Interaction between Dissolved Organic Matter and Long-Chain Ionic Liquids: A Microstructural and Spectroscopic Correlation Study

The production and use of ionic liquids (ILs) increase the potential risk after their emission into the environment. After entering the environment, ILs will readily interact with dissolved organic matter (DOM), and their environmental behavior will be impacted by DOM, which is abundant in the environment and has various functional groups. However, to date, the interaction between DOM and ILs, especially long-chain ILs, remains unclear. In this work, the interaction between long-chain ILs and humic acid (HA), a representative DOM, was investigated using synchronous fluorescence, Fourier transform infrared spectroscopy, dynamic light scattering, and zeta potential techniques, which were integrated with two-dimensional correlation spectroscopy (2DCOS), hetero-2DCOS, and perturbation-correlation moving-window analyses. The results show that cation exchange by the carboxylic groups in humic-like fractions was primarily responsible for interaction at low IL concentrations. As a result, the decrease in electrostatic repulsion and the increase in hydrophobicity facilitated the loose aggregation of HA. With an increase in IL concentration, the aromatic and carbonyl groups were involved in the interaction via the π-π interaction and dipole-dipole interaction, respectively, which resulted in the disruption of the intramolecular hydrogen bond and promoted the compaction of HA under the hydrophobic effect. The intensity transition sequence of various groups in HA was elucidated more specifically by 2DCOS. With these results, a comprehensive view of the structural changes of DOM in its IL-binding process was obtained, and the fate and environmental impact of ILs could be better understood. Furthermore, the superior potential of such an integrated approach in investigating the complex interactions in the environment was also demonstrated.