Hostname: page-component-76fb5796d-22dnz Total loading time: 0 Render date: 2024-04-26T20:33:55.524Z Has data issue: false hasContentIssue false
  • English
  • Français

Sorption of Nitroaromatics by Ammonium- and Organic Ammonium-Exchanged Smectite: Shifts from Adsorption/Complexation to a Partition-Dominated Process

Published online by Cambridge University Press:  01 January 2024

Michael G. Roberts ,
Hui Li ,
Brian J. Teppen  and
Stephen A. Boyd
Michael G. Roberts
Affiliation:
Department of Crop and Soil Sciences, Environmental Science and Policy Program, Michigan State University, East Lansing, Michigan 48824-1325, USA
Hui Li
Affiliation:
Department of Crop and Soil Sciences, Environmental Science and Policy Program, Michigan State University, East Lansing, Michigan 48824-1325, USA
Brian J. Teppen
Affiliation:
Department of Crop and Soil Sciences, Environmental Science and Policy Program, Michigan State University, East Lansing, Michigan 48824-1325, USA
Stephen A. Boyd*
Affiliation:
Department of Crop and Soil Sciences, Environmental Science and Policy Program, Michigan State University, East Lansing, Michigan 48824-1325, USA
*
*E-mail address of corresponding author: boyds@msu.edu
Get access Rights & Permissions [Opens in a new window]

Abstract

Nitroaromatic compounds (NACs) are components of munitions commonly found as soil contaminants at military training sites and elsewhere. These compounds pose possible threats to human health and ecological systems. Recent studies indicate that these compounds are strongly retained by smectite clays. The adsorption mechanisms are not fully reconciled, but it is known that the type of exchangeable cation strongly affects NAC affinity for smectites. This study examined the sorption of 1,3-dinitrobenzene, 2,4-dinitrotoluene and naphthalene from water by a smectite clay (SWy-2) saturated with ammonium, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA). In all cases, we observed greater sorption of 2,4-dinitrotoluene compared with 1,3-dinitrobenzene. The sorption isotherms for 2,4-dinitrotoluene and 1,3-dinitrobenzene displayed a concave-downward curve for NH4-SWy-2 and TMA-SWy-2, whereas the isotherms for sorption of HDTMA-SWy-2 and TMPA-SWy-2 were essentially linear. The magnitude of sorption followed the order: NH4-SWy-2 > TMA-SWy-2 > TMPA-SWy-2 > HDTMA-SWy-2 for both compounds. The greater affinity of NACs for NH4- and TMA-SWy-2 is due in part to complex formation between the exchangeable cation and −NO2 groups. These clays also provide near optimal interlayer distances that approximate the molecular thickness of NACs hence promoting the simultaneous interaction of the planar aromatic rings with opposing siloxane surfaces and solute dehydration. Both processes are energetically favorable. In HDTMA-SWy-2, sorption of all solutes is via a partition-dominated process. Solute competition (diminished uptake of one solute in the presence of a second) was observed for TMA-SWy-2 but not HDTMA-SWy-2. This is consistent with an adsorptive mechanism for TMA-SWy-2 and a partitioning mechanism for HDTMA-SWy-2. This study demonstrates that the dominant molecular mechanism of NAC sorption by smectite changes fundamentally from complexation between −NO2 groups and the exchangeable cation (viz. NH4 and TMA) to partitioning for a systematic series of ammonium and quaternary ammonium cations in which the locus of positive charge (the central N atom) is progressively shielded by organic moieties of increasing size.

Keywords

MunitionsNitroaromatic CompoundsSmectiteSoil Contamination
Type
Research Article
Information
Clays and Clay Minerals , Volume 54 , Issue 4 , August 2006 , pp. 426 - 434
Copyright
Copyright © 2006, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Barrer, R.M. and Perry, G. S. (1961) Sorption of mixtures, and selectivity in alkylammonium montmorillonite. Part II. Tetramethylammonium montmorillonite: Journal of Chemistry Society, 850–858.Google Scholar
Boyd, S.A. Lee, J.F. and Mortland, M.M., (1988) Attenuating organic contaminant mobility by soil modification Nature 333 345–347 10.1038/333345a0.CrossRefGoogle Scholar
Boyd, S.A. Mortland, M.M. and Chiou, C.T., (1988) Sorption characteristics of organic compounds on hexadecyltrimethylammonium-smectite Soil Science Society of America Journal 52 652–657 10.2136/sssaj1988.03615995005200030010x.CrossRefGoogle Scholar
Boyd, S.A. Sheng, G. Teppen, B.J. and Johnston, C.T., (2001) Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays Environmental Science and Technology 35 4227–4234 10.1021/es010663w.CrossRefGoogle ScholarPubMed
Burris, D.R. and Anthworth, C.P., (1992) In situ modification of aquifer material by a cationic surfactant to enhance retardation of organic contaminants Journal of Contaminant Hydrology 10 325–337 10.1016/0169-7722(92)90014-6.CrossRefGoogle Scholar
Chiou, C.T., (2002) Partition and Adsorption of Organic Contaminants in Environmental Systems Hoboken, New Jersey John Wiley & Sons, Inc. 10.1002/0471264326.CrossRefGoogle Scholar
Ford, G.P. and Wang, B., (1992) The optimized ellipsoidal cavity and its application to the self-consistent reaction field calculation of hydration energies of cations and neutral molecules Journal of Computation Chemistry 13 229–239 10.1002/jcc.540130214.CrossRefGoogle Scholar
Haderlein, S.B. and Schwarzenbach, R.P., (1993) Adsorption of substituted nitrobenzenes and nitrophenols to mineral surfaces Environmental Science and Technology 27 316–326 10.1021/es00039a012.CrossRefGoogle Scholar
Haderlein, S.B. Weissmahr, K.W. and Schwarzenbach, R.P., (1996) Specific adsorption of nitroaromatic explosives and pesticides to clay minerals Environmental Science and Technology 30 612–622 10.1021/es9503701.CrossRefGoogle Scholar
Hundal, L.S. Thompson, M.L. Laird, D.A. and Carmo, A.M., (2001) Sorption of phenanthrene by reference smectites Environmental Science and Technology 35 3456–3461 10.1021/es001982a.CrossRefGoogle ScholarPubMed
Jaynes, W.F. and Boyd, S.A., (1990) Trimethylphenylammonium-smectite as an effective adsorbent of water-soluble aromatic hydrocarbons Journal of Air and Waste Management Association 40 1649–1653 10.1080/10473289.1990.10466811.CrossRefGoogle ScholarPubMed
Jaynes, W.F. and Boyd, S.A., (1991) Clay mineral type and organic compound sorption by hexadecyltrimethylammonium-exchanged clays Soil Science Society of America Journal 55 43–48 10.2136/sssaj1991.03615995005500010007x.CrossRefGoogle Scholar
Jaynes, W.F. and Boyd, S.A., (1991) Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water Clays and Clay Minerals 39 428–436 10.1346/CCMN.1991.0390412.CrossRefGoogle Scholar
Johnston, C.T. de Oliveria, M.F. Teppen, B.J. Sheng, G. and Boyd, S.A., (2001) Spectroscopic study of nitroaromatic-smectite sorption mechanisms Environmental Science and Technology 35 4767–4772 10.1021/es010909x.CrossRefGoogle ScholarPubMed
Johnston, C.T. Sheng, G. Teppen, B.J. Boyd, S.A. and Oliveira, M.F.d., (2002) Spectroscopic study of dinitrophenol herbicide sorption on smectite Environmental Science and Technology 36 5067–5074 10.1021/es025760j.CrossRefGoogle ScholarPubMed
Lee, J.F. Crum, J.R. and Boyd, S.A., (1989) Enhanced retention of organic contaminants by soils exchanged with organic cations Environmental Science and Technology 23 1365–1372 10.1021/es00069a006.CrossRefGoogle Scholar
Lee, J.F. Mortland, M.M. Chiou, C.T. Kile, D.E. and Boyd, S.A., (1990) Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities Clays and Clay Minerals 38 113–120 10.1346/CCMN.1990.0380201.CrossRefGoogle Scholar
Li, H. Teppen, B.J. Laird, D.A. Johnston, C.T. and Boyd, S.A., (2004) Geochemical modulation of pesticide sorption on smectite clay Environmental Science and Technology 38 5393–5399 10.1021/es0494555.CrossRefGoogle ScholarPubMed
Li, H. Teppen, B.J. Johnston, C.T. and Boyd, S.A., (2004) Thermodynamics of nitroaromatic compounds adsorption from water by smectite clay Environmental Science and Technology 38 5433–5442 10.1021/es035054y.CrossRefGoogle ScholarPubMed
Marcus, Y., (1985) Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed-solvents. 2. Enthalpies and entropies of transfer to nonaqueous solvents Pure and Applied Chemistry 57 1103–1128 10.1351/pac198557081103.CrossRefGoogle Scholar
McBride, M.B. Pinnavaia, T.J. Mortland, M.M. and Suffet, I.H., (1977) Adsorption of aromatic molecules by clays in aqueous suspension Fate of Pollutants in the Air and Water Environment. Part 1 New York Wiley-Interscience 145–154.Google Scholar
Mortland, M.M. Sun, S. and Boyd, S.A., (1986) Clay-organic complexes as adsorbents for phenol and chlorophenols Clays and Clay Minerals 34 581–585 10.1346/CCMN.1986.0340512.CrossRefGoogle Scholar
Sheng, G. Xu, S. and Boyd, S.A., (1996) Mechanism(s) controlling sorption of neutral organic contaminants by surfactant-derived and natural organic matter Environmental Science and Technology 30 1553–1557 10.1021/es9505208.CrossRefGoogle Scholar
Sheng, G. Wang, X. Wu, S. and Boyd, S.A., (1998) Enhanced sorption of organic contaminants by smectitic soils modified with a cationic surfactant Journal of Environmental Quality 27 806–814 10.2134/jeq1998.00472425002700040013x.CrossRefGoogle Scholar
Sheng, G. Johnston, C.T. Teppen, B.J. and Boyd, S.A., (2002) Adsorption of dinitrophenol herbicides from water by montmorillonites Clays and Clay Minerals 50 25–34 10.1346/000986002761002630.CrossRefGoogle Scholar
Van Olphen, H. and Fripiat, J.J., (1979) Data Handbook for Clay Minerals and other Non-metallic Minerals New York Pergamon Press.Google Scholar
Weissmahr, K.W. Haderlein, S.B. and Schwarzenbach, R.P., (1998) Complex formation of soil minerals with nitroaromatic explosives and other pi-acceptors Soil Science Society of America Journal 62 369–378 10.2136/sssaj1998.03615995006200020012x.CrossRefGoogle Scholar
Weissmahr, K.W. Hildenbrand, M. Schwarzenbach, R.P. and Haderlein, S.B., (1999) Laboratory and field scale evaluation of geochemical controls on groundwater transport of nitroaromatic ammunition residues Environmental Science and Technology 33 2593–2600 10.1021/es981107d.CrossRefGoogle Scholar
Wolfe, T.A. Demerirel, T. and Baumann, E.R., (1985) Interaction of aliphatic amines with montmorillonite to enhance adsorption of organic pollutants Clays and Clay Minerals 33 301–311 10.1346/CCMN.1985.0330405.CrossRefGoogle Scholar
Xu, S. and Boyd, S.A., (1995) Cationic surfactant adsorption by swelling and nonswelling layer silicates Langmuir 11 2508–2514 10.1021/la00007a033.CrossRefGoogle Scholar
Xu, S. Sheng, G. and Boyd, S.A., (1997) Use of organoclays in pollution abatement Advances in Agronomy 59 25–61 10.1016/S0065-2113(08)60052-8.CrossRefGoogle Scholar
Zhu, D. Herbert, B.E. Schlautman, M.A. Carraway, E.R. and Hur, J., (2004) Cation-π bonding: a new perspective on the sorption of polycyclic aromatic hydrocarbons to mineral surfaces Journal of Environmental Quality 33 1322–1330 10.2134/jeq2004.1322.CrossRefGoogle ScholarPubMed