance of lead white in painting was evident even in the early twentieth century. Lead white was used both as a pure white pigment for highest highlights and specular highlights, and in mixtures for the lightening of specific colours. It was also used as an extender in ground layers and as a siccative pigment in oil paints. Chemically, lead white is basic lead carbonate, with lead content up to 80%, which is significant for its use in lead isotope analysis [ 10 ]. The primary lead ore, galena, often contains silver, and its value contributed to the development of lead mining and use as early as in ancient Rome [ 9 ]. The historical process of smelting of galena was simple and similar across various geographical regions. It involved heating the ore in simple hearths, i.e., stone chimneys with a channel for molten metal and at temperatures slightly exceeding 300°C [ 9 ]. Since antiquity, lead white was produced by placing thin sheets of lead above a vessel containing acetic acid, i.e., vinegar. The acetic acid vapors reacted with lead to form a white product, which was then scraped off, dried, powdered, and sieved, and subsequently mixed with, e.g., linseed oil to produce paint [ 18 , 21 ]. 2.2. Lead isotope Most chemical elements show isotopic variation, i.e. they occur in variants with the same atomic number (the same number of protons in the atomic nucleus), yet they differ in the number of neutrons within the atomic nucleus. This results in e.g., the variability of the isotopic composition of metal ores, such as lead, as well as of the products derived from them. Lead has four natural stable isotopes— ²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb —which occur in varying relative proportions of components in soils and rocks. The latter three isotopes are radiogenic, i.e., they are derived partly from the radioactive decay of uranium and thorium. The abundances of ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb vary among deposits (particularly as a function of uranium and thorium content), yet ²⁰⁴Pb is non-radiogenic and thus its abundance remains constant over time. The isotopic composition of lead can be demonstrated as plots of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios, which is a standard procedure in geochronological studies. Lead is an element characterised by substantial isotopic heterogeneity across different geological regions, which enables the determination of the origin of the lead ore from which it was extracted [ 1 ]. What needs to be stressed is the fact that galenas from different ore deposits have distinct lead isotopic composition; however, the proportions of lead isotopes do not undergo significant changes during the conversion of ore into white pigment. This is a key factor in the application of lead isotope ratios in studies aimed at the properties and origin of lead-based materials. As a result, artefacts or objects containing lead compounds derived from the same source can be identified and the fact whether a given lead sample originates from a northern or a southern deposit can be established. 2.3. The research object Eighteen paintings by Józef Szermentowski were selected for the lead white analysis. Art historians have dated their execution to the period 1852–1874. Half of these works bear the artist’s original signatures with execution dates, while the remaining paintings were dated primarily on the basis of stylistic analysis (Table 1 ). The paintings come from the collections of two museums—the National Museum in Wrocław and the National Museum in Kielce; the latter holds the most extensive collection of the artist’s paintings. Specific artworks were selected due to their availability and the possibility of conducting invasive analyses, i.e. analyses performed on samples taken from the paintings. The selection of works also aimed to ensure that the lead white pigments present in the works were representative of the key periods of the artist’s career. Eleven paintings date back to Szermentowski’s early creative period, consistent with his education and life spent in Poland—mainly in Warsaw and the Kielce region—up to 1860. One painting is dated to ca. 1860, without a clear indication as to whether it was completed in Poland or abroad. Two paintings were attributed to the post-1860 period, corresponding to the artist’s relocation to France, when he painted plein-air studies in the vicinity of Bourron-Marlotte and Fontainebleau. Four paintings were created during the final years of the artist’s life in Paris, France. Table 1 List of Józef Szermentowski’s examined paintings with the results of lead isotope ratio measurements Place of execution Title Museum ID Date Signature and date 208 Pb/ 204 Pb 207 Pb / 204 Pb 206 Pb / 204 Pb 208 Pb / 206 Pb 207 Pb / 206 Pb Sample no Poland Study of a horse MNKi/M/36 ok. 1852 38.508 15.666 18.366 2.0960 0.8530 2 Market Square in Szydlowiec MNKi/M/280 1854 + 38.615 15.647 18.514 2.0850 0.8452 3 View of Sandomierz from the Vistula River MNKi/M/27 1855 + 38.459 15.631 18.432 2.0857 0.8481 4 Baptism in the village MNKi/M/1116 1856 + 38.137 15.609 18.184 2.0965 0.8584 5 Village cemetery MNWr VIII-383 1856‒1857 38.162 15.612 18.195 2.0966 0.8580 6 Landscape on the Vistula River MNWr VIII-1389 1856‒1858 38.152 15.614 18.194 2.0978 0.8589 7 Chęciny MNKi/M/33 1857 + 38.519 15.668 18.372 2.0959 0.8529 8 After work MNWr VIII-425 1858 + 38.163 15.611 18.202 2.0958 0.8577 10 Holy Cross Monastery MNKi/M/1118 1859 + 38.515 15.667 18.370 2.0958 0.8528 11 Landscape of the Kielce region MNKi/M/277 przed 1860 38.158 15.613 18.203 2.0955 0.8577 12 View from the Bobrza River MNKi/M/71 1855‒1856? 38.489 15.664 18.354 2.0979 0.8541 19 Cottage by the river MNKi/M/1328 ok. 1860 38.556 15.673 18.377 2.0973 0.8529 17 France (Bourron-Merolotte/ Fontainebleau) The park MNKi/M/320 po 1860? 38.526 15.668 18.359 2.0977 0.8534 18 A tree MNKi/M/280 po 1860 38.520 15.667 18.354 2.0979 0.8536 20 France (Paris) Road to the village MNKi/M/1330 1872 38.518 15.669 18.372 2.0958 0.8529 13 River landscape MNKi/M/283 1873 (Paris) + 38.519 15.669 18.372 2.0958 0.8528 14 In the park MNWr VIII-142 1873 (Paris) + 38.452 15.655 18.356 2.0942 0.8529 15 Village church in the region of Krakow MNKi/M/79 1874 (Paris) + 38.520 15.665 18.369 2.0962 0.8528 16 2.4. Methodology Lead isotope ratio measurements were performed using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). After dissolution in dilute nitric acid (V), the sample was introduced into the measuring instrument as an aerosol. The sample components undergo ionisation within the plasma, and then specific ion beams are separated by the mass analyser and their intensity is monitored by a detector array. MC-ICP-MS is a technique specifically designed for isotope measurements. Owing to the instrument’s design, signals of individual isotopes are measured simultaneously, thus allowing analytical precision that is unmatched by any other commercially available mass spectrometer. A major advantage of this technique is the ability to analyse extremely small sample amounts, and just one microgram is enough to determine lead isotope ratios. For this reason, MC-ICP-MS is particularly well adjusted for the analysis of Old Master paintings where, due to their unique nature and great value, sample sizes must be limited to an absolute minimum. Data visualisations were produced using the R programming language with the ggplot2 package. 3. Results The analyses demonstrated that the lead isotope ratios in the lead white pigments used in the artist’s paintings range from 18.184 to 18.514 for ²⁰⁶Pb/²⁰⁴Pb, from 15.609 to 15.673 for ²⁰⁷Pb/²⁰⁴Pb, and from 38.137 to 38.615 for ²⁰⁸Pb/²⁰⁴Pb (Table 1 ). The lead isotope data are presented in bivariate diagrams comparing ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁶Pb versus ²⁰⁶Pb/²⁰⁴Pb, and ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁸Pb/²⁰⁴Pb (Fig. 1 ). The results indicate variability in the source of lead used to produce the lead white pigments employed by Józef Szermentowski. The plotted diagrams also demonstrate distinct clustering of sample groups. The first and largest cluster comprises samples 2, 8, 11, and 13–20; the second cluster includes samples 5, 6, 7, 10, and 12; while the third and smallest cluster consists of samples 3 and 4. The clustering of samples reveals three distinct data clusters associated with the type of lead white that was used by Szermentowski in certain artistic environments across two key chronological ranges—1852–1860 and 1860–1874 (Fig. 2 ). Samples 5, 6, 7, 10, and 12 form a single cluster and correspond to works produced during Szermentowski’s stay in Poland, i.e., in Warsaw and in the Kielce region. During this period, the artist employed lead white manufactured from lead originating from the same geological deposits. The paintings are dated to the years 1856–1860. This group includes the works Baptism in the village (1856) (signed and dated), Village cemetery (c. 1856–1857), Landscape on the Vistula River (c. 1856–1858), After work (1858) (signed and dated), and Landscape of the Kielce region (before 1860). These paintings are stylistically closely related and seem to be rather study and workshop works rather than plein-air studies. The second cluster comprises samples 2, 8, 11, and 13–20 taken from paintings executed both during the artist’s stay in Poland prior to 1860 and after his departure to France. This group includes works painted shortly after 1860, when Szermentowski painted plein-air studies in the vicinity of Bourron-Marlotte and Fontainebleau, as well as paintings from his final years in Paris. The lead whites in this cluster and used in Poland were identified in the following works: Study of a horse , dated to ca. 1852; Chęciny (1857) (signed and dated); Holy Cross Monastery (1859) (signed and dated); and Cottage by the river , dated to ca. 1860. This group also includes View from the Bobrza River , dated by art historians to 1855–1856; however, this dating seems to be rather uncertain. The painting bears the artist’s signature “Szermentowski” on the recto, whereas prior to his relocation to France the artist signed his works using the surname “Szermętowski”. The paintings Chęciny and Holy Cross Monastery were executed on supports of similar size and within a closely related time frame, which accounts for the use of a similar lead white pigment. The “Polish” works in this cluster are not study works but rather plein-air paintings, and they therefore differ in nature from those discussed above. The similarity in lead isotope ratios observed in paintings executed in Poland and in France indicates that the artist employed lead white from the same geological deposit. Consequently, it is not possible to distinguish between Szermentowski’s French and Polish works solely on the basis of lead isotope analysis. Samples 3 and 4 are consistent with the lead white used in Market Square in Szydlowiec (1854) and View of Sandomierz from the Vistula River (1855), both painted in Poland. Both canvases are signed and dated. They share the same dimensions, which is suggestive of a closely related time of execution. It is probable that the artist painted them near Sandomierz and Szydłowiec—towns located in the Kielce region near his native Bodzentyn. During this period, while studying at the Warsaw School of Fine Arts, the artist undertook field excursions in the Kielce region to study the Polish landscape. In these works, he employed a lead white pigment different from the one more frequently identified in paintings from 1856–1860. The source of the white pigment used by the artist at this time was therefore different. An analysis of these data indicates that during his stay in Poland the artist employed lead whites of higher isotopic variability than in the paintings completed in France. This higher variability of lead white used by Szermentowski between 1849 and 1860, when he was active in the Kingdom of Poland, reflects his artistic activity across multiple locations. Initially, Szermentowski studied in Kielce and, from 1853 to 1857, at the Warsaw School of Fine Arts. In the summer of 1856, he painted his plein-air studies in Volhynia. After 1853, he worked both in Warsaw and in Kielce and its surrounding areas. This is where he began his education and spent his final years before leaving for France. The artist also undertook field excursions throughout the country. The sources of lead white available for artistic purposes in the Kingdom of Poland at that time possibly were heterogeneous. The changes in his locations resulted in the observation, in the presented diagrams, of three distinct lead whites used by the artist during this period, with substantial differences in lead isotope composition. In the case of paintings executed in France, only minor differences in lead isotope composition are observed in the white paint samples. This is also reflected in the artist’s limited geographical activity as during this period Szermentowski worked in Paris or in the vicinity of Fontainebleau, and he probably relied on one supplier or manufacturer for his lead white. It should be stressed that this pigment was produced from the same lead deposit as the lead white used by the artist for his plein-air works in Poland, yet it differs from that identified in works painted in the Kielce region and in studio-based works from his “Polish” period. It was probably a product from the same manufacturer, whose distribution range at the time was broad, as evidenced by the presence of this lead white in both the “Polish” and “French” works of the artist. The presented results, unfortunately, do not allow for precise and detailed differentiation between paintings produced in France and those created in Poland. Consequently, refining the dating of Cottage by the river and The park , as well as confirming the dating of View from the Bobrza River , solely through lead isotope ratio analysis is not currently feasible. These results pertain to only 18 paintings out of more than 100 present in the Polish collections, and thus require further investigation. 4. Discussion The identification of temporal variability in lead isotope ratios in the lead white pigments of Józef Szermentowski’s paintings enables to differentiate works produced in various artistic centres and, in some cases, to distinguish early from late works. The differences between the lead whites used in Poland in the Kielce region around 1854–1855, as well as between studio-based studies and plein-air works are particularly prominent. The artist probably employed a different lead white when painting rural landscapes from nature than when painting his studio works. The observed isotope differences in the lead whites used by the artist may therefore serve as an additional tool for art historians and researchers of his oeuvre to expand the knowledge regarding the provenance of his painting materials and, sometimes, to provide support in dating his works. Considering the fact that the analyses were conducted on a limited number of samples, further systematic study of lead white in the artist’s paintings appears justified in order to assess the efficacy of this technique for dating his works. Declarations Funding sources This research was funded by Nicolaus Copernicus University in Toruń under the ‘Excellence Initiative – Research University’ (IDUB) programme, the 6th edition of the ‘ID-Debiuty’ competition, project No 4101.000000066, project title ”Preliminary research on the use of lead isotope ratio analysis in dating of paintings”, 2023. Author Contribution ED-S selected the pictures for testing, took samples, analyzed and interpreter the isotope tests and wrote the text.JK carried out isotope studies and interpreter the results of these studies.PR Data produced visualisations with the use of the R programming language with the ggplot2 package.ED-S and JK read and approved the fiinal manuscript. Acknowledgement We gratefully acknowledge Ewa Kościałkowska-Okońska for her assistance with the language editing of this paper. Data Availability All data supporting the findings of this study are available within the paper and its Supplementary Information. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8584692","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":579269181,"identity":"d585006d-ee22-45f1-84bc-b90079ab98e0","order_by":0,"name":"Ewa Doleżyńska-Sewerniak","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2UlEQVRIiWNgGAWjYFCCBCjNDIQfGBgMgKwG4rUwzgBrYSRWC1ATMw8xWvjZE5g/fGyzyTdnZ35sbNu2zZhBuhG/FsmeB2ySM9vSLHc2sxkn57bdNmOQOYhfi8GNBDZm3m2HDQwOMxgfBmqxYZBIxK/F/kYC8+e/2/4DtbB/PmxJjBYDiQQGacZtB4BaeIyTGUEOI6RF4gzQL73/kkFaig17zt02ZiPkF/52YIj9OGNnYHD++GaJH2W3Dfulmw/g1QLU9AGVzyZBQAM2t5KuZRSMglEwCoY3AABwG0RKhq+ODgAAAABJRU5ErkJggg==","orcid":"","institution":"Nicolaus Copernicus University","correspondingAuthor":true,"prefix":"","firstName":"Ewa","middleName":"","lastName":"Doleżyńska-Sewerniak","suffix":""},{"id":579269182,"identity":"5a4816b9-98ef-4003-b93d-c1795a1f890d","order_by":1,"name":"Jakub Karasiński","email":"","orcid":"","institution":"University in Warsaw","correspondingAuthor":false,"prefix":"","firstName":"Jakub","middleName":"","lastName":"Karasiński","suffix":""},{"id":579269183,"identity":"47a6512e-49fd-4844-b7da-da3fd8b10153","order_by":2,"name":"Piotr Radziński","email":"","orcid":"","institution":"University in Warsaw","correspondingAuthor":false,"prefix":"","firstName":"Piotr","middleName":"","lastName":"Radziński","suffix":""}],"badges":[],"createdAt":"2026-01-12 18:38:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8584692/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8584692/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":101338251,"identity":"9db7db68-f277-47c5-83f7-81bf69fd0ea7","added_by":"auto","created_at":"2026-01-28 15:47:51","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":68442,"visible":true,"origin":"","legend":"\u003cp\u003eLead isotope ratios in the paintings of Józef Szermentowski. Three lead isotope plots show: (A) ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁷Pb/²⁰⁴Pb, (B) ²⁰⁷Pb/²⁰⁶Pb versus ²⁰⁶Pb/²⁰⁴Pb, and (C) ²⁰⁸Pb/²⁰⁶Pb versus ²⁰⁶Pb/²⁰⁴Pb for the studied works by Józef Szermentowski. Performed by. J. Karasiński and P. Radziński\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-8584692/v1/d44eb9ca720ce23c81e1f01e.png"},{"id":101338252,"identity":"50d8d466-e714-4773-a096-5ceb2f8c0655","added_by":"auto","created_at":"2026-01-28 15:47:51","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":74203,"visible":true,"origin":"","legend":"\u003cp\u003eLead isotope ratios in the paintings of Józef Szermentowski, with indication of the place of execution. The three lead isotope plots show: (A) ²⁰⁶Pb/²⁰⁴Pb versus ²⁰⁷Pb/²⁰⁴Pb, (B) ²⁰⁷Pb/²⁰⁶Pb versus ²⁰⁶Pb/²⁰⁴Pb, and (C) ²⁰⁸Pb/²⁰⁶Pb versus ²⁰⁶Pb/²⁰⁴Pb for the studied works of Józef Szermentowski. Performed by J. Karasiński and P. Radziński\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-8584692/v1/d59e25aa85539b4acc42c9db.png"},{"id":101397823,"identity":"96269751-daac-4e37-9121-15737ed55e81","added_by":"auto","created_at":"2026-01-29 09:37:26","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":700153,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8584692/v1/8f5c2ab4-cf54-4746-9298-a2a9ff7656e7.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Lead isotope analysis of lead white as a tool for the dating Józef Szermentowski’s paintings","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eLead isotope composition analysis enables the description of the geological origin of lead and has been widely employed in e.g., forensic science, environmental studies, and geochemistry [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. This method has also been applied in archaeology and geology for the dating of minerals and artefacts [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. The field literature, although less frequently, also offers examples of this method\u0026rsquo;s applications to the study of painting. The objectives of previous analyses have included, e.g., the identification of the origin of lead white used in specific works [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], the characterisation of this pigment in individual paintings [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e], the authentication of attribution and provenance of paintings [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], and dating studies [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eResearchers have demonstrated that variability in lead isotope ratios can be used to establish the provenance of artefacts. Analyses of types of lead white within specific chronological ranges and geographical regions provide information on the availability of this pigment in various artistic centres and on its trade [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. This approach may, at times, enable the identification of the place of execution of a painting and the artistic group that employed characteristic types of lead white. Isotopic analysis may also be a complementary tool for confirming attribution and dating of paintings of disputed dating [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], as well as for reconstructing the workshop practice of an individual artist or artistic groups [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe trade and distribution networks of lead white in Europe were complex and often correlated with various historical events [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. The interpretation of analytical results may thus be challenging due to the absence of systematic studies on this issue and the limited availability of databases on the lead isotope composition of all major, or most frequently exploited, deposits. Until detailed data on the mining sources of lead used for artistic purposes and its trade routes are established, the difficulties associated with determining the provenance of artefacts must be acknowledged. This issue is particularly complex in the case of industrially manufactured lead whites from the nineteenth century onwards. At that time, there were some large enterprises whose core activity was paint production; their products were exported over long distances, which was also facilitated by the development of steam railways and maritime transport.\u003c/p\u003e \u003cp\u003eThe key research objective of this study was to determine the lead isotope composition of representative lead white samples taken from paintings by the Polish painter J\u0026oacute;zef Szermentowski, who was active in the third quarter of the nineteenth century. Szermentowski was a pioneer and leading figure of realist landscape painting in Poland. His artistic formation was rooted in the Warsaw milieu of the 1850s. After 1860, he relocated to France, where he initially worked in the vicinity of Fontainebleau and Bourron-Marlotte\u0026mdash;centres associated with the Barbizon School and artists from all over the world\u0026mdash;before settling permanently in Paris, where he died [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIt was essential to verify whether any measurable differences in the lead isotope composition of lead white can be identified in the artist\u0026rsquo;s works executed in geographically distant artistic centres, namely in Poland (Warsaw and the Kielce region) and in France (Bourron-Marlotte, Fontainebleau and Paris). We sought to determine whether, when working in Poland and abroad, the artist used lead whites derived from the same sources, for example acquired from the same manufacturers. We also wanted to assess whether lead isotope analyses could corroborate the already existing dating of unsigned works, and to investigate whether, in the second half of the nineteenth century, lead whites produced from lead ores originating from specific ore mining regions were prevalent on the artistic markets in the regions where the artist was active, as well as to establish the possible range of their distribution.\u003c/p\u003e \u003cp\u003eLead isotope ratios were determined using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) with an internal standardisation approach. To date, this method has been applied primarily to the analysis of lead whites used by early modern artists. An additional objective of this study was therefore to evaluate its usefulness for the analysis of lead whites, used by artists active years later, in a period when industrially manufactured white pigments\u0026mdash;often mixtures of different white pigments and extenders\u0026mdash;had become commonly used by artists.\u003c/p\u003e"},{"header":"2. Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Lead white\u003c/h2\u003e \u003cp\u003eWhite pigment is the fundamental pigment that has been used in painting of the past and the present. Lead white occupies a prominent position among the variety of whites, primarily due to its long-term presence in painting materials [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. It was used from the earliest times and only began to lose its dominant status in the second half of the nineteenth century [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Lead white is also one of the oldest synthetic pigments.\u003c/p\u003e \u003cp\u003eIt has a number of advantages: high opacity, good lightfastness, and good drying properties in drying oils [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. These distinctive properties set it apart from other white pigments. Yet, it also has its major drawbacks: it blackens upon exposure to hydrogen sulphide and is highly toxic [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. The latter property resulted in its replacement by other pigments, one of which was zinc white, which gained popularity in painting in the nineteenth century [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e] and which was widely used in oil paints from around 1850. It has lower opacity in oil than lead white, does not act as a siccative, and has a tendency to form cracks when applied in thicker layers. Consequently, in the second half of the nineteenth century, lead white still remained the dominant white pigment that was frequently employed, especially towards the end of the century, in mixtures with other white pigments and extenders. This dominance of lead white in painting was evident even in the early twentieth century.\u003c/p\u003e \u003cp\u003eLead white was used both as a pure white pigment for highest highlights and specular highlights, and in mixtures for the lightening of specific colours. It was also used as an extender in ground layers and as a siccative pigment in oil paints.\u003c/p\u003e \u003cp\u003eChemically, lead white is basic lead carbonate, with lead content up to 80%, which is significant for its use in lead isotope analysis [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe primary lead ore, galena, often contains silver, and its value contributed to the development of lead mining and use as early as in ancient Rome [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. The historical process of smelting of galena was simple and similar across various geographical regions. It involved heating the ore in simple hearths, i.e., stone chimneys with a channel for molten metal and at temperatures slightly exceeding 300\u0026deg;C [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eSince antiquity, lead white was produced by placing thin sheets of lead above a vessel containing acetic acid, i.e., vinegar. The acetic acid vapors reacted with lead to form a white product, which was then scraped off, dried, powdered, and sieved, and subsequently mixed with, e.g., linseed oil to produce paint [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Lead isotope\u003c/h2\u003e \u003cp\u003eMost chemical elements show isotopic variation, i.e. they occur in variants with the same atomic number (the same number of protons in the atomic nucleus), yet they differ in the number of neutrons within the atomic nucleus. This results in e.g., the variability of the isotopic composition of metal ores, such as lead, as well as of the products derived from them.\u003c/p\u003e \u003cp\u003eLead has four natural stable isotopes\u0026mdash; \u0026sup2;⁰⁴Pb, \u0026sup2;⁰⁶Pb, \u0026sup2;⁰⁷Pb, and \u0026sup2;⁰⁸Pb \u0026mdash;which occur in varying relative proportions of components in soils and rocks. The latter three isotopes are radiogenic, i.e., they are derived partly from the radioactive decay of uranium and thorium. The abundances of \u0026sup2;⁰⁶Pb, \u0026sup2;⁰⁷Pb, and \u0026sup2;⁰⁸Pb vary among deposits (particularly as a function of uranium and thorium content), yet \u0026sup2;⁰⁴Pb is non-radiogenic and thus its abundance remains constant over time. The isotopic composition of lead can be demonstrated as plots of \u0026sup2;⁰⁶Pb/\u0026sup2;⁰⁴Pb and \u0026sup2;⁰⁷Pb/\u0026sup2;⁰⁴Pb ratios, which is a standard procedure in geochronological studies. Lead is an element characterised by substantial isotopic heterogeneity across different geological regions, which enables the determination of the origin of the lead ore from which it was extracted [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eWhat needs to be stressed is the fact that galenas from different ore deposits have distinct lead isotopic composition; however, the proportions of lead isotopes do not undergo significant changes during the conversion of ore into white pigment. This is a key factor in the application of lead isotope ratios in studies aimed at the properties and origin of lead-based materials. As a result, artefacts or objects containing lead compounds derived from the same source can be identified and the fact whether a given lead sample originates from a northern or a southern deposit can be established.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. The research object\u003c/h2\u003e \u003cp\u003eEighteen paintings by J\u0026oacute;zef Szermentowski were selected for the lead white analysis. Art historians have dated their execution to the period 1852\u0026ndash;1874. Half of these works bear the artist\u0026rsquo;s original signatures with execution dates, while the remaining paintings were dated primarily on the basis of stylistic analysis (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The paintings come from the collections of two museums\u0026mdash;the National Museum in Wrocław and the National Museum in Kielce; the latter holds the most extensive collection of the artist\u0026rsquo;s paintings. Specific artworks were selected due to their availability and the possibility of conducting invasive analyses, i.e. analyses performed on samples taken from the paintings. The selection of works also aimed to ensure that the lead white pigments present in the works were representative of the key periods of the artist\u0026rsquo;s career. Eleven paintings date back to Szermentowski\u0026rsquo;s early creative period, consistent with his education and life spent in Poland\u0026mdash;mainly in Warsaw and the Kielce region\u0026mdash;up to 1860. One painting is dated to ca. 1860, without a clear indication as to whether it was completed in Poland or abroad. Two paintings were attributed to the post-1860 period, corresponding to the artist\u0026rsquo;s relocation to France, when he painted plein-air studies in the vicinity of Bourron-Marlotte and Fontainebleau. Four paintings were created during the final years of the artist\u0026rsquo;s life in Paris, France.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eList of J\u0026oacute;zef Szermentowski\u0026rsquo;s examined paintings with the results of lead isotope ratio measurements\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"11\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePlace of execution\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTitle\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMuseum ID\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eDate\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSignature and date\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003csup\u003e208\u003c/sup\u003ePb/\u003csup\u003e204\u003c/sup\u003ePb\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e207\u003c/sup\u003ePb /\u003csup\u003e204\u003c/sup\u003ePb\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003e\u003csup\u003e206\u003c/sup\u003ePb /\u003csup\u003e204\u003c/sup\u003ePb\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003e\u003csup\u003e208\u003c/sup\u003e Pb /\u003csup\u003e206\u003c/sup\u003e Pb\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c10\"\u003e \u003cp\u003e\u003csup\u003e207\u003c/sup\u003ePb /\u003csup\u003e206\u003c/sup\u003e Pb\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c11\"\u003e \u003cp\u003eSample no\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"11\" rowspan=\"12\"\u003e \u003cp\u003ePoland\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eStudy of a horse\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eok. 1852\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.508\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.666\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.366\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0960\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8530\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eMarket Square in Szydlowiec\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/280\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1854\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.615\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.647\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.514\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0850\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8452\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eView of Sandomierz from the Vistula River\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/27\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1855\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.459\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.631\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.432\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0857\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8481\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eBaptism in the village\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/1116\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1856\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.137\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.609\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.184\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0965\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8584\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eVillage cemetery\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNWr VIII-383\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1856‒1857\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.162\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.612\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.195\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0966\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8580\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eLandscape on the Vistula River\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNWr VIII-1389\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1856‒1858\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.152\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.614\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.194\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0978\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8589\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eChęciny\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1857\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.668\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.372\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0959\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8529\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eAfter work\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNWr VIII-425\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1858\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.163\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.611\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.202\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0958\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8577\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eHoly Cross Monastery\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/1118\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1859\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.515\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.667\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.370\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0958\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8528\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e11\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eLandscape of the Kielce region\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/277\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eprzed 1860\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.158\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.613\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.203\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0955\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8577\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e12\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eView from the Bobrza River\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/71\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1855‒1856?\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.489\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.664\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.354\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0979\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8541\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e19\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eCottage by the river\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/1328\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eok. 1860\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.556\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.673\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.377\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0973\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8529\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e17\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eFrance\u003c/p\u003e \u003cp\u003e(Bourron-Merolotte/\u003c/p\u003e \u003cp\u003eFontainebleau)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eThe park\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/320\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003epo 1860?\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.526\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.668\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.359\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0977\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8534\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e18\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eA tree\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/280\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003epo 1860\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.520\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.667\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.354\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0979\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8536\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\" morerows=\"3\" rowspan=\"4\"\u003e \u003cp\u003eFrance\u003c/p\u003e \u003cp\u003e(Paris)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eRoad to the village\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/1330\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1872\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.518\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.669\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.372\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0958\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8529\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e13\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eRiver landscape\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/283\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1873 (Paris)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.669\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.372\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0958\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8528\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e14\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eIn the park\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNWr VIII-142\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1873 (Paris)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.452\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.655\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.356\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0942\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8529\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eVillage church in the region of Krakow\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMNKi/M/79\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1874 (Paris)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e+\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.520\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e15.665\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e18.369\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e2.0962\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c10\"\u003e \u003cp\u003e0.8528\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c11\"\u003e \u003cp\u003e16\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Methodology\u003c/h2\u003e \u003cp\u003eLead isotope ratio measurements were performed using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). After dissolution in dilute nitric acid (V), the sample was introduced into the measuring instrument as an aerosol. The sample components undergo ionisation within the plasma, and then specific ion beams are separated by the mass analyser and their intensity is monitored by a detector array. MC-ICP-MS is a technique specifically designed for isotope measurements. Owing to the instrument\u0026rsquo;s design, signals of individual isotopes are measured simultaneously, thus allowing analytical precision that is unmatched by any other commercially available mass spectrometer.\u003c/p\u003e \u003cp\u003eA major advantage of this technique is the ability to analyse extremely small sample amounts, and just one microgram is enough to determine lead isotope ratios. For this reason, MC-ICP-MS is particularly well adjusted for the analysis of Old Master paintings where, due to their unique nature and great value, sample sizes must be limited to an absolute minimum.\u003c/p\u003e \u003cp\u003eData visualisations were produced using the R programming language with the ggplot2 package.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results","content":"\u003cp\u003eThe analyses demonstrated that the lead isotope ratios in the lead white pigments used in the artist\u0026rsquo;s paintings range from 18.184 to 18.514 for \u0026sup2;⁰⁶Pb/\u0026sup2;⁰⁴Pb, from 15.609 to 15.673 for \u0026sup2;⁰⁷Pb/\u0026sup2;⁰⁴Pb, and from 38.137 to 38.615 for \u0026sup2;⁰⁸Pb/\u0026sup2;⁰⁴Pb (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The lead isotope data are presented in bivariate diagrams comparing \u0026sup2;⁰⁶Pb/\u0026sup2;⁰⁴Pb versus \u0026sup2;⁰⁷Pb/\u0026sup2;⁰⁴Pb, \u0026sup2;⁰⁷Pb/\u0026sup2;⁰⁶Pb versus \u0026sup2;⁰⁶Pb/\u0026sup2;⁰⁴Pb, and \u0026sup2;⁰⁶Pb/\u0026sup2;⁰⁴Pb versus \u0026sup2;⁰⁸Pb/\u0026sup2;⁰⁴Pb (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The results indicate variability in the source of lead used to produce the lead white pigments employed by J\u0026oacute;zef Szermentowski.\u003c/p\u003e \u003cp\u003eThe plotted diagrams also demonstrate distinct clustering of sample groups. The first and largest cluster comprises samples 2, 8, 11, and 13\u0026ndash;20; the second cluster includes samples 5, 6, 7, 10, and 12; while the third and smallest cluster consists of samples 3 and 4.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe clustering of samples reveals three distinct data clusters associated with the type of lead white that was used by Szermentowski in certain artistic environments across two key chronological ranges\u0026mdash;1852\u0026ndash;1860 and 1860\u0026ndash;1874 (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eSamples 5, 6, 7, 10, and 12 form a single cluster and correspond to works produced during Szermentowski\u0026rsquo;s stay in Poland, i.e., in Warsaw and in the Kielce region. During this period, the artist employed lead white manufactured from lead originating from the same geological deposits. The paintings are dated to the years 1856\u0026ndash;1860. This group includes the works \u003cem\u003eBaptism in the village\u003c/em\u003e (1856) (signed and dated), \u003cem\u003eVillage cemetery\u003c/em\u003e (c. 1856\u0026ndash;1857), \u003cem\u003eLandscape on the Vistula River\u003c/em\u003e (c. 1856\u0026ndash;1858), \u003cem\u003eAfter work\u003c/em\u003e (1858) (signed and dated), and \u003cem\u003eLandscape of the Kielce region\u003c/em\u003e (before 1860). These paintings are stylistically closely related and seem to be rather study and workshop works rather than plein-air studies.\u003c/p\u003e \u003cp\u003eThe second cluster comprises samples 2, 8, 11, and 13\u0026ndash;20 taken from paintings executed both during the artist\u0026rsquo;s stay in Poland prior to 1860 and after his departure to France. This group includes works painted shortly after 1860, when Szermentowski painted plein-air studies in the vicinity of Bourron-Marlotte and Fontainebleau, as well as paintings from his final years in Paris.\u003c/p\u003e \u003cp\u003eThe lead whites in this cluster and used in Poland were identified in the following works: \u003cem\u003eStudy of a horse\u003c/em\u003e, dated to ca. 1852; \u003cem\u003eChęciny\u003c/em\u003e (1857) (signed and dated); \u003cem\u003eHoly Cross Monastery\u003c/em\u003e (1859) (signed and dated); and \u003cem\u003eCottage by the river\u003c/em\u003e, dated to ca. 1860. This group also includes \u003cem\u003eView from the Bobrza River\u003c/em\u003e, dated by art historians to 1855\u0026ndash;1856; however, this dating seems to be rather uncertain. The painting bears the artist\u0026rsquo;s signature \u0026ldquo;Szermentowski\u0026rdquo; on the recto, whereas prior to his relocation to France the artist signed his works using the surname \u0026ldquo;Szermętowski\u0026rdquo;.\u003c/p\u003e \u003cp\u003eThe paintings \u003cem\u003eChęciny\u003c/em\u003e and \u003cem\u003eHoly Cross Monastery\u003c/em\u003e were executed on supports of similar size and within a closely related time frame, which accounts for the use of a similar lead white pigment. The \u0026ldquo;Polish\u0026rdquo; works in this cluster are not study works but rather plein-air paintings, and they therefore differ in nature from those discussed above. The similarity in lead isotope ratios observed in paintings executed in Poland and in France indicates that the artist employed lead white from the same geological deposit. Consequently, it is not possible to distinguish between Szermentowski\u0026rsquo;s French and Polish works solely on the basis of lead isotope analysis.\u003c/p\u003e \u003cp\u003eSamples 3 and 4 are consistent with the lead white used in \u003cem\u003eMarket Square in Szydlowiec\u003c/em\u003e (1854) and \u003cem\u003eView of Sandomierz from the Vistula River\u003c/em\u003e (1855), both painted in Poland. Both canvases are signed and dated. They share the same dimensions, which is suggestive of a closely related time of execution. It is probable that the artist painted them near Sandomierz and Szydłowiec\u0026mdash;towns located in the Kielce region near his native Bodzentyn. During this period, while studying at the Warsaw School of Fine Arts, the artist undertook field excursions in the Kielce region to study the Polish landscape. In these works, he employed a lead white pigment different from the one more frequently identified in paintings from 1856\u0026ndash;1860. The source of the white pigment used by the artist at this time was therefore different.\u003c/p\u003e \u003cp\u003eAn analysis of these data indicates that during his stay in Poland the artist employed lead whites of higher isotopic variability than in the paintings completed in France. This higher variability of lead white used by Szermentowski between 1849 and 1860, when he was active in the Kingdom of Poland, reflects his artistic activity across multiple locations. Initially, Szermentowski studied in Kielce and, from 1853 to 1857, at the Warsaw School of Fine Arts. In the summer of 1856, he painted his plein-air studies in Volhynia. After 1853, he worked both in Warsaw and in Kielce and its surrounding areas. This is where he began his education and spent his final years before leaving for France. The artist also undertook field excursions throughout the country. The sources of lead white available for artistic purposes in the Kingdom of Poland at that time possibly were heterogeneous. The changes in his locations resulted in the observation, in the presented diagrams, of three distinct lead whites used by the artist during this period, with substantial differences in lead isotope composition.\u003c/p\u003e \u003cp\u003eIn the case of paintings executed in France, only minor differences in lead isotope composition are observed in the white paint samples. This is also reflected in the artist\u0026rsquo;s limited geographical activity as during this period Szermentowski worked in Paris or in the vicinity of Fontainebleau, and he probably relied on one supplier or manufacturer for his lead white. It should be stressed that this pigment was produced from the same lead deposit as the lead white used by the artist for his plein-air works in Poland, yet it differs from that identified in works painted in the Kielce region and in studio-based works from his \u0026ldquo;Polish\u0026rdquo; period. It was probably a product from the same manufacturer, whose distribution range at the time was broad, as evidenced by the presence of this lead white in both the \u0026ldquo;Polish\u0026rdquo; and \u0026ldquo;French\u0026rdquo; works of the artist.\u003c/p\u003e \u003cp\u003eThe presented results, unfortunately, do not allow for precise and detailed differentiation between paintings produced in France and those created in Poland. Consequently, refining the dating of \u003cem\u003eCottage by the river\u003c/em\u003e and \u003cem\u003eThe park\u003c/em\u003e, as well as confirming the dating of \u003cem\u003eView from the Bobrza River\u003c/em\u003e, solely through lead isotope ratio analysis is not currently feasible. These results pertain to only 18 paintings out of more than 100 present in the Polish collections, and thus require further investigation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"4. Discussion","content":"\u003cp\u003eThe identification of temporal variability in lead isotope ratios in the lead white pigments of J\u0026oacute;zef Szermentowski\u0026rsquo;s paintings enables to differentiate works produced in various artistic centres and, in some cases, to distinguish early from late works. The differences between the lead whites used in Poland in the Kielce region around 1854\u0026ndash;1855, as well as between studio-based studies and plein-air works are particularly prominent. The artist probably employed a different lead white when painting rural landscapes from nature than when painting his studio works. The observed isotope differences in the lead whites used by the artist may therefore serve as an additional tool for art historians and researchers of his oeuvre to expand the knowledge regarding the provenance of his painting materials and, sometimes, to provide support in dating his works.\u003c/p\u003e \u003cp\u003eConsidering the fact that the analyses were conducted on a limited number of samples, further systematic study of lead white in the artist\u0026rsquo;s paintings appears justified in order to assess the efficacy of this technique for dating his works.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eFunding sources\u003c/h2\u003e \u003cp\u003eThis research was funded by Nicolaus Copernicus University in Toruń under the \u0026lsquo;Excellence Initiative \u0026ndash; Research University\u0026rsquo; (IDUB) programme, the 6th edition of the \u0026lsquo;ID-Debiuty\u0026rsquo; competition, project No 4101.000000066, project title \u0026rdquo;Preliminary research on the use of lead isotope ratio analysis in dating of paintings\u0026rdquo;, 2023.\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eED-S selected the pictures for testing, took samples, analyzed and interpreter the isotope tests and wrote the text.JK carried out isotope studies and interpreter the results of these studies.PR Data produced visualisations with the use of the R programming language with the ggplot2 package.ED-S and JK read and approved the fiinal manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eWe gratefully acknowledge Ewa Kościałkowska-Okońska for her assistance with the language editing of this paper.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eAll data supporting the findings of this study are available within the paper and its Supplementary Information.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eKrzciuk, K. The study of stable lead iosotopes \u0026ndash; analytical issues and practical importance [In Polish]. \u003cem\u003eAparatura Badawcza i Dydaktyczna\u003c/em\u003e \u003cstrong\u003e27\u003c/strong\u003e (4), 29\u0026ndash;35, (2012).\u003c/li\u003e\n\u003cli\u003eYip, Y., Lam, J.Ch., Tong, W. Applications of lead isotope ratio measurements. \u003cem\u003eTrends in Analytical Chemistry\u003c/em\u003e \u003cstrong\u003e27\u003c/strong\u003e (5), 460‒480 (2008).\u003c/li\u003e\n\u003cli\u003eErel, Y. et al. Transboundary atmospheric lead pollution. \u003cem\u003eEnvironmental Science and Technology\u003c/em\u003e \u003cstrong\u003e36\u003c/strong\u003e, 3230\u0026ndash;3233 (2002).\u003c/li\u003e\n\u003cli\u003eKom\u0026aacute;rek, M., Ettler, V., Chrastn\u0026yacute;, V. 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Supplementing the eye: The technical analysis of Frans Hals\u0026rsquo;s paintings \u0026ndash; II. \u003cem\u003eBurlington Magazine\u003c/em\u003e \u003cstrong\u003e161\u003c/strong\u003e (1401), 996\u0026ndash;1003 (2019).\u003c/li\u003e\n\u003cli\u003eJakimowicz, I\u003cem\u003e. J\u0026oacute;zef Szermentowski 1833\u0026ndash;1876\u003c/em\u003e [In Polish] (Wydawnictwa Artystyczne i Filmowe, 1963).\u003c/li\u003e\n\u003cli\u003eGettens, R.J. Stout G.L. (ed.), \u003cem\u003ePainting Materials. \u003c/em\u003e\u003cem\u003eA short Encyclopedia\u003c/em\u003e (Dover Publications, 1966), 174\u0026ndash;178.\u003c/li\u003e\n\u003cli\u003eSl\u0026aacute;nsk\u0026yacute;, B. \u003cem\u003ePainting Techniques\u003c/em\u003e, vol. I, 24\u0026ndash;26 [In Polish] (Arkady, 1965).\u003c/li\u003e\n\u003cli\u003eHopliński, J. \u003cem\u003ePaints and Binding Media\u003c/em\u003e, 135\u0026ndash;137 [In Polish] (Zakład Narodowy im. Ossolińskich, 1990).\u003c/li\u003e\n\u003cli\u003eK\u0026uuml;hn, H. Zink white. In \u003cem\u003eArtists\u0026rsquo; Pigments. A Handbook of Their History and Characteristics\u003c/em\u003e (ed. Feller, R. L.), vol. 1, 169\u0026ndash;172 (National Gallery of Art, 1986).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"npj-heritage-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"hsci","sideBox":"Learn more about [Heritage Science](http://heritagesciencejournal.springeropen.com)","snPcode":"40494","submissionUrl":"https://submission.nature.com/new-submission/40494/3","title":"npj Heritage Science","twitterHandle":"@SpringerOpen","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"BMC/SO AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-8584692/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8584692/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis paper presents the results of lead isotope composition analyses of lead white samples taken from paintings by J\u0026oacute;zef Szermentowski, a Polish painter. The examination of works by the artist revealed changes in the source of lead in the white paint samples that were associated with his activity in various artistic centres. This indicates that while working in Poland as well as in various regions of France, Szermentowski used lead white derived from a variety of geological deposits. Differences in the lead isotope composition may be a potential for broader future applications of this method in determining the date and place of execution of works whose precise provenance has not yet been established. The results also provide information on the availability of specific types of lead white in certain geographical areas, making a comparative reference framework for other paintings from this period and for the nineteenth-century lead white trade networks.\u003c/p\u003e","manuscriptTitle":"Lead isotope analysis of lead white as a tool for the dating Józef Szermentowski’s paintings","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-28 15:47:42","doi":"10.21203/rs.3.rs-8584692/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-02-13T18:53:42+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-13T15:39:21+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-09T10:55:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"31258412800299329711728435102202076830","date":"2026-01-23T08:52:46+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"279565571312433797619057783086619056462","date":"2026-01-23T08:42:08+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-01-23T08:09:30+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-01-22T16:00:34+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-01-22T10:56:29+00:00","index":"","fulltext":""},{"type":"submitted","content":"npj Heritage Science","date":"2026-01-22T10:25:40+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"npj-heritage-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"hsci","sideBox":"Learn more about [Heritage Science](http://heritagesciencejournal.springeropen.com)","snPcode":"40494","submissionUrl":"https://submission.nature.com/new-submission/40494/3","title":"npj Heritage Science","twitterHandle":"@SpringerOpen","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"BMC/SO AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"be3c9047-ef4e-4e05-9492-e68c542ddb3e","owner":[],"postedDate":"January 28th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-04-15T13:56:04+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-28 15:47:42","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8584692","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8584692","identity":"rs-8584692","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}