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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 (μ-Raman), and micro-Fourier transform infrared spectroscopy in reflection mode (μ-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.

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The public expected color from the early photographic images, yet, daguerreotypes—the first commercially available photographic process—failed to register the natural colors. Daguerreotypists developed several coloring methods to solve this inconvenience after 1840. Scientific analyses of the hand-colored daguerreotypes are limited, and the primary information sources available are manuals and patents. This study aims to contribute to the knowledge of hand-coloring techniques, which impacts conservation practices, mainly the cleaning procedures and complements technical art history investigations. We studied nine colored daguerreotypes with a non-invasive methodology based on three spectroscopic techniques: X-ray fluorescence (XRF), micro-Raman spectroscopy (μ-Raman), and micro-Fourier-transform infrared spectroscopy in reflection mode (μ-rFTIR). The results revealed the different colorants and some of their mixtures employed by the colorist. It also adds information regarding the photographic production of three studios: Désiré François Millet, active in Paris between 1840 and 1868; Antoine Claudet (1797–1867), active in London; and the James E. McClees and Washington Lafayette Germon studio, operative between 1846 and 1855 in Philadelphia, USA. These technical details constitute a helpful comparison to future studies on Daguerreian studios and colored daguerreotypes.