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

  • Soils, Sec 1 • Soil Organic Matter Dynamics and Nutrient Cycling • Research Article
  • Published:
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Abstract

Purpose

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.

Materials and methods

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.

Results and discussion

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.

Conclusions

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.

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Acknowledgments

This research was supported by grants from the National Science Foundation (CBET 0853682 and 0853950 and EAR 1226323).

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Old Dominion University, 4541 Hampton Blvd, Norfolk, VA, 23529, USA

    Xiaoyan Cao & Jingdong Mao

  2. Department of Environmental Sciences, The Connecticut Agricultural Experiment Station, P.O. Box 1106, New Haven, CT, 06504, USA

    Charisma Lattao & Joseph J. Pignatello

  3. Department of Chemistry, Brandeis University, 415 South Street, Waltham, MA, 02453, USA

    Klaus Schmidt-Rohr

Authors
  1. Xiaoyan Cao
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  2. Charisma Lattao
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  3. Klaus Schmidt-Rohr
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  4. Jingdong Mao
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  5. Joseph J. Pignatello
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Corresponding authors

Correspondence to Jingdong Mao or Joseph J. Pignatello.

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Responsible editor: Francisco Javier González-Vila

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Cao, X., Lattao, C., Schmidt-Rohr, K. et al. Investigation of sorbate-induced plasticization of Pahokee peat by solid-state NMR spectroscopy. J Soils Sediments 16, 1841–1848 (2016). https://doi.org/10.1007/s11368-016-1378-5

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  • DOI: https://doi.org/10.1007/s11368-016-1378-5

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