Comparison of elemental content on modern and ancient papers by EDXRF

We report on the use of elemental composition, determined by energy dispersive X-ray fluorescence (EDXRF), to identify different types of paper. The concentrations of S, Cl, K, Ca, Ti, Mn, Fe, Co, Cu, Zn, As, Br, Rb, Sr, Ba and Pb were determined in papers from 1555, 1575, 1724, 1748, 1779, 1782, 1787, 1806, 1861, 1919, 1941 and 2005. A preliminary analysis was made with the use of a dendrogram. The Euclidian distances evidenced a big fluctuation in the elemental composition on most recent papers. The dendrogram also allowed us to catalogue the analysed samples into ten types of paper. Calcium, Cu, Fe, Zn and Sr were the only elements found in all paper samples. However the content of each element was different in every paper type. Calcium is the predominant element in all paper types. Applying Spearman coefficients correlations to these papers for Ca, Cu, Fe, Zn and Sr, we found moderate negative correlations between Ca-Cu. Positive correlations were also found between Fe-Cu, though not very strong. High levels of the toxic elements, Co, Ni, As and Pb were present in papers from 1779 and 1787. From this work it becomes clear that the number of elements in modern papers is lower than in older ones. PACS 39.30.+W; 78.70.En; 89.90.+n