Study of the role of sulfur functionalities in humic acids for uranium(VI) complexation

Sulfur containing humic acid model substances have been synthesized to study the role of sulfur functionalities for the complexation behavior of humic acids towards U(VI). Humic acids type M1-S with different sulfur contents (1.9, 3.9, 6.9 wt. %) were synthesized and characterized. The identity of the sulfur species was determined by X-ray photoelectron spectroscopy (XPS). Reduced sulfur species, such as thiols, dialkylsulfides and/or disulfides, were determined as the dominating sulfur functionalities in the used humic acids. The U(VI) complexation of humic acids with different sulfur contents has been studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and TRLFS with ultrashort femtosecond laser pulses (fs-TRLFS) in comparison to a sulfur-free humic acid type M1 (pH 3.80 +/- 0.02; I = 0.1 M NaClO(4); p(CO2), = 10(-3.5) atm). For all studied humic acids, similar coniplexation constants were determined. However, with increasing sulfur contents of the humic acids (> 2 wt. %) an increase of the number of humic acid binding sites for U(VI) was determined which is reflected in increasing U(VI) loading capacities and increasing total humic acid ligand concentrations for U(VI) measured by TRLFS and fs-TRLFS, respectively. This increase of the fraction of humic acid binding sites for U(VI) points to an involvement of reduced sulfur functionalities, such as thiol groups, in the complexation between U(V1) and humic acid. However, for environmentally relevant sulfur contents of humic acids (<2 wt. %) it can be concluded that, compared to oxygen functionalities, especially carboxylic groups, reduced sulfur functionalities play only a subordinate role for the U(VI) complexation by humic acids in the acidic pH range.