A qualitative approach to discern the relative contributions of 137Cs and 90Sr in-solution with a monitoring probe is described, based on a comparison of X- and γ-ray photon spectra. The bremsstrahlung yield from 90Sr has been measured as a function of distance (x) from a cerium bromide scintillation detector relative to the 137Cs γ-ray full-energy peak response. The utility of two, count-independent shape factor parameters has been compared: the ratio of the sum of the counts in the 60–800 keV region to the full-energy peak response associated with the 137Cs 662 keV γ-ray line, termed for the benefit of this paper as SF1, and the ratio of counts in the 60–350 keV region to those in the 350–450 keV region, defined in this work as SF2. These parameters probe the presence of isotopes associated with clear full-energy spectral lines and bremsstrahlung, respectively. They have been calibrated as a function of x with sealed sources in the laboratory and both are observed to be asymptotic as x→0. This approach has been tested with a variety of open, laboratory-based liquid samples comprising 90Sr and 137Cs, and in a water-based, contaminated medium in the field associated with a sump at a low-level waste disposal facility on the former fast reactor site at Dounreay, UK. The highest response in both SF1 and SF2 measured in this work is observed in these on-site measurements, consistent with x→0, implying both 90Sr and 137Cs presenting together in solution. This is consistent with prior, laboratory-based analysis of the sump media, and suggests that the β−-emitter contribution (anticipated to comprise 90Sr and 90Y) is very near the probe, consistent with the solution being in contact with it. This is of relevance where the β−/γ composition of contaminated groundwater, in-situ, is not well understood or where migratory changes in activity are suspected.