The daguerreotype image, composed of nanosized silver-mercury or silver-mercury-gold amalgam particles formed on a polished silver substrate, is particularly sensitive to deterioration by chlorine-containing compounds resulting in the formation of AgCl that generates redeposited silver upon exposure to UV and visible lights. In the present study, alterations caused by chlorides on daguerreotype test samples prepared following 19th century recipes were studied. The dependence of variations in the production steps of daguerreotypes, such as multiple sensitization and gilding, on the impact of the exposure to chlorine were analyzed by scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS) and atomic force microscopy (AFM), complemented by X-ray fluorescence (XRF) and Raman spectroscopy. It was observed that AgCl nucleates on the image particles and in the substrate defects, regardless of the particle density or the sensitization process. In gilded samples, Au was observed over the image particles and the polished silver substrate as a tightly packed grainy layer, which conformably follows the polishing irregularities. For the first time it is shown that Au preferentially accumulates on top of the image particles. This gold layer does not protect the image from chlorine-induced deterioration. © 2011 Springer-Verlag.