Metabolic models for fractionations produced by sulfate-reducing Bacteria and Archaea derived from experimental observations are the cornerstone of our interpretation of ancient and modern biogeochemical cycles. Although recent studies have called into question a traditionally accepted model, experimental evidence has been lacking for such a claim. We present data from all four sulfur isotopes that suggest that the internal fractionations associated with the sulfate reduction network are larger than previous estimates. Models of a traditional sulfate reduction network, as well as a more recent incarnation of the sulfate reduction network (with multiple sulfur intermediates) are constructed to aid in the understanding of new experimental data. These data also allow for the further development of additional minor isotope relationships, one of which is easily measurable in geologic settings and accurately depicts the net effect of an environment, whereas the other is more applicable to modern environments and may better illuminate the specific process(es) controlling the fractionation in those environments. This approach illustrates the uses of systems containing more than two isotopes.