We used the 7-μm polyacrylate ion-exchange SPME fibers to investigate C12-benzalkonium sorption to 10 mg/L natural organic matter at concentrations well below the cation-exchange capacity. C12-BAC sorption at constant medium conditions differed within 0.4 log units for two humic acids (Aldrich, Leonardite) and peat (Sphagnum, Pahokee), with similar nonlinear sorption isotherms (K_F ∼ 0.8). Sorption to the SPME fibers and Aldrich humic acid (AHA) was reduced at both low pH and high electrolyte concentration, and reduced more strongly by Ca²⁺ compared with Na⁺ at similar concentrations. Sorption isotherms for AHA (5–50–500 mM Na⁺, pH 6) was modeled successfully by the NICA-Donnan approach, resulting in an intrinsic sorption coefficient of 5.35 (C_aq = 1 nM). The NICA-Donnan model further explained the stronger specific binding of Ca²⁺ compared to Na⁺ by differences in Boltzmann factors. This study provides relevant information to interpret bioavailability of quaternary ammonium compounds, and possibly for other organic cations.