Fractionation of Suwannee River fulvic acid and Aldrich humic acid on $\alpha$-Al$_2$O$_3$: spectroscopic evidence

Abstract : Sorptive fractionation of Suwannee River Fulvic Acid (SRFA) and Purified Aldrich Humic Acid (PAHA) on $\alpha$-Al$_2$O$_3$ at pH 6 was probed in the supernatant using different spectroscopic techniques. Comparison of dissolved organic carbon (DOC) analysis with UV/Vis spectrophotometric measurements at 254 nm, including Specific UV absorbance (SUVA) calculation, revealed a decrease in chromophoric compounds for the non sorbed extracts after a 24 h contact time. This fractionation, only observable below a certain ratio between initial number of sites of humic substances and of $\alpha$-Al$_2$O$_3$, seems to indicate a higher fractionation for PAHA. C(1s) near-edge X-ray absorption fine structure spectroscopy (NEXAFS) confirmed this trend and points to a decrease in phenolic moieties in the supernatant and to an eventual increase in phenolic moieties on the surface. Time-resolved luminescence spectroscopy (TRLS) of Eu(III) as luminescent probe showed a decrease in the ratio between the $^5$D0$\rightarrow$$^7$F$_2$ and $^5$D0$\rightarrow$$^7$F$_1$ transitions for the fractionated organic matter (OM) that is thought to be associated to a lower energy transfer from the OM to Eu(III) due to the loss of polar aromatics. These modifications in the supernatant are a hint for the modification of sorbed humic extracts on the surface.