Investigation of sorbate-induced plasticization of Pahokee peat by solid-state NMR spectroscopy

Abstract

Sorbate-induced swelling and plasticization of sorbent have been linked to sorption hysteresis of organic compounds in the natural organic matter of isolated humic acids, soils, and coals. The above processes, which have important implications for the fate and bioavailability of organic and inorganic contaminants, are mostly based on macroscopic changes and require molecular-level confirmation. This study aimed to investigate the presence or absence of sorbate-induced plasticization of Pahokee peat soil as a function of different sorbates. The plasticization of Pahokee peat soil was studied upon sorption of different proton-free solutes including C6D6, CDCl3, CCl4, C2Cl4, CBr4, C6D5Cl, and C5D5N, covering apolar and polar aromatic and aliphatic compounds. The swelling and plasticization of Pahokee peat soil were verified at the molecular level by 1H wideline and two-dimensional wideline separation (2D WISE) NMR. The use of 1H wideline shapes is the traditional technique for studying molecular dynamics but hampered by the lack of spectral resolution, with one dimension displaying 13C chemical shifts and the second showing 1H wideline shapes, is capable of providing information on molecular dynamics of specific functional groups. Our results showed that the segments of Pahokee peat soil sorbed with C6D6, C2Cl4, and C5D5N became more mobile, but the changes due to the plasticization were small. Both C6D6 and C5D5N selectively increased the mobility of specific components, C6D6 of the nonpolar alkyl domains, and C5D5N of both the nonpolar alkyl domains and aromatic components. Some liquid solutes at high concentrations (2–5 wt%) are capable of slightly “softening” natural organic matter of a soil, and this provides support for the hypothesis that natural organic matter in Pahokee peat soil is in a glassy state that is subject to plasticization.