{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T02:08:59Z","timestamp":1760234939777,"version":"build-2065373602"},"reference-count":38,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2021,6,28]],"date-time":"2021-06-28T00:00:00Z","timestamp":1624838400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>In this work, decorative wallpapers (19th century) from an historical palace located in Oiartzun (Basque Country, Spain) were analyzed before their restoration. Micro-energy dispersive X-ray fluorescence spectroscopy, Raman spectroscopy, and attenuated total reflectance infrared spectroscopy were used to investigate the elemental and molecular composition of pigments, the presence of binders, and the state of conservation of the paper support. The aim of the investigation was trying to understand the possible degradation pathways and identify the raw materials in order to choose the best restoration protocol according to the original aspect of wallpapers. As stated from both the elemental distribution and the identification of mineral phases by Raman spectroscopy, the most used pigment was lead chromate. It was mixed with other pigments such as ultramarine blue, zinc chromate, hematite, and atacamite among others to obtain different shades and they were applied mixed with an animal glue. Brass, identified thanks to elemental micro-EDXRF maps, was employed as a shiny decorative element. In addition, a partial degradation of cellulose was detected due to its natural ageing, the acidic nature of lignin, and to a phenomenon of humidity of the walls. Probably the deposition of black particulate matter was the cause of the darkening of the painting surfaces.<\/jats:p>","DOI":"10.3390\/s21134416","type":"journal-article","created":{"date-parts":[[2021,6,28]],"date-time":"2021-06-28T13:39:22Z","timestamp":1624887562000},"page":"4416","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Non-Destructive Analytical Investigation of Decorative Wallpapers Samples of the Nineteenth Century before Their Restoration"],"prefix":"10.3390","volume":"21","author":[{"given":"Ilaria","family":"Costantini","sequence":"first","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV\/EHU, P.O. Box 644, 48080 Bilbao, Basque Country, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kepa","family":"Castro","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV\/EHU, P.O. Box 644, 48080 Bilbao, Basque Country, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Maria Dolores","family":"Rodriguez-Laso","sequence":"additional","affiliation":[{"name":"Department of Painting, University of the Basque Country, P.O. Box 644, 48080 Bilbao, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1685-6335","authenticated-orcid":false,"given":"Juan Manuel","family":"Madariaga","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV\/EHU, P.O. Box 644, 48080 Bilbao, Basque Country, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gorka","family":"Arana","sequence":"additional","affiliation":[{"name":"Department of Analytical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV\/EHU, P.O. Box 644, 48080 Bilbao, Basque Country, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,6,28]]},"reference":[{"key":"ref_1","first-page":"113","article-title":"La f\u00e1brica de papeles pintados Santa Isabel de Vitoria a mediados del siglo XIX","volume":"9","year":"2019","journal-title":"Ars Bilduma"},{"key":"ref_2","unstructured":"Lynn, C., and Frangiamore, C.L. (1977). Wallpapers in Historic Preservation."},{"key":"ref_3","unstructured":"Hoskins, L. (2005). The Papered Wall: The History, Patterns and Techniques of Wallpaper, Thames & Hudson."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"582","DOI":"10.1016\/j.sab.2009.04.004","article-title":"Study of a XVIII century hand-painted Chinese wallpaper by multianalytical non-destructive techniques","volume":"64","author":"Pessanha","year":"2009","journal-title":"Spectrochim. Acta Part B At. Spectrosc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"308","DOI":"10.1016\/j.saa.2014.01.017","article-title":"Determination of the pigments present in a wallpaper of the middle nineteenth century: The combination of mid-diffuse reflectance and far infrared spectroscopies","volume":"124","author":"Arrizabalaga","year":"2014","journal-title":"Spectrochim. Acta. A Mol. Biomol. Spectrosc."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3453","DOI":"10.1039\/c0an00832j","article-title":"Surface-enhanced Raman spectroscopy analysis of house paint and wallpaper samples from an 18th century historic property","volume":"136","author":"Harroun","year":"2011","journal-title":"Analyst"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"104","DOI":"10.1016\/j.saa.2012.12.059","article-title":"Finnish wallpaper pigments in the 18th\u201319th century: Presence of KFe3(CrO4)2(OH)6 and odd pigment mixtures","volume":"106","author":"Castro","year":"2013","journal-title":"Spectrochim. Acta. A Mol. Biomol. Spectrosc."},{"key":"ref_8","first-page":"76","article-title":"Deadly D\u00e9cor: A Short History of Arsenic Poisoning in the Nineteenth Century","volume":"21","author":"Haslam","year":"2013","journal-title":"Res. Med."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Ball, P. (2003). William Morris made poisonous wallpaper. Nature.","DOI":"10.1038\/news030609-11"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1179\/019713681806028749","article-title":"Wallpaper on Walls: Problems of Climate and Substrate","volume":"20","author":"Phillips","year":"1981","journal-title":"J. Am. Inst. Conserv."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1179\/019713604806112588","article-title":"Investigation, Analysis, and Authentication of Historic Wallpaper Fragments","volume":"43","author":"Welsh","year":"2004","journal-title":"J. Am. Inst. Conserv."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1401","DOI":"10.1016\/j.nimb.2011.03.027","article-title":"Assessment of the weathering effects on cellulose based materials through a multianalytical approach","volume":"269","author":"Castro","year":"2011","journal-title":"Nucl. Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. At."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"347","DOI":"10.1016\/j.trac.2007.02.003","article-title":"Vibrational spectroscopy at the service of industrial archaeology: Nineteenth-century wallpaper","volume":"26","author":"Castro","year":"2007","journal-title":"TrAC Trends Anal. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"847","DOI":"10.1007\/s00216-006-0593-0","article-title":"Non-invasive and non-destructive micro-XRF and micro-Raman analysis of a decorative wallpaper from the beginning of the 19th century","volume":"387","author":"Castro","year":"2007","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"674","DOI":"10.1007\/s00216-004-2642-x","article-title":"Micro-Raman analysis of coloured lithographs","volume":"379","author":"Castro","year":"2004","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2357","DOI":"10.1016\/j.saa.2005.02.035","article-title":"Improvements in the wallpaper industry during the second half of the 19th century: Micro-Raman spectroscopy analysis of pigmented wallpapers","volume":"61","author":"Castro","year":"2005","journal-title":"Spectrochim. Acta. A. Mol. Biomol. Spectrosc."},{"key":"ref_17","unstructured":"Janssens, K., and Grieken, R.V. (2004). Non-Destructive Micro Analysis of Cultural Heritage Materials, Elsevier."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"192","DOI":"10.1002\/jrs.2667","article-title":"Pigment identification of a rare 18th century wallpaper from Buffon library","volume":"42","author":"Colomban","year":"2011","journal-title":"J. Raman Spectrosc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1179\/sic.2002.47.s3.026","article-title":"An Eighteenth-Century Chinese Wallpaper: Historical Context and Conservation","volume":"47","author":"Lambert","year":"2002","journal-title":"Stud. Conserv."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1002\/jrs.807","article-title":"Fourier transform Raman spectroscopic study of pigments present in decorative wallpapers of the middle nineteenth century from the Santa Isabel factory (Vitoria, Basque Country, Spain)","volume":"33","author":"Castro","year":"2002","journal-title":"J. Raman Spectrosc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1455","DOI":"10.1002\/jrs.2021","article-title":"Raman spectroscopy of synthetic organic pigments used in 20th century works of art","volume":"39","author":"Schulte","year":"2008","journal-title":"J. Raman Spectrosc."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"981","DOI":"10.1002\/jrs.1582","article-title":"Application of surface-enhanced Raman scattering techniques to the ultrasensitive identification of natural dyes in works of art","volume":"37","author":"Leona","year":"2006","journal-title":"J. Raman Spectrosc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1119","DOI":"10.1002\/jrs.1595","article-title":"Raman spectroscopy of Japanese artists\u2019 materials: The Tale of Genji by Tosa Mitsunobu","volume":"37","author":"Eremin","year":"2006","journal-title":"J. Raman Spectrosc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"125","DOI":"10.1016\/j.microc.2013.12.011","article-title":"Complementary analytical methods in identifying gilding and painting techniques of ancient clay-based polychromic sculptures","volume":"114","author":"Wang","year":"2014","journal-title":"Microchem. J."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"150","DOI":"10.1179\/2047058413Y.0000000091","article-title":"A multi-analytical approach to the examination of nineteenth-century European wallpapers in Vasiq-Ansari House in Isfahan, Iran","volume":"59","author":"Holakooei","year":"2014","journal-title":"Stud. Conserv."},{"key":"ref_26","unstructured":"Scott, D.A. (1991). Metallography and Microstructure of Ancient and Historic Metals, Thr Getty Conservation Institute. Available online: https:\/\/books.google.com.hk\/books?hl=zh-CN&lr=&id=8blOAgAAQBAJ&oi=fnd&pg=PP1&dq=Metallography+and+Microstructure+of+Ancient+and+Historic+Metal&ots=5c1wqAO2oW&sig=5wbMA8wMKySu76B4BzfGKDqdHnU&redir_esc=y&hl=zh-CN&sourceid=cndr#v=onepage&q=Metallography%20and%20Microstructure%20of%20Ancient%20and%20Historic%20Metal&f=false."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"30","DOI":"10.1007\/s40735-017-0087-y","article-title":"\u03b1-Brass and (\u03b1 + \u03b2) Brass Degradation Processes in Azrou Soil Medium Used in Plumbing Devices","volume":"3","author":"Galai","year":"2017","journal-title":"J. Bio-Tribo-Corros."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"265","DOI":"10.1039\/C0NR00589D","article-title":"The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, viavaterite","volume":"3","author":"Shaw","year":"2011","journal-title":"Nanoscale"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"226","DOI":"10.1016\/j.vibspec.2008.12.004","article-title":"Infrared, optical absorption, and EPR spectroscopic studies on natural gypsum","volume":"50","author":"Anbalagan","year":"2009","journal-title":"Vib. Spectrosc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"719","DOI":"10.1007\/s00339-006-3548-6","article-title":"Technique and palette of XIIIth century painting in the monastery of Mileseva","volume":"83","author":"Zorba","year":"2006","journal-title":"Appl. Phys. A"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"529","DOI":"10.1080\/01490451.2013.806612","article-title":"Novel Comparative Efficiency of Ozone and Gamma Sterilization on Fungal Deterioration of Archeological Painted Coffin, Saqqara Excavation, Egypt","volume":"31","author":"Geweely","year":"2014","journal-title":"Geomicrobiol. J."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1214","DOI":"10.1021\/ac102424h","article-title":"Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Synchrotron X-ray Spectromicroscopy and Related Methods. 1. Artificially Aged Model Samples","volume":"83","author":"Monico","year":"2011","journal-title":"Anal. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"10804","DOI":"10.1021\/ac502841g","article-title":"Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Spectromicroscopic Methods. Part 5. Effects of Nonoriginal Surface Coatings into the Nature and Distribution of Chromium and Sulfur Species in Chrome Yellow Paints","volume":"86","author":"Monico","year":"2014","journal-title":"Anal. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"521","DOI":"10.1016\/j.polymdegradstab.2004.12.013","article-title":"Physico-chemical and thermal characterization of cellulose from barley straw","volume":"88","author":"Sun","year":"2005","journal-title":"Polym. Degrad. Stab."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3397","DOI":"10.1021\/cr000115l","article-title":"Oxidative Mechanisms Involved in Lignin Degradation by White-Rot Fungi","volume":"101","author":"Teunissen","year":"2001","journal-title":"Chem. Rev."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"163","DOI":"10.5109\/24366","article-title":"Surface Characterization of Naturally Degraded Wood\u2013Free Papers by Near lnfrared Fourier\u2014Transform Raman Spectroscopy","volume":"45","author":"Chen","year":"2000","journal-title":"J. Fac. Agric. Kyushu Univ."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1527","DOI":"10.1002\/jrs.2294","article-title":"Near-IR surface-enhanced Raman spectrum of lignin","volume":"40","author":"Agarwal","year":"2009","journal-title":"J. Raman Spectrosc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"2131","DOI":"10.1007\/s00216-009-3178-x","article-title":"Fourier-transform Raman spectroscopic study of a Neolithic waterlogged wood assemblage","volume":"395","author":"Petrou","year":"2009","journal-title":"Anal. Bioanal. Chem."}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/21\/13\/4416\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:25:31Z","timestamp":1760163931000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/21\/13\/4416"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,6,28]]},"references-count":38,"journal-issue":{"issue":"13","published-online":{"date-parts":[[2021,7]]}},"alternative-id":["s21134416"],"URL":"https:\/\/doi.org\/10.3390\/s21134416","relation":{},"ISSN":["1424-8220"],"issn-type":[{"type":"electronic","value":"1424-8220"}],"subject":[],"published":{"date-parts":[[2021,6,28]]}}}