The darkening of chromate-pigments, including chrome yellows (PbCr1-xSxO4), is a surface phenomenon affectinglate 19th-early 20thc. paintings, such as those by Van Gogh. Exploring analytical strategies that contribute to a deep understanding of darkening is therefore significant for the long-term conservation of unique masterpieces.Here, we examined the capabilities of Cr K-edge XANES spectroscopy collected at the same time in X-ray fluorescence yield (XFY) and total electron yield (TEY) detection modes to selectively study the surface composition of darkened oil paint mock-ups composed of chrome yellow (PbCr0.2S0.8O4) or potassium chromate.By discussing advantages and drawbacks in using XFY/TEY modes in relation to XFY µ-XANES analysis from sectioned samples, we aim at assessing if TEY-XANES spectroscopy: (i) is a selective surface method to determine the abundance of different Cr-species from paint fragments; (ii) can contribute to optimize the analytical strategy by limiting time consuming sample preparation procedures; (iii) can decrease the probability of radiation damage.