Mixing models provide a useful null hypothesis against which to evaluate processes controlling stream water chemical data. Because conservative mixing of end-members with constant concentration is a linear process, a number of simple mathematical and multivariate statistical methods can be applied to this problem. Although mixing models have been most typically used in the context of mixing soil and groundwater end-members, an extension of the mathematics of mixing models is presented that assesses the “fit” of a multivariate data set to a lower dimensional mixing subspace without the need for explicitly identified end-members. Diagnostic tools are developed to determine the approximate rank of the data set and to assess lack of fit of the data. This permits identification of processes that violate the assumptions of the mixing model and can suggest the dominant processes controlling stream water chemical variation. These same diagnostic tools can be used to assess the fit of the chemistry of one site into the mixing subspace of a different site, thereby permitting an assessment of the consistency of controlling end-members across sites. This technique is applied to a number of sites at the Panola Mountain Research Watershed located near Atlanta, Georgia.