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Adsorption of Emerging Munitions Contaminants on Cellulose Surface: A Combined Theoretical and Experimental Investigation

Abstract

This manuscript reports results of an integrated theoretical and experimental investigation of adsorption of two emerging contaminants (DNAN and FOX-7) and legacy compound TNT on cellulose surface. Cellulose was modeled as trimeric form of the linear chain of 1 → 4 linked of β-D-glucopyranos in 4C1 chair conformation. Geometries of modeled cellulose, munitions compounds and their complexes were optimized at the M06-2X functional level of Density Functional Theory using the 6-31G(d,p) basis set in gas phase and in water solution. The effect of water solution was modeled using the CPCM approach. Nature of potential energy surfaces was ascertained through harmonic vibrational frequency analysis. Interaction energies were corrected for basis set superposition error and the 6-311G(d,p) basis set was used. Molecular electrostatic potential mapping was performed to understand the reactivity of the investigated systems. It was predicted that adsorbates will be weakly adsorbed on the cellulose surface in water solution than in the gas phase.

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Acknowledgments

The use of trade, product, or firm names in this report is for descriptive purposes only and does not imply endorsement by the U.S. Government. The tests described and the resulting data presented herein, unless otherwise noted, were obtained from research conducted under the Environmental Quality Technology Program of the United States Army Corps of Engineers and the Environmental Security Technology Certification Program of the Department of Defense by the USAERDC. Permission was granted by the Chief of Engineers to publish this information. The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents. The authors thank Dr. Guilherme Lotufo, and Dr. Chris Griggs of USACE for their editorial comments.

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Correspondence to Manoj K. Shukla.

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Shukla, M.K., Poda, A. Adsorption of Emerging Munitions Contaminants on Cellulose Surface: A Combined Theoretical and Experimental Investigation. Bull Environ Contam Toxicol 96, 784–790 (2016). https://doi.org/10.1007/s00128-016-1791-x

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Keywords

  • 2,4-dinitroanisole (DNAN)
  • 1,1-diamino-2,2-dinitroethene (FOX-7)
  • 2,4,6-trinitrotoluene (TNT)
  • Cellulose
  • Adsorption
  • DFT level