Mechanical investigation of U(VI) on pyrrhotite by batch, EXAFS and modeling techniques

The interaction mechanism of U(VI) on pyrrhotite was demonstrated by batch, spectroscopic and modeling techniques. Pyrite was selected as control group in this study. The removal of U(VI) on pyrite and pyrrhotite significantly decreased with increasing ionic strength from 0.001 to 0.1mol/L at pH 2.0-6.0, whereas the no effect of ionic strength was observed at pH >6.0. The maximum removal capacity of U(VI) on pyrite and pyrrhotite calculated from Langmuir model was 10.20 and 21.34mgg^-1 at pH 4.0 and 333K, respectively. The XPS analysis indicated the U(VI) was primarily adsorbed on pyrrhotite and pyrite and then approximately 15.5 and 9.8% of U(VI) were reduced to U(IV) by pyrrhotite and pyrite after 20 days, respectively. Based on the XANES analysis, the adsorption edge of uranium-containing pyrrhotite located between U^IVO₂(s) and U^VIO₂²⁺ spectra. The EXAFS analysis demonstrated the inner-sphere surface complexation of U(VI) on pyrrhotite due to the occurrence of U-S shell, whereas the U-U shell revealed the reductive co-precipitates of U(VI) on pyrrhotite/pyrite with increasing reaction times. The surface complexation modeling showed that outer- and inner-surface complexation dominated the U(VI) removal at pH<4 and pH>5.0, respectively. The findings presented herein play a crucial role in the removal of radionuclides on iron sulfide in environmental cleanup applications.