Fe and/or Mn‐containing yellow ochre, red ochre, and umber earth pigments are omnipresent in 17th century paintings. Less common in the materials used in historical paintings of this period is the Fe and Mn‐rich earth pigment sienna. Different uses of historical pigments in one painting by Georg Flegel (1566–1638) and another version of the same painting but of disputed attribution were recently uncovered by means of macro‐x‐ray fluorescence (MA‐XRF) scanning and other non‐invasive analytical techniques. In this paper, an approach solely based upon the correlation of Fe and Mn MA‐XRF maps with the optical image of the painting is compared to the use of Mn/Fe correlation plots. The identification of clusters within a plot of the Fe counts vs. the Mn counts can aid to infer whether an area with a certain color matches with the use of the earth pigments found in the two paintings and to ultimately shed light on the different usage of these pigments. The analytical thresholds found in the Mn/Fe correlation plots allowed to identify clusters differing in composition, which matched an area of a certain color with the earth pigments used therein. This highlighted the differences and similarities between the two paintings, ultimately ascertaining the lower value of the painting of disputed attribution. The analysis of single‐pixel spectra allowed refining the interpretation of specific Mn/Fe correlation plots. The purpose of these data evaluation steps is presented and the limitations of the proposed methodology are also discussed.

Until today, iron gall ink is classified as an exceptional underdrawing material for paintings. Its study and definite identification is usually based on invasive analysis. This article presents a new non-destructive approach using micro-X-ray fluorescence scanning (MA-XRF), LED-excited IRR (LEDE-IRR) based on a narrow wavelength-range of infrared radiation (IR) for illumination and stereomicroscopy for studying and visualising iron gall ink underdrawings. To assess possibilities and limits of these analytical techniques, the approach was tested on panel paintings by Hans Holbein the Elder and Giovanni Battista Cima da Conegliano. Results are compared to invasive examinations on cross-sections using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX). The holistic setup could successfully visualise iron gall ink underdrawings, allowing to harness the formerly invisible underdrawing lines for interdisciplinary studies.