In-situ versus laboratory characterization of historical site in marine environment using X-ray fluorescence and Raman spectroscopy

Abstract Raman spectroscopy and X-ray fluorescence spectrometry are powerful analytical techniques that allow for molecular and elemental analysis, respectively. Recent developments allowed for the miniaturization of equipment to an extent that in-situ experiments become available. There are many advantages in using portable instruments, but this requires sacrifices regarding the acquisition of the spectra and the quality of the analysis. How much information is lost with this exchange is not clear, neither how important this is for the use of these techniques as forensic tools. In this work, the damage of a facade of Villa Belza, a historic building in Biarritz, France, was evaluated using both portable and benchtop versions of X-ray fluorescence (XRF) and Raman spectroscopy and the approaches were compared. As the comparison of instruments designed for different conditions is not straightforward, the authors use a number of settings to discuss what would be a realistic juxtaposition of results and how this affects the diagnosis of the structure. Furthermore, some hand-held XRF spectrometers are not connected to appropriate software to proceed with the data treatment and the processing of such signals can be tedious or too time consuming. Thus this work also proposes an algorithm for the automatic identification and comparison of elements in the XRF spectra acquired on site. After discussing the trade-off involved with each technique and the respective effect in the limit of detection, the authors conclude that the extra information from benchtop instruments was negligible for this case study.