Characterization of humic substances and non-ideal phenanthrene sorption as affected by clay-humic interactions.

摘要

Humic substances (HS) are major components of soil organic matter (SOM). Advances on characterization of HS and their interaction with minerals can provide a more fundamental understanding of HS functions in soils. The objectives of this research were to investigate potential fractionation of humic acid (HA) upon adsorption on minerals and to determine any variation on structure and sorption properties of humin extracted by different methods. Nuclear magnetic resonance (NMR) spectra, for the first time, provided direct evidence that HA was fractionated during adsorption on mineral surfaces. Aliphatic fractions of HA were preferentially adsorbed while aromatic fractions were more likely to be left in solution. The bound HA fractions had higher sorption linearity (N) and affinity (KOC) for phenanthrene than the source HA. For montmorillonite and kaolinite, the KOC values of adsorbed HA were up to several times higher than that of the source HA as a result of fractionation. Extraction procedures had substantial influences in structure and sorption characteristics of humin. Humin from 0.1 M NaOH exhaustive extraction and 6 M HF/HCl extraction at 60°C had relatively more aliphatic components as compared with 1 M HF extracted humin. The treatment of 6 M HF/HCl at 60°C reduced more than 50% carbohydrate components (50-108 ppm) and enriched amorphous poly(methylene) domains. The NaOH exhaustively extracted humin had the most nonlinear sorption isotherms and the HF extracted humin had the lowest KOC. We concluded that both NaOH and NaOH-HF procedures were appropriate approaches for humin extraction but the extraction with 6 M HF/HCl at 60 °C would be discouraged for use due to structural modifications of humin both chemically and physically. Segmental mobility of HA in solution was also explored by NMR relaxation. Proton spin-lattice relaxation time (T1) of HAs ranged from 0.3 to 0.8 s in d6-DMSO, and from 0.26 to 2.3 s in 0.5 M NaOD at 300 MHz. Proton correlation time of HA in solvents was in an order of 10-10 s. Carbohydrate was identified as the largest and the most immobile components while aliphatic and aromatic fragments were relatively smaller and more mobile in aqueous solution.