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In time-of-flight secondary ion mass spectrometry (ToF-SIMS), multivariate analysis (MVA) methods such as principal component analysis (PCA) are routinely employed to differentiate spectra. However, additional insights can often be gained by comparing processes, where each process is characterized by its own start and end spectra, such as when identical samples undergo slightly different treatments or when slightly different samples receive the same treatment. This study proposes a strategy to compare such processes by decomposing the loading vectors associated with them, which highlights differences in the relative behavior of the peaks. This strategy identifies key information beyond what is captured by the loading vectors or the end spectra alone. While PCA is widely used, partial least-squares discriminant analysis (PLS-DA) serves as a supervised alternative and is the preferred method for deriving process-related loading vectors when classes are narrowly separated. The effectiveness of the decomposition strategy is demonstrated using artificial spectra and applied to a ToF-SIMS materials science case study on the photodegradation of N719 dye, a common dye in photovoltaics, on a mesoporous TiO2 anode. The study revealed that the photodegradation process varies over time, and the resulting fragments have been identified accordingly. The proposed methodology, applicable to both labeled (supervised) and unlabeled (unsupervised) spectral data, can be seamlessly integrated into most modern mass spectrometry data analysis workflows to automatically generate a list of peaks whose relative behavior varies between two processes, and is particularly effective in identifying subtle differences between highly similar physicochemical processes. [ABSTRACT FROM AUTHOR]