More than XRF Mapping: STEAM (Statistically Tailored Elemental Angle Mapper) a Pioneering Analysis Protocol for Pigment Studies

Among the possible variants of X-Ray Fluorescence (XRF), applications exploiting scanning Macro-XRF (MA-XRF) are lately widespread as they allow the visualization of the element distribution maintaining a non-destructive approach. The surface is scanned with a focused or collimated X-ray beam of millimeters or less: analyzing the emitted fluorescence radiation, also elements present below the surface contribute to the elemental distribution image obtained, due to the penetrative nature of X-rays. The importance of this method in the investigation of historical paintings is so obvious—as the elemental distribution obtained can reveal hidden sub-surface layers, including changes made by the artist, or restorations, without any damage to the object—that recently specific international conferences have been held. The present paper summarizes the advantages and limitations of using MA-XRF considering it as an imaging technique, in synergy with other hyperspectral methods, or combining it with spot investigations. The most recent applications in the cultural Heritage field are taken into account, demonstrating how obtained 2D-XRF maps can be of great help in the diagnostic applied on Cultural Heritage materials. Moreover, a pioneering analysis protocol based on the Spectral Angle Mapper (SAM) algorithm is presented, unifying the MA-XRF standard approach with punctual XRF, exploiting information from the mapped area as a database to extend the comprehension to data outside the scanned region, and working independently from the acquisition set-up. Experimental application on some reference pigment layers and a painting by Giotto are presented as validation of the proposed method.

Band-Limited Reference-Free Speckle Spectroscopy: Probing the Fluorescent Media in the Vicinity of the Noise-Defined Threshold

A method of reference-free speckle spectroscopy based on the statistical analysis of intensity spatial fluctuations of the spectrally-selected multiple-scattered fluorescence radiation is examined in the case of the finite-band spectral selection of fluorescence light emitted by the laser-pumped random medium, and detection conditions far from the ideal case. Intensity fluctuations are recorded during point-to-point scanning of the surface of a random multiple-scattering medium, which is characterized by the dependences of the second- and third-order statistical moments of intensity on the wavelength of detected spectrally selected light. In turn, the statistical moments of intensity fluctuations are determined by the average propagation path of fluorescent radiation in the medium. This makes it possible to analyze the features of the light-medium interactions at a scale of the order of the transport mean free path of radiation propagation in the medium. Depending on the spectral selection conditions, the method is applicable for characterizing micro- or nano-structured fluorescent layers with thicknesses from tens of micrometers to several millimeters. In the examined case, the finite-band spectral selection results in the values of coherence length of the detected fluorescence radiation compared with the ensemble-averaged absolute value of the path-length difference between the stochastically interfering and spectrally selected partial contributions to the fluorescence field. In addition, non-ideal detection conditions (usage of a multimode optical fiber in the light-collecting unit) cause additional strong damping of the detected speckle intensity fluctuations. These factors lead to a remarkable suppression of spatial fluctuations of the fluorescence intensity in the course of spatially- and spectrally-resolved surface scanning of the laser-pumped probed random medium. Nevertheless, with appropriate procedures of the intrinsic noise reduction and data correction, the obtained spectral dependencies of the normalized third-order statistical moment of the band-limited fluorescence intensity clearly indicate the fluorescence propagation features in the probed multiple-scattering random media (such as a strong influence of the scattering strength and multiple self-absorption–re-emission events on the average propagation path of light in the medium).The possibilities of noise reduction and data correction in the case of applying the band-limited reference-free spectroscopic instrumentation with low spectral and spatial resolution are illustrated by the experimental results obtained using the Rhodamine-6G-doped and continuous wave (CW)-laser-pumped layers of the densely packed titania and silica particles.