Trace element quantification of lead based roof sheets of historical monuments by Laser Induced Breakdown Spectroscopy

• Quantification of trace elements (Ag, Bi, Cu and Sn) in a lead matrix by LIBS and LA-ICP-MS
• Low limit of detection for Ag, Bi, Cu and Sn by using LIBS portable instrumentation
• Set up a specific data processing combining PCA and GIS for cultural heritage application
• Comparison of LIBS and LA-ICP-MS results with 263 samples
• 488 samples analyzed by LIBS

The aim of this paper is to identify the different periods of construction or restoration of the lead roof of a historic monument. Trace elements in a lead matrix can be a signature of the metallurgical processes, allowing identification of a specific time period for the production of the lead used to build the roof. The ability of LIBS (Laser Induced Breakdown Spectroscopy) to detect such trace elements in a lead matrix is therefore explored and checked by comparing its results with LA-ICP-MS as a reference method (Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry). Concentrations of 263 samples were compared between LIBS and LA-ICP-MS data and their correlation was evaluated. Another way to compare their results is also suggested by combining PCA (Principal Component Analysis) and GIS (Geographic Information System). As a result statistical mappings were created, highlighting metallurgical groups of samples across the roof of the building. This innovative approach links concentration and spatial location resulting in an easily interpretable graphical presentation of the data.The results of both spectrometry methods lead to similar conclusions with distinctive areas of different lead compositions and by extension different lead dating across the roof. But since LIBS is portable we can conclude that it is a suitable and reliable instrument for in-situ applications on historic monuments.