Compared with colorimetric imaging, multispectral imaging has the advantage of retrieving spectral reflectance factor of each pixel of a painting. Using this spectral information, pigment mapping is concerned with decomposing the spectrum into its constituent pigments and their relative contributions. The output of pigment mapping is a series of spatial concentration maps of the pigments comprising the painting. This approach was used to study Vincent van Gogh's The Starry Night. The artist's palette was approximated using ten oil pigments, selected from a large database of pigments used in oil paintings and a priori analytical research on one of his self portraits, executed during the same time period. The pigment mapping was based on single-constant Kubelka-Munk theory. It was found that the region of blue sky where the stars were located contained, predominantly, ultramarine blue while the swirling sky and region surrounding the moon contained, predominantly, cobalt blue. Emerald green, used in light bluish-green brushstrokes surrounding the moon, was not used to create the dark green in the cypresses. A measurement of lead white from Georges Seurat's La Grande Jatte was used as the white when mapping The Starry Night. The absorption and scattering properties of this white were replaced with a modern dispersion of lead white in linseed oil and used to simulate the painting's appearance before the natural darkening and yellowing of lead white oil paint. Pigment mapping based on spectral imaging was found to be a viable and practical approach for analyzing pigment composition, providing new insight into an artist's working method, the possibility for aiding in restorative inpainting, and lighting design.

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Near-infrared diffuse reflectance imaging spectroscopy (NIR-RIS, 1000 to 2500 nm) was used to map the use of alkyd and oil paints in Jackson Pollock'sNumber 1, 1950(Lavender Mist), one of his most important ‘drip’ or ‘poured’ paintings.

Jackson Pollock's Number 1A, 1948 painting was investigated using in situ scanning macro-x-ray fluorescence mapping (MA-XRF) to help characterize the artist's materials and his creative process. A multivariate curve resolution-alternating least squares (MCR-ALS) approach was used to examine the hyperspectral data and obtain distribution maps and signature spectra for the paints he used. The composition of the paints was elucidated based on the chemical elements identified in the signature spectra and a tentative list of pigments, fillers and other additives is proposed for eleven different paints and for the canvas. The paint distribution maps were used to virtually reconstruct the artist process and document the sequence and manner in which Pollock applied the different paints, using deliberate and specific gestures.