Development of more effective, reliable, and fast methods for monitoring process streams is a growing opportunity for analytical applications. Many fields can benefit from online monitoring, including the nuclear fuel cycle where improved methods for monitoring radioactive materials will facilitate maintenance of proper safeguards and ensure safe and efficient processing of materials. Online process monitoring with a focus on optical spectroscopy can provide a fast, nondestructive method for monitoring chemical species. However, identification and quantification of species can be hindered by the complexity of the solutions if bands overlap or show condition-dependent spectral features. Plutonium(IV) is one example of a species which displays significant spectral variation with changing nitric acid concentration. Single variate analysis (i.e., Beer's Law) is difficult to apply to the quantification of Pu(IV) unless the nitric acid concentration is known and separate calibration curves have been made for all possible acid strengths. Multivariate or chemometric analysis is an approach that allows for the accurate quantification of Pu(IV) without a priori knowledge of nitric acid concentration.