Spectroscopic Characteristics and Speciation Distribution of Fe(III) Binding to Molecular Weight-Dependent Standard Pahokee Peat Fulvic Acid.

Peat-derived organic matter, as powerful chelators, is of great significance for the transport of Fe to the ocean and the enhancement of dissolved Fe. However, the iron binding capacity of molecular weight (MW)-fractionated dissolved organic matter is variable, due to its structure and composition heterogeneity. In this work, we used the standard Pahokee Peat fulvic acid (PPFA) as an example, and investigated the spectroscopy properties and Fe(III) binding ability of PPFA and different molecular weight fractions by UV−Vis absorbance and fluorescence spectroscopy and the Donnan Membrane Technique (DMT). The results showed binding sites for Fe(III) at the 263 nm and >320 nm regions in differential absorbance spectra. Upon increasing the iron concentration to 18.00 μmol·L−1, the critical binding capacity was exceeded, which resulted in a decrease in absorbance. Fe(III) was found to prefer to bind to humic-like components, and ultraviolet humic-like fluorophores displayed stronger binding strength. High molecular weight PPFA fractions (>10 kDa) possessed more aromatic and hydrophobic components, displayed a higher degree of humification, and exhibited higher metal binding potential. Furthermore, the speciation analysis and stability constant (cK) were calculated using Donnan membrane equilibrium. The correlation between cK values and PPFA spectral properties demonstrated that aromaticity, hydrophobicity, molecular weight and humification degree were crucial indices of PPFA−Fe(III) affinity. Significantly, the humification degree, represented by HIX, showed the strongest correlation (r = 0.929, p = 0.003), which could be used to estimate the binding strength. This study provides further understanding of the complexation mechanism of iron and DOM in the peat environment and identifies the considerable effect of molecular weight.