Molecular insight into biomass-burning smoke water-soluble organic matter binding with Cd(II): Comprehensive analysis from fluorescence EEM-PARAFAC, FT-ICR-MS and two-dimensional correlation spectroscopy.

The deposition of biomass-burning smoke water-soluble organic matter (BBS-WSOM) significantly affects the environmental behavior of heavy metals in aqueous environments. However, the interactions between BBS-WSOM and heavy metals at the molecular level remain unknown. This study combined FT-ICR-MS, fluorescence spectrum, FTIR, and two-dimensional correlation spectroscopy to anatomize the molecular characteristics of BBS-WSOM binding with Cd(II). The results show that CHO and CHOP compounds were responsible for the fluorescence response of BBS-WSOM at Ex: 225 nm and 275 nm/Em: 325 nm, and abundant proteins or CHON compounds were responsible for the fluorescence response of BBS-WSOM at Ex: 225-250 nm/Em: 350-450 nm and Ex: 300-350 nm/Em: 350-450 nm, which was very different from the fluorescence molecules in natural organic matters. Fluorescence change after Cd(II) addition indicated that CHOP and CHOS compounds enhanced BBS-WSOM binding with Cd(II). Differently, the CHON compounds could weaken the binding of other compounds with Cd(II). Different compounds binding with Cd(II) generally followed the order: CHON/CHOS compounds>CHOP compounds>CHO compounds, and the chemical groups binding with Cd(II) generally followed the prioritization: -COO> -NH/SO>P = O/P-O>aromatic ring>CO>C-OH of phenol/alcohol>C-O-C. This study provides a profound insight into the interaction between BBS-WSOM and Cd(II) at the molecular level.