A fluorescence labeling approach to assess the deterioration state of aged papers

Deterioration of historical papers is caused by several processes, such as acid hydrolysis or autoxidation due to the presence of metal ions contained in inks or pigments. Both processes can be studied by fluorescence labeling of carbonyl and carboxyl groups in combination with GPC-MALLS. This technique allows to determine not only the extent of hydrolysis, but also the concentration of oxidized functionalities within very low sample amounts.The thermally induced aging of rag papers with lines of copper pigment has been investigated, simulating green or blue copper pigments in historic wall papers. The cellulose parts with pigment coverage and adjacent pigment-free regions were analyzed separately and compared to paper parts not affected by metal ions. The cellulose underneath and close to the applied pigment strokes was severely affected. Although there was no difference in the molecular weight distribution, distinct differences in the carbonyl and carboxyl content were observed. Copper ion migration is suggested to be one possible explanation for this observation as a strong correlation between distribution of copper ions and carbonyl groups was found. For the first time, a detailed examination of cellulose damage in spatial proximity to metal-containing pigment lines is thus presented.