Spectral fingerprints of DOM-tungsten interactions: Linking molecular binding to conformational changes

Tungsten (W), a widely used yet understudied emerging contaminant, forms oxyanions in aqueous environments, distinguishing it from conventional heavy metals. While dissolved organic matter (DOM) demonstrates considerable potential for W binding, DOM-W interactions remain largely unexplored. Of particular significance, yet frequently overlooked, are the conformational changes in DOM during W binding processes. This study proposes a novel theoretical framework integrating superposition and charge transfer models to elucidate the complexity of these interactions. By combining spectroscopic techniques and photophysical models, we revealed that aromatic compounds containing 1-3 rings, especially monocyclic aromatic protein-like components, exhibit high affinity for W (logK=3.74-4.00). Phenolic hydroxyls served as primary binding sites for W, with aromatic rings facilitating binding through π interactions. Importantly, W binding to aromatic compounds induced conformational changes in DOM, transitioning from a loosely aggregated state to a more compact configuration. These changes facilitated W encapsulation within DOM through the synergistic effects of hydrophobic interactions, hydrogen/π-hydrogen bonding and π-stacking, potentially leading to stable trapping of W. Two-dimensional correlation spectroscopy analysis elucidated the sequential encapsulation process, involving phenolic, aromatic carboxylic/aliphatic carboxylic, polysaccharides, and aliphatics. The intricate behavior of DOM-W binding profoundly reshapes DOM's conformation, subtly yet significantly orchestrating W's binding affinity, environmental transport, and bioavailability in aquatic ecosystems.