FT-IR and synchronous fluorescence two-dimensional correlation spectroscopic analysis on the binding properties of mercury onto humic acids as influenced by pH modification and sulfide addition

Mercuric Hg²⁺ ion forms strong complexes with dissolved organic matter (DOM) in natural waters. The complexation of Hg²⁺ by sulfhydryl groups of DOM was regarded as the main mechanism for Hg²⁺-DOM interactions, particularly in anoxic sulfur and DOM-rich environments. In the present study, the influences of pH and sulfide addition on the molecular structure of Hg²⁺-DOM complexes and the characteristics of Hg²⁺ binding to DOM were investigated using FT-IR and synchronous fluorescence two-dimensional correlation spectroscopic analysis. Results showed that, during the Hg²⁺ binding process, the aromatic hydrogen CH in humic acids (HA) gave the fastest responses to pH perturbation and the S-reacted HA (S-HA) exhibited different reaction patterns from the unreacted HA. In S-HA, the esters/alcohols CO and carboxyl CO gave the fastest responses to Hg²⁺ binding. In the process of S-HA binding to Hg²⁺, the protein-like fractions including proteins, amino acids or monoaromatics played the leading role. Sulfide addition of HA enhanced the reactivity of small molecular weight compounds with low aromaticity and improved the binding ability of protein-like fractions to Hg²⁺. These findings provide a better understanding of the interaction mechanisms between Hg²⁺ and DOM at a molecular level and have important environmental implications in Hg²⁺ biogeochemical transformation, transport and cycling.