The transition away from PFAS-based aqueous film forming foams (AFFF) has created an urgent need for effective fluorine-free alternatives for fuel fire suppression. To match the performance of AFFF, these alternatives must exhibit the required adsorption kinetics and foaming characteristics at fluid interfaces. This work investigates the surfactant transport to fluid interfaces for several PFAS-free formulations. We use tensiometry techniques like pendant drop and capillary pressure microtensiometer (CPM) to characterize dynamic interface tension and observe a stepwise adsorption in commercial surfactant products owing to their chemical heterogeneity. A multi-stage adsorption model is developed to extract key equilibrium parameters and diffusivity for individual surfactant components in the product to understand the behavior of promising fluorine-free firefighting candidates. Additionally, experiments are conducted across temperatures (23ᵒC and 60ᵒC) with interface curvatures ranging 1.5 mm to 60 µm to understand the effect of temperature and curvature on adsorption dynamics. These findings contribute to understanding the chemical composition of essential commercial surfactants, paving the way for optimized formulations of PFAS-free firefighting foam. Further, complementary studies on dilatational interfacial rheology using CPM and bulk foam stability using a dynamic foam analyzer are performed to correlate the microscopic interfacial properties to macroscopic foam behavior. Finally, we propose alternate synergistic formulations of catanionic surfactant mixtures that exhibit the required adsorption and foaming behavior.