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Quantitative chemical imaging with appropriate pixel size relative to the granular particle size enhances the localized sensitivity to reveal the molecular structural composition of wheat millstreams. Simultaneous microspectroscopic scanning of individual pixels in an array of detectors is performed with the objective of determining the endosperm analyte (product) concentration in a heterogeneous matrix of solids that includes nonproduct. The spectral organic chemical features of the isolated endosperm analyte (primarily starch and protein) are defined using a robust spectral library and compared to those of the nonendosperm components. Rather than a binary scheme, each pixel in the image is assigned a % endosperm score based on a partial least squares data treatment. Quantitation is achieved by summation of % endosperm concentration scores for all pixels in the field of view. Replicate fields of view are interrogated and coadded. In the industrial commodity processing scheme, the weighted combination of product concentrations are determined and cited in order of descending purity. Because endosperm purity is determined rather than focusing on nonendosperm (impurity), a sequential cumulative millers’ curve reveals the streams that need to be included to meet the contract purity specifications. This enables informed product stream selectivity following refinement via a series of processing separation steps. The increased sensitivity of the endosperm purity method described is anticipated to be useful in assessing the effects of equipment installation or changes in operational settings on the commercial milling process. Application of quantitative chemical imaging to a newly constructed mill with design for a unique function is cited to exemplify the utility of this approach to optimize individual unit processes. The preliminary results are presented in this report.