Flowback and produced water generated by the hydraulic fracturing of unconventional oil and gas plays contain a suite of cations (e.g., metals) typically in a high salt (e.g., NaCl) matrix. Here, we analyzed the chemical (cation) composition of production fluids associated with natural gas and oil development (e.g., flowback, produced water, impoundment fluids), along with mine drainage, and surface and ground water samples using ICP-OES and ICP-MS. ICP-MS and ICP-OES analytical performance and interference effects were evaluated. Both platforms exhibited excellent analytical spike recoveries, detection limits for blank and spiked solutions, and accuracy for standard certified reference materials. Mass ratio analyses using Ca/Sr, Ca/Mg, Ba/Sr, Mg/Sr, and B and Li, were assessed for their efficacy in differentiation among brines from conventional oil wells, produced water from unconventional oil and gas wells and impoundments, mine drainage treatment pond water, groundwater, and surface water. Examination of Mg/Sr ratios when compared with Li concentrations provide clear separation among the different types of samples, while Ca/Mg versus Ca/Sr correlations were useful for distinguishing between conventional and unconventional oil and gas fluids.