{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,21]],"date-time":"2026-01-21T08:55:49Z","timestamp":1768985749716,"version":"3.49.0"},"reference-count":55,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2023,4,27]],"date-time":"2023-04-27T00:00:00Z","timestamp":1682553600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Tuscany Region, POR FSC 2014\u20132020-Axis Employment GiovaniS\u00ec","award":["CUP B53D21008070008"],"award-info":[{"award-number":["CUP B53D21008070008"]}]},{"name":"Tuscany Region, POR FSC 2014\u20132020-Axis Employment GiovaniS\u00ec","award":["CNR-INO"],"award-info":[{"award-number":["CNR-INO"]}]},{"name":"Museo Galileo, El.En. group, and the National Institute of Optics from the National Council of Research","award":["CUP B53D21008070008"],"award-info":[{"award-number":["CUP B53D21008070008"]}]},{"name":"Museo Galileo, El.En. group, and the National Institute of Optics from the National Council of Research","award":["CNR-INO"],"award-info":[{"award-number":["CNR-INO"]}]},{"name":"Opificio delle Pietre Dure (OPD)","award":["CUP B53D21008070008"],"award-info":[{"award-number":["CUP B53D21008070008"]}]},{"name":"Opificio delle Pietre Dure (OPD)","award":["CNR-INO"],"award-info":[{"award-number":["CNR-INO"]}]},{"name":"Fondazione Alinari per la Fotografia","award":["CUP B53D21008070008"],"award-info":[{"award-number":["CUP B53D21008070008"]}]},{"name":"Fondazione Alinari per la Fotografia","award":["CNR-INO"],"award-info":[{"award-number":["CNR-INO"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Sensors"],"abstract":"<jats:p>Preserving and analytically examining daguerreotypes is particularly challenging because of their multi-material and multi-component structure. Various sensors have been exploited to examine mainly the image plates of the daguerreotypes even though the degradation goes beyond this component. Micro-analyses have been the preferred method due to the nanoscale structure of the image particles. In this work, we propose comprehensive multi-modal non-invasive sensing to investigate the corrosion products present in nine daguerreotypes from the Fondazione Alinari per la Fotografia (FAF, Florence, Italy). The methodology proposed includes chemical and morphological analyses: portable X-ray fluorescence spectrometry (pXRF), Raman microspectroscopy (\u03bc-Raman), and micro-Fourier transform infrared spectroscopy in reflection mode (\u03bc-rFTIR) for the chemical identification. For the first time, optical coherence tomography (OCT) was deployed to record the cross-sectional and morphological data of the relevant corrosion formations on daguerreotypes in a contactless way. The results allowed the characterization, in a non-invasive mode at a microscopic level, of a wide range of degradation products produced by the interaction of the different elements present in the structure of the daguerreotypes. The aim was to verify the performance of the proposed methodology and to link the chemical and physical complexity of the entire structure, disclosed by the state-of-art sensors, to the daguerreotype degradation. The results draw attention to the need to monitor not only the image condition but the whole object as a partially closed system in constant interaction internally and with the environment.<\/jats:p>","DOI":"10.3390\/s23094341","type":"journal-article","created":{"date-parts":[[2023,4,28]],"date-time":"2023-04-28T02:02:23Z","timestamp":1682647343000},"page":"4341","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["The Degradation of Daguerreotypes and the Relationship with Their Multi-Material Structure: A Multimodal Investigation"],"prefix":"10.3390","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5072-5198","authenticated-orcid":false,"given":"Diego","family":"Quintero Balbas","sequence":"first","affiliation":[{"name":"National Research Council-National Institute of Optics (CNR-INO), Largo E. Fermi 6, 50125 Florence, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1986-256X","authenticated-orcid":false,"given":"Barbara","family":"Cattaneo","sequence":"additional","affiliation":[{"name":"Laboratorio di Restauro Cartacei e Membranacei, Opificio delle Pietre Dure\u2013MiC, Viale F. Strozzi, 1, 50129 Firenze, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andrea","family":"Cagnini","sequence":"additional","affiliation":[{"name":"Laboratorio Scientifico, Opificio delle Pietre Dure\u2013MiC, Viale F. Strozzi, 1, 50129 Firenze, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Paolo","family":"Belluzzo","sequence":"additional","affiliation":[{"name":"Laboratorio di Restauro Oreficerie, Opificio delle Pietre Dure\u2013MiC, Via degli Alfani 78, 50121 Firenze, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sandra","family":"Rossi","sequence":"additional","affiliation":[{"name":"Laboratorio di Restauro Cartacei e Membranacei, Opificio delle Pietre Dure\u2013MiC, Viale F. Strozzi, 1, 50129 Firenze, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Raffaella","family":"Fontana","sequence":"additional","affiliation":[{"name":"National Research Council-National Institute of Optics (CNR-INO), Largo E. Fermi 6, 50125 Florence, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0790-4689","authenticated-orcid":false,"given":"Jana","family":"Striova","sequence":"additional","affiliation":[{"name":"National Research Council-National Institute of Optics (CNR-INO), Largo E. Fermi 6, 50125 Florence, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,27]]},"reference":[{"key":"ref_1","unstructured":"Barger, M.S., and White, W.B. (2000). The Daguerreotype: Nineteenth-Century Technology and Modern Science, Johns Hopkins University Press."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"55","DOI":"10.1007\/s00339-011-6570-2","article-title":"The Formation of Chlorine-Induced Alterations in Daguerreotype Image Particles: A High Resolution SEM-EDS Study","volume":"105","author":"Centeno","year":"2011","journal-title":"Appl. Phys. A"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"030504-1","DOI":"10.2352\/J.ImagingSci.Technol.2016.60.3.030504","article-title":"An Electron Microscopy Study of the ImageMaking Process of the Daguerreotype, the 19th Century\u2019s First Commercially Viable Photographic Process","volume":"60","author":"Ravines","year":"2016","journal-title":"J. Imaging Sci. Technol."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"13791","DOI":"10.1073\/pnas.1904331116","article-title":"Nineteenth-Century Nanotechnology: The Plasmonic Properties of Daguerreotypes","volume":"116","author":"Schlather","year":"2019","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1730","DOI":"10.1002\/cplu.201900467","article-title":"Highly Photosensitive Daguerreotypes and Their Reproduction: Physico-chemical Elucidation of Innovative Processes in Photography Developed around 1840 in Vienna","volume":"84","author":"Kautek","year":"2019","journal-title":"ChemPlusChem"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1037","DOI":"10.1017\/S1431927619000709","article-title":"Characterizing the Image Forming Particles of Modern Ungilded Daguerreotypes Using XRD and SEM","volume":"25","author":"Ravines","year":"2019","journal-title":"Microsc. Microanal."},{"key":"ref_7","unstructured":"McElhone, J.P. (1998). Photographic Materials Conservation Catalog, American Institute for Conservation of Historic and Artistic Works."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"4306","DOI":"10.3390\/heritage5040221","article-title":"The Colors of the Butterfly Wings: Non-Invasive Microanalytical Studies of Hand-Coloring Materials in 19th-Century Daguerreotypes","volume":"5","author":"Cattaneo","year":"2022","journal-title":"Heritage"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"438","DOI":"10.1016\/j.corsci.2015.02.018","article-title":"Exposing the Sub-Surface of Historical Daguerreotypes and the Effects of Sulfur-Induced Corrosion","volume":"94","author":"Marquis","year":"2015","journal-title":"Corros. Sci."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"12","DOI":"10.1186\/s40494-018-0171-8","article-title":"Exploring Tarnished Daguerreotypes with Synchrotron Light: XRF and \u039c-XANES Analysis","volume":"6","author":"Kozachuk","year":"2018","journal-title":"Herit. Sci."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"84","DOI":"10.1179\/sic.1984.29.2.84","article-title":"Nondestructive Assessment of Daguerreotype Image Quality by Diffuse Reflectance Spectroscopy","volume":"29","author":"Barger","year":"1984","journal-title":"Stud. Conserv."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"98","DOI":"10.1080\/00393630.2020.1773056","article-title":"Silver and Acid-Thiourea Silver Dips: Rinsing and Aging Monitored by Electrochemistry","volume":"66","author":"Selwyn","year":"2021","journal-title":"Stud. Conserv."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1179\/019713696806124584","article-title":"Investigation of a Surface Tarnish Found on 19th-Century Daguerreotypes","volume":"35","author":"Daffner","year":"1996","journal-title":"J. Am. Inst. Conserv."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"2000","DOI":"10.1017\/S1431927614011738","article-title":"Examination of a 19th Century Daguerreotype Photograph Using High Resolution Scanning Transmission Electron Microscopy for 2D and 3D Nanoscale Imaging and Analysis","volume":"20","author":"Vicenzi","year":"2014","journal-title":"Microsc. Microanal."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"138","DOI":"10.1179\/174329408X298175","article-title":"Surface Characterisation of Daguerreotypes with the Optical Metrological Technique of Confocal Microscopy","volume":"24","author":"Ravines","year":"2008","journal-title":"Surf. Eng."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1215","DOI":"10.1177\/0003702818773760","article-title":"Imaging the Surface of a Hand-Colored 19th Century Daguerreotype","volume":"72","author":"Kozachuk","year":"2018","journal-title":"Appl. Spectrosc."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"423","DOI":"10.1366\/0003702021955079","article-title":"Laser-Induced Breakdown Spectroscopy for the Analysis of 150-Year-Old Daguerreotypes","volume":"56","author":"Anglos","year":"2002","journal-title":"Appl. Spectrosc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"914","DOI":"10.1002\/jrs.1934","article-title":"The Daguerreotype Surface as a SERS Substrate: Characterization of Image Deterioration in Plates from the 19th Century Studio of Southworth & Hawes","volume":"39","author":"Centeno","year":"2008","journal-title":"J. Raman Spectrosc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1186\/s40494-020-0349-8","article-title":"FTIR Surface Analysis for Conservation","volume":"8","author":"Thickett","year":"2020","journal-title":"Herit. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"568","DOI":"10.3390\/heritage2010037","article-title":"Recovering Past Reflections: X-ray Fluorescence Imaging of Electrocleaned 19th Century Daguerreotypes","volume":"2","author":"Kozachuk","year":"2019","journal-title":"Heritage"},{"key":"ref_21","first-page":"1","article-title":"Hyperspectral Imaging of Daguerreotypes","volume":"33","author":"Goltz","year":"2012","journal-title":"Restaur. Int. J. Preserv. Libr. Arch. Mater."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1179\/1945233013Y.0000000014","article-title":"Multimodality Imaging of Daguerreotypes and Development of a Registration Program for Image Evaluation","volume":"53","author":"Ravines","year":"2014","journal-title":"J. Am. Inst. Conserv."},{"key":"ref_23","unstructured":"Stork, D.G., Coddington, J., and Bentkowska-Kafel, A. (2010). Digital Analysis and Restoration of Daguerreotypes, SPIE."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1343","DOI":"10.1007\/PL00020219","article-title":"Characterization of Corrosion Products on Old Protective Glass, Especially Daguerreotype Cover Glasses","volume":"24","author":"Barger","year":"1989","journal-title":"J. Mater. Sci."},{"key":"ref_25","unstructured":"Roemich, H. (2010). When Glass and Metal Corrode Together, II: A Black Forest Sch\u00e4ppel and Further Occurrences of Socoformacite, ICOM."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"342","DOI":"10.1080\/00393630.2017.1359472","article-title":"When Glass and Metal Corrode Together, V: Sodium Copper Formate","volume":"63","author":"Fischer","year":"2018","journal-title":"Stud. Conserv."},{"key":"ref_27","unstructured":"(2022, October 24). Catalogo Immagini Archivio Fotografico\u2014FAF Toscana. Available online: https:\/\/www.alinari.it\/en\/explore-unicum-objects."},{"key":"ref_28","unstructured":"Chiesa, G., and Gosio, P. (2020). Daguerreotype Hallmarks, Gabriele Chiesa & Paolo Gosio. [1st ed.]."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1016\/j.nimb.2020.11.006","article-title":"Estimation of Ag Coating Thickness by Different Methods Using a Handheld XRF Instrument","volume":"486","author":"Brocchieri","year":"2021","journal-title":"Nucl. Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. At."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"789","DOI":"10.1002\/jrs.1540","article-title":"The Use of Raman Spectrometry to Predict the Stability of Historic Glasses","volume":"37","author":"Robinet","year":"2006","journal-title":"J. Raman Spectrosc."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"12","DOI":"10.1154\/1.1649316","article-title":"Synchrotron Applications in Archaeometallurgy: Analysis of High Zinc Brass Astrolabes","volume":"19","author":"Newbury","year":"2004","journal-title":"Powder Diffr."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1007\/s41061-016-0025-3","article-title":"New Frontiers in Application of FTIR Microscopy for Characterization of Cultural Heritage Materials","volume":"374","author":"Prati","year":"2016","journal-title":"Top. Curr. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1605","DOI":"10.3390\/heritage4030089","article-title":"Retrieving Tarnished Daguerreotype Content Using X-ray Fluorescence Imaging\u2014Recent Observations on the Effect of Chemical and Electrochemical Cleaning Methods","volume":"4","author":"Stark","year":"2021","journal-title":"Heritage"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"852","DOI":"10.1002\/jrs.4900","article-title":"Micro-Raman Innovative Methodology to Identify Ag-Cu Mixed Sulphides as Tarnishing Corrosion Products: Micro-Raman Innovative Methodology","volume":"47","author":"Caschera","year":"2016","journal-title":"J. Raman Spectrosc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"770","DOI":"10.1002\/jrs.4276","article-title":"Micro-Raman Investigations of Early Stage Silver Corrosion Products Occurring in Sulfur Containing Atmospheres","volume":"44","author":"Martina","year":"2013","journal-title":"J. Raman Spectrosc."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"6017","DOI":"10.1002\/anie.201901630","article-title":"Silver Tarnishing Mechanism Revealed by Molecular Dynamics Simulations","volume":"58","author":"Saleh","year":"2019","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_37","unstructured":"Cattaneo, B. (2012). Il Restauro Della Fotografia. MATERIALI Fotografici e Cinematografici, Analogici e Digitali, Nardini Editore."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"153","DOI":"10.1007\/s11224-016-0792-z","article-title":"Structural Complexity and Crystallization: The Ostwald Sequence of Phases in the Cu2(OH)3Cl System (Botallackite\u2013Atacamite\u2013Clinoatacamite)","volume":"28","author":"Krivovichev","year":"2017","journal-title":"Struct. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"175","DOI":"10.1002\/jrs.5550","article-title":"The Raman Spectra of the Na2SO4-K2SO4 System: Applicability to Soluble Salts Studies in Built Heritage","volume":"50","author":"Veneranda","year":"2019","journal-title":"J. Raman Spectrosc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"443","DOI":"10.1007\/s11356-008-0078-0","article-title":"Weathering Patinas on the Medieval (S. XIV) Stained Glass Windows of the Pedralbes Monastery (Barcelona, Spain)","volume":"16","author":"Aulinas","year":"2009","journal-title":"Environ. Sci. Pollut. Res."},{"key":"ref_41","unstructured":"Bridgland, J. (2011). When Glass and Metal Corrode Together, III: The Formation of Dicoppertrihydroxyformate, ICOMM."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1007","DOI":"10.1017\/S1431927616011636","article-title":"On the Chemical Signature and Origin of Dicoppertrihydroxyformate (Cu2(OH)3HCOO) Formed on Copper Miniatures of 17th and 18th Centuries","volume":"22","author":"Veiga","year":"2016","journal-title":"Microsc. Microanal."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"eabl6769","DOI":"10.1126\/sciadv.abl6769","article-title":"Novel Optical Photothermal Infrared (O-PTIR) Spectroscopy for the Noninvasive Characterization of Heritage Glass-Metal Objects","volume":"8","author":"Marchetti","year":"2022","journal-title":"Sci. Adv."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"237","DOI":"10.1179\/sic.2003.48.4.237","article-title":"Corrosion of Copper and Lead by Formaldehyde, Formic and Acetic Acid Vapours","volume":"48","author":"Cano","year":"2003","journal-title":"Stud. Conserv."},{"key":"ref_45","doi-asserted-by":"crossref","unstructured":"Casadio, F., Keune, K., Noble, P., Van Loon, A., Hendriks, E., Centeno, S.A., and Osmond, G. (2019). Metal Soaps in Art, Springer International Publishing. Cultural Heritage Science.","DOI":"10.1007\/978-3-319-90617-1"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"138","DOI":"10.1016\/j.polymdegradstab.2014.01.026","article-title":"The Role of Zinc White Pigment on the Degradation of Shellac Resin in Artworks","volume":"102","author":"Poli","year":"2014","journal-title":"Polym. Degrad. Stab."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"2513","DOI":"10.3390\/heritage2030154","article-title":"Magic Lantern Glass Slides Materials and Techniques: The First Multi-Analytical Study","volume":"2","author":"Rodrigues","year":"2019","journal-title":"Heritage"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1186\/s40494-015-0052-3","article-title":"Faded Shine\u2026. The Degradation of Brass Powder in Two Nineteenth Century Paintings","volume":"3","author":"Ferreira","year":"2015","journal-title":"Herit. Sci."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"152","DOI":"10.1080\/00393630.2019.1677081","article-title":"When Glass and Metal Corrode Together, VI: Chalconatronite","volume":"65","author":"Fischer","year":"2020","journal-title":"Stud. Conserv."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"217","DOI":"10.1179\/sic.2002.47.4.217","article-title":"The Characterization of a New Pale Blue Corrosion Product Found on Copper Alloy Artifacts","volume":"47","author":"Trentelman","year":"2002","journal-title":"Stud. Conserv."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"172","DOI":"10.1016\/j.corsci.2009.08.054","article-title":"Acetic and Formic Acids Emitted from Wood Samples and Their Effect on Selected Materials in Museum Environments","volume":"52","author":"Gibson","year":"2010","journal-title":"Corros. Sci."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1186\/s40494-021-00499-z","article-title":"The Formation of Formates: A Review of Metal Formates on Heritage Objects","volume":"9","author":"Eggert","year":"2021","journal-title":"Herit. Sci."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"662","DOI":"10.1002\/jrs.1133","article-title":"A Raman Spectroscopic Study of Pollution-Induced Glass Deterioration","volume":"35","author":"Robinet","year":"2004","journal-title":"J. Raman Spectrosc."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"1468","DOI":"10.1002\/jrs.2786","article-title":"Verdigris Pigment: A Mixture of Compounds. Input from Raman Spectroscopy","volume":"41","author":"Baonza","year":"2010","journal-title":"J. Raman Spectrosc."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"101","DOI":"10.1007\/BF01244522","article-title":"Characterization of Formate Complexes Formed as Corrosion Products on Copper by Raman Spectroscopy","volume":"98","author":"Jeziorowski","year":"1989","journal-title":"Microchim. Acta"}],"container-title":["Sensors"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1424-8220\/23\/9\/4341\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:24:52Z","timestamp":1760124292000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1424-8220\/23\/9\/4341"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,4,27]]},"references-count":55,"journal-issue":{"issue":"9","published-online":{"date-parts":[[2023,5]]}},"alternative-id":["s23094341"],"URL":"https:\/\/doi.org\/10.3390\/s23094341","relation":{},"ISSN":["1424-8220"],"issn-type":[{"value":"1424-8220","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,4,27]]}}}