A Multi-Analytical Approach for the Investigation of Black Crusts on Two Monuments in Athens, Greece

Analytical studies of archeological materials often face challenges, such as the merging of heterogeneous, multidimensional datasets from complementary analytical techniques, and incorporating site- and user-defined parameters. In this study, a data fusion methodology is applied that combines micro-X-ray fluorescence (micro-XRF) spectrometry and handheld Raman spectroscopy to investigate degradation layers and identify pollution sources on two monuments in an urban background: the Temple of Hephaestus and the Byzantine Church of Ag. Theodoroi, in Athens, Greece. A total of 12 samples were collected for laboratory measurements and 32 in situ measurements were conducted. Statistical and unsupervised machine learning tools, namely correlation analysis, Principal Component Analysis and k-means clustering, were applied to the merged datasets. Additionally, selected elements’ ratios were calculated to infer their sources. The black crusts were identified as heterogeneous mixtures of calcium sulfate dihydrate, calcite, and particulate pollutants, with their composition reflecting their preservation state. Vehicular emission indicators were dominant in both sites, while secondary domestic heating pollutant indicators were more prevalent at Ag. Theodoroi. Orientation had a minor role compared to pollutant sources in differentiating degradation patterns. The integrated comparison of the different outputs highlighted the interpretive potential of the approach, particularly in improving the readability of the multivariate structure and supporting the development of targeted conservation strategies for monuments in polluted urban contexts.