Sorption of Denatonium to Kaolinite Clay from Water

Garry S. Crosson, Stephanie Thorpe, Yun-Yun Zhou, James Dawson

Department of Chemistry and Biochemistry, University of Dayton, Dayton, USA.

DOI: 10.4236/jep.2013.49107                

Abstract

Denatonium benzoate is an aversive agent proposed for use in certain anti-freeze formulations to reduce poisoning events of pets and humans. Unfortunately, the sorption properties of denatonium cations to soil and/or soil components have not been investigated. In this paper, denatonium sorption to reference kaolinite clay under varied pH, ionic strength, and cation identity is described. The data clearly indicate that the nature of the background electrolyte cation modulates denatonium sorption with enhanced sorption occurring the presence of potassium ions versus minimal sorption occurring in a calcium chloride electrolyte at each pH studied as estimated using Dubinin-Raduskevich (D-R) isotherms. The effect of background electrolyte concentration on sorption was consistent with an ion-exchange process wherein the sorption capacity increased with decreased background electrolyte concentration. An interesting and unexpected observation of increased sorption capacity (estimated using the D-R model) with decreasing pH was observed in 10 mM CaCl₂ in contrast to an observed and expected increase in denatonium sorption to kaolinite in the presence of either of 10 mM NaCl or 10 mM KCl. Estimates of the mean sorption energy using D-R isotherms ranging from 2.65 kJ/mol in 10 mM CaCl₂ at pH 4 to 4.68 kJ/mol at pH 10 suggesting that the sorption process is not exclusively ion-exchange.

Keywords

Denatonium; Sorption Isotherms; Kaolinite; Clay Minerals; Water Quality

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	M. C. Henderson, C. M. Neumann and D. R. Buhler, “Analysis of Denatonium Benzoate in Oregon Consumer Products by HPLC,” Chemosphere, Vol. 36, No 1, 1998, pp. 203-210. doi:10.1016/S0045-6535(97)10033-9
[2]	D. Zuba, C. Oewiegoda, B. Byrska and W. Lechowicz, “Assessment of the Effectiveness of Denationium Benzoate (BITREX) Removal from Denatured Spirit Preparations Using Sodium Hypochlorite,” Problems of Forensic Sciences, Vol. 113, 2005, pp. 288-298.
[3]	D. Zuba, C. Oewiegoda, B. Byrska and W. Lechowicz, “Determination of Denatonium Benzoate (BITREX) in Denatured Spirit Preparations,” Problems of Forensic Sciences, Vol. 113, No. 2005, pp. 275-287.
[4]	US House of Representatives, “Statement of the American Waterworks Association before the Energy and Hazardous Materials Subcommittee Concerning H.R. 2537 The Antifreeze Bittering Act of 2005,” Energy and Hazardous Materials Subcommittee Committee of Energy and Commerce, 2005.
[5]	B. J. Brownawell, H. Chen, J. M. Collier and J. C. Westall, “Adsorption of Organic Cations to Natural Materials,” Environmental Science & Technology, Vol. 24, No. 8, 1990, pp. 1234-1241. doi:10.1021/es00078a011
[6]	J. A. Smith, P. R. Jaffe and C. T. Chiou, “Effect of Ten Quaternary Ammonium Cations on Tetrachloromethane Sorption to Clay from Water,” Environmental Science & Technology, Vol. 24, No. 8, 1990, pp. 1167-1172. doi:10.1021/es00078a003
[7]	A. Purohit, M. C. Kopferschmitt-Kubler, C. Moreau, E. Popin, M. Blaumeiser and G. Pauli, “Quaternary Ammonium Compounds and Occupational Asthma,” International Archives of Occupational and Environmental Health, Vol. 73, No. 6, 2000, pp. 423-427. doi:10.1007/s004200000162
[8]	M. S. Rodriguez-Cruz, M. S. Andrades, A. M. Parada, M. J. M. Sanchez-Martín, “Effect of Different Wood Pretreatments on the Sorption-Desorption of Linuron and Metalaxyl by Woods,” Journal of Agricultural and Food Chemistry, Vol. 56, No. 16, 2008, pp. 7339-7346. doi:10.1021/jf800980w
[9]	M. Mingorance, L. Sanchez and A. Pena, “Pesticide Adsorption on a Calcareous Soil Modified with Sewage Sludge and Quaternary Alkyl-Ammonium Cationic Surfactants,” Environmental Science and Pollution Research, Vol. 15, No. 1, 2008, pp. 8-14. doi:10.1065/espr2007.02.387
[10]	M. M. Ariffin and R. A. Anderson, “LC/MS/MS Analysis of Quaternary Ammonium Drugs and Herbicides in Whole Blood,” 43rd International Conference of the International-Association-of-Forensic-Toxicologists (TIAFT), Seoul, 29 August-2 September 2005, pp. 91-97.
[11]	M. Pateiro-Moure, E. Martinez-Carballo, M. Arias-Estevez and J. Simal-Gandara,”Determination of Quaternary Ammonium Herbicides in Soils-Comparison of Digestion, Shaking and Microwave-Assisted Extractions,” 10th International Symposium on Advances in Extraction Techniques, Bruges, 28-30 January 2008, pp. 110-116.
[12]	C. Willms, Z. H. Li, L. Allen and C. V. Evans, “Desorption of Cesium from Kaolinite and Illite Using Alkylammonium Salts,” Applied Clay Science, Vol. 25, No. 3-4, 2004, pp. 125-133. doi:10.1016/j.clay.2003.10.001
[13]	S. A. Boyd, M. M. Mortland and C. T. Chiou, “Sorption Characteristics of Organic-Compounds on Hexadecyltrimethylammonium-Smectite,” Soil Science Society of America Journal, Vol. 52, No. 3, 1988, pp. 652-657. doi:10.2136/sssaj1988.03615995005200030010x
[14]	D. L. Sparks, “Environmental Soil Chemistry,” 4th Edition, Academic Press, San Diego, 1995.
[15]	M. Pateiro-Moure, C. Perez-Novo, M. Arias-Estevez, R. Rial-Otero and J. Simal-Gandara, “Effect of Organic Matter and Iron Oxides on Quaternary Herbicide sorption-Desorption in Vineyard-Devoted Soils,” Journal of Colloid and Interface Science, Vol. 333, No. 2, 2009, pp. 431-438. doi:10.1016/j.jcis.2009.02.019
[16]	W. D. Burgos, N. Pisutpaisal, M. C. Mazzarese and J. Chorover, “Adsorption of Quinoline to Kaolinite and Montmorillonite,” Environmental Engineering Science, Vol. 19, No. 2, 2002, pp. 59-68. doi:10.1089/10928750252953697
[17]	OECD, “Test No. 106: Adsorption: Desorption Using a Batch Equilibrium Method,” OECD. Paris, 2000. doi:10.1787/9789264069602-en
[18]	R.-L. Tseng and F.-C. Wu, “Inferring the Favorable Adsorption Level and the Concurrent Multi-Stage Process with the Freundlich Constant,” Journal of Hazardous Materials, Vol. 155, No. 1-2, 2008, pp. 277-287. doi:10.1016/j.jhazmat.2007.11.061
[19]	T. Shahwan and H. N. Erten, “Thermodynamic Parameters of Cs+ Sorption on Natural Clays,” Journal of Radioanalytical and Nuclear Chemistry, Vol. 253, No. 1, 2002, pp. 115-120. doi:10.1023/A:1015824819940
[20]	G. Limousin, J. P. Gaudet, L. Charlet, S. Szenknect, V. Barthes and M. Krimissa, “Sorption Isotherms: A Review on Physical Bases, Modeling and Measurement,” Applied Geochemistry, Vol. 22, No. 2, 2007, pp. 249-275. doi:10.1016/j.apgeochem.2006.09.010
[21]	C. Appel, L. Q. Ma, R. Dean Rhue and E. Kennelley, “Point of Zero Charge Determination in Soils and Minerals via Traditional Methods and Detection of Electroacoustic Mobility,” Geoderma, Vol. 113, No. 1-2, 2003, pp. 77-93. doi:10.1016/S0016-7061(02)00316-6
[22]	K. Draoui, R. Denoyel, M. Chgoura and J. Rouquerol, “Adsorption of Paraquat on Minerals. A Thermodynamic Study,” Journal of Thermal Analysis and Calorimetry, Vol. 58, No. 3, 1999, pp. 597-606. doi:10.1023/A:1010152411288
[23]	A. R. Tehrani-Bagha, H. Nikkar, N. M. Mahmoodi, M. Markazi and F. M. Menger, “The Sorption of Cationic Dyes onto Kaolin: Kinetic, Isotherm and Thermodynamic Studies,” Desalination, Vol. 266, No. 1-3, 2011, pp. 274-280. doi:10.1016/j.desal.2010.08.036
[24]	N. R. Joseph, “The Dissociation Constants of Organic Calcium Complexes,” Journal of Biological Chemistry, Vol. 164, No. 2, 1946, pp. 529-541.
[25]	S. Sen, P. Yu, V. P. Klyuev and B. Z. Pevzner, “Atomic Structure of Beryllium Boroaluminate Glasses: A Multi-Nuclear NMR Spectroscopic Study,” Journal of Non-Crystalline Solids, Vol. 354, No. 33, 2008, pp. 4005-4011. doi:10.1016/j.jnoncrysol.2008.06.002
[26]	A. G. Christy, “A Monte Carlo Study of Short- and Long-Range Order of Tetrahedral Cations in Sapphirine and Khmaralite,” American Mineralogist, Vol. 94, No. 2-3, 2009, pp. 270-282. doi:10.2138/am.2009.2956
[27]	P. Behra, E. Lecarme-Theobald, M. Bueno and J. J. Herhardt, “Sorption of Tributyltin onto a Natural Quartz Sand,” Journal of Colloid and Interface Science, Vol. 263, No. 1, 2003, pp. 4-12. doi:10.1016/S0021-9797(03)00238-8
[28]	D. A. Ellis, J. W. Martin, D. C. G. Muir and S. A. Mabury, “Development of an 19F NMR Method for the Analysis of Fluorinated Acids in Environmental Water Samples,” Analytical Chemistry, Vol. 72, No. 4, 2000, pp. 726-731. doi:10.1021/ac9910280
[29]	W. Yan, S. Hu and C. Jing, “Enrofloxacin Sorption on Smectite Clays: Effects of pH, Cations, and Humic Acid,” Journal of Colloid and Interface Science, Vol. 372, No. 1, 2012, pp. 141-147. doi:10.1016/j.jcis.2012.01.016
[30]	H. Gulley-Stahl, P. A. Hogan, W. L. Schmidt, S. J. Wall, A. Buhrlage and H. A. Bullen, “Surface Complexation of Catechol to Metal Oxides: An ATR-FTIR, Adsorption, and Dissolution Study,” Environmental Science & Technology, Vol. 44, No. 11, 2010, pp. 4116-4121. doi:10.1021/es902040u
[31]	H. Li, B. J. Teppen, D. A. Laird, C. T. Johnston and S. A. Boyd, “Geochemical Modulation of Pesticide Sorption on Smectite Clay,” Environmental Science & Technology, Vol. 38, No. 20, 2004, pp. 5393-5399. doi:10.1021/es0494555
[32]	S. B. Haderlein and R. P. Schwarzenbach, “Adsorption of Substituted Nitrobenzenes and Nitrophenols to Mineral Surfaces,” Environmental Science & Technology, Vol. 27, No. 2, 1993, pp. 316-326. doi:10.1021/es00039a012
[33]	G. Y. Sheng, C. T. Johnston, B. J. Teppen and S. A. Boyd, “Adsorption of Dinitrophenol Herbicides from Water by Montmorillonites,” Clays and Clay Minerals, Vol. 50, No. 1, 2002, pp. 25-34. doi:10.1346/000986002761002630
[34]	K. Gupta, T. Basu and U. C. Ghosh, “Sorption Characteristics of Arsenic(V) for Removal from Water Using Agglomerated Nanostructure Iron(III)-Zirconium(IV) Bimetal Mixed Oxide”, Journal of Chemical & Engineering Data, Vol. 54, No. 8, 2009, pp. 2222-2228. doi:10.1021/je900282m
[35]	L. Mihaly Cozmuta, A. Mihaly Cozmuta, A. Peter, C. Nicula, E. Bakatula Nsimba and H. Tutu, “The Influence of pH on the Adsorption of Lead by Na-Clinoptilolite: Kinetic and Equilibrium Studies,” Water Sa, Vol. 38, No. 2, 2012, pp. 269-278.
[36]	Y. S. Ho, J. F. Porter and G. McKay, “Equilibrium Isotherm Studies for the Sorption of Divalent Metal Ions onto Peat: Copper, Nickel and Lead Single Component Systems,” Water, Air and Soil Pollution, Vol. 141, 2002, pp. 1-33.
[37]	S. S. Tahir and N. Rauf, “Removal of a Cationic Dye from Aqueous Solutions by Adsorption onto Bentonite Clay,” Chemosphere, Vol. 63, No. 11, 2006, pp. 1842-1848. doi:10.1016/j.chemosphere.2005.10.033
[38]	M. Akcay, “Characterization and Adsorption Properties of Tetrabutylammonium Montmorillonite (TBAM) Clay: Thermodynamic and Kinetic Calculations,” Journal of Colloid and Interface Science, Vol. 296, No. 1, 2006, pp. 16-21. doi:10.1016/j.jcis.2005.08.031