This work introduces a novel method to multivariate analysis applied to fused hyperspectral datasets in the field of Cultural Heritage (CH). Hyperspectral Imaging is a well-established approach for the non-invasive examination of artworks, offering insights into their composition and conservation status. In CH field, a combination of hyperspectral techniques is usually employed to reach a comprehensive understanding of the artwork. To deal with hyperspectral data, multivariate statistical methods are essential due to the complexity of the data. The process involves factorizing the data matrix to highlight components and reduce dimensionality, with techniques such as Non-negative Matrix Factorization (NMF) gaining prominence. To maximize the synergies between multimodal datasets, the fusion of hyperspectral datasets can be coupled with multivariate analysis, with potential applications in CH. In this work, I will show examples of this approach with different combinations of datasets, including reflectance and transmittance spectral imaging, Fluorescence Lifetime Imaging and Time-Gated Hyperspectral Imaging, and Raman and fluorescence spectroscopy micro-mapping.

Macroscopic x-ray fluorescence imaging spectroscopy (MA-XRF) and reflectance imaging spectroscopy (RIS) are important tools in the analysis of cultural heritage objects, both for conservation and art historical research purposes. The elemental and molecular distributions provided by MA-XRF and RIS respectively, are particularly useful for the identification and mapping of pigments in easel paintings. While MA-XRF has relatively established data processing methods based on modeling of the underlying physics, RIS data cannot be modeled with sufficient precision and its processing has considerable room for improvements. This work seeks to improve RIS data processing workflows in the short wavelength infrared range (SWIR, 1000–2500 nm) with a novel method that fits Gaussian profiles to pigment-specific absorption features, and we compare its performance to MA-XRF for the task of semi-quantitative pigment mapping, evaluating their limits of detection (LODs) and the matrix effects that affect their signals. Two pigments are considered in this work, lead white and blue verditer, which are mapped in SWIR RIS using the first overtone of -OH stretching of their primary compounds, hydrocerussite (Pb₃(CO₃)₂(OH)₂) and azurite (Cu₃(CO₃)₂(OH)₂), at 1447 and 1497 nm respectively, and in MA-XRF using the Pb-L and Cu-K fluorescence signals. The methods are evaluated using two sets of custom-prepared paint samples, as well as a 16th-century painting, discussing the identification, mapping, and semi-quantitative analysis of the considered pigments. We found SWIR RIS to be a pigment-specific method with a longer linear range but inferior LODs and penetration depth when compared to MA-XRF, the latter is often not capable of discriminating between different pigments with identical elemental markers. We furthermore present a novel color scale that allows the simultaneous visualization of signals above and below a confidence limit.