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


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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  1. Bemm U, Ostmark H (1998) 1,1-Diamino-2,2-dinitroethylene: a novel energetic material with infinite layers in two dimensions. Acta Cryst C54:1997–1999

    CAS  Google Scholar 

  2. Bledzki AK, Gassan J (1999) Composites reinforced with cellulose based fibers. Prog Polym Sci 24:221–274

    CAS  Article  Google Scholar 

  3. Boys SF, Bernardi F (1970) Calculation of small molecular interactions by differences of separate total energies—some procedures with reduced errors. Mol Phys 19:553–566

    CAS  Article  Google Scholar 

  4. Carper WR, Davis LP, Extine MW (1982) Molecular structure of 2,4,6-trinitrotoluene. J Phys Chem 86:459–462

    CAS  Article  Google Scholar 

  5. Cossi M, Rega N, Scalmani G, Barone V (2003) Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model. J Comp Chem 24:669–681

    CAS  Article  Google Scholar 

  6. Craig VSJ, Plunkett MJ (2003) Determination of coupled solvent mass in quartz crystal microbalance measurements using deuterated solvents. J Colloid Interface Sci 262:126–129

    CAS  Article  Google Scholar 

  7. Fält S, Wågberg L, Vesterlind E-L (2003) Swelling of model films of cellulose having different charge densities and comparison to the swelling behavior of corresponding fibers. Langmuir 19:7895–7903

    Article  Google Scholar 

  8. Felt DR, Johnson JL, Larson S, Hubbard B, Henry K, Nestler C, Ballard JH (2013) Evaluation of treatment technologies for wastewater from insensitive munitions production phase I: technology down-selection. U.S. Army Engineer Research and Development Center, ERDC/EL TR-13-20, Vicksburg

  9. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, IzmaylovAF Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision A.1. Gaussian Inc., Wallingford

    Google Scholar 

  10. Marx KA (2003) Quartz crystal microbalance: a useful tool for studying thin polymer films and complex biomolecular systems at the solution-surface interface. Biomacromol 4:1099–1120

    CAS  Article  Google Scholar 

  11. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994

    CAS  Article  Google Scholar 

  12. Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082

    CAS  Article  Google Scholar 

  13. Nyburg SC, Faerman CH, Prasad L, Palleros D, Nudelman N (1987) Structures of 2,4-dinitroanisole and 2,6-dinitroanisole. Acta Cryst C43:686–689

    CAS  Google Scholar 

  14. Päakkö M, Ankerfors M, Kosonen H, Nykanen A, Ahola S, Osterberg M, Ruokolainen J, Laine J, Larsson PT, Ikkala O, Lindstrom T (2007) Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels. Biomacromolecules 6:1934–1941

    Article  Google Scholar 

  15. Politzer P, Laurence PR, Jayasuriya K (1985) Molecular electrostatic potentials: an effective tool for the elucidation of biochemical phenomena. Environ Health Perspect 61:191–202

    CAS  Article  Google Scholar 

  16. Sauerbrey G (1959) Verwendung von Schwingquarzenzur Wagungdunner Schichten und zur Mikrowagung. Zeitschrift für Physik 155:206–222

    CAS  Article  Google Scholar 

  17. Taylor S, Park E, Bullion K, Dontsova K (2015) Dissolution of three insensitive munitions formulations. Chemosphere 119:342–348

    CAS  Article  Google Scholar 

  18. Thorn KA, Pennington JC, Hyes CA (2002) 15N NMR investigation of the reduction and binding of TNT in an aerobic bench scale reactor simulating windrow composting. Environ Sci Technol 36:3797–3805

    CAS  Article  Google Scholar 

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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).

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