Optical property of iron binding to Suwannee River fulvic acid

Abstract

In this work, absorbance and fluorescence spectra were used to study iron binding to standard Suwannee River fulvic acid (SRFA). The differential logarithm-transformed absorbance and fluorescence spectra of SRFA induced by iron binding were processed to examine the nature of the observed phenomena and to investigate the contributions of discrete binding sites present in SRFA. Both the Fe-differential log-transformed absorbance and fluorescence were well correlated to the bound iron concentrations predicted based on the Non-ideal Competitive Adsorption (NICA-Donnan) model at iron concentrations below 10.0μM (R2>0.99 for absorbance and R2>0.97 for fluorescence) and over a wide pH range of 3.5–8.0. At pH3.5, both the Fe-differential log-transformed absorbance and fluorescence vs. iron bound spectra exhibited significantly lower slopes than those at pH5.0, 7.0, and 8.0. These results suggest that a different set of complexation-active chromophores and fluorophores are responsible for iron binding at low pH values or that the NICA-Donnan model is limited at low pH. Because phenolic and carboxylic complex sites of different fluorophores respond to iron quenching, the fluorescence data indicate three stages of iron binding to phenolic, carboxylic, and Donnan gels (electrostatic interactions) in SRFA (with R2>0.99 at each stage). The agreement between observations from spectroscopic indices and established metal-binding models shows that the absorbance and fluorescence spectra provide important information about the involvement of metal complexation of specific functional groups typical for fulvic acids.