Direct-contact heat and mass transfer processes are widely employed in saline wastewater treatment. However, these processes are accompanied by serious ultrafine particle emission, a phenomenon associated with the solute’s transition across the gas–liquid interface. A thorough comprehension of the solute’s behavior at this gas–liquid interface is vital for clarifying the crossing process and guiding particle control strategies. Here, solutions containing saturated inorganic ions and humic substances were evaporated to analyze their behaviors at the gas–liquid interface in an experimental simulation of direct-contact heat and mass transfer processes. It was found that these substances co-precipitated at this interface. Humic substances can bind with inorganic ions via chemical bonds, monovalent ions through cation-π interactions, and divalent ions through electrostatic and chelation interactions. Moreover, humic substances can act as nucleation sites for precipitating inorganic crystals. These distinctive binding mechanisms caused a synergistic relationship between humic substances and inorganic ions during precipitation. Amidst precipitation, humic substances with high humification degrees and large molecular weights were predominantly enriched. Inorganic ions, comprising over 93% of the total precipitate mass, constituted the principal constituents. Among these, Na+, with an enrichment factor of 2.10, precipitated more readily at the gas–liquid interface compared to divalent ions. These conclusions concerning the binding mechanisms of humic substances and inorganic ions, along with their precipitation characteristics, were validated in the submerged combustion evaporation process of membrane-concentrated leachate.