JWARP  Vol.6 No.8 , June 2014
Activated Carbon and Clay Minerals for the Sorptive Removal of Denatonium Ions from Denatonium Benzoate Solutions

This study assessed the feasibility of utilizing activated carbon and clay minerals for treating water impacted with the bittering agent denatonium benzoate (DB). Our specific study objectives were to 1) evaluate denatonium ion sorption to smectite clay minerals (bentonite and hectorite) and activated carbon (powdered and granular) at constant pH and ionic strength and 2) examine the impact of pH on denatonium ion sorption to each solid material. The experimental results indicated that high doses (33,000 mg/L) of as-received granular activated carbon and as-received clay minerals completely removed denatonium from aqueous solutions containing 100 - 1000 mg/L denatonium benzoate. Powdered activated carbon at doses of 5 - 100 mg/L exhibited favorable monolayer sorption of denatonium ions from a pH 6.95, 70 mg/L aqueous denatonium benzoate solution with a Langmuir separation factor (r) of 0.481, a maximum sorption capacity (Sm) of 74 mg/g, and a Langmuir constant of 15.3 L/g. A maximum removal of 23% of denatonium was achieved at the highest powdered activated carbon dosage employed. Denatonium ion removal with peroxide treated bentonite and peroxide treated hectorite did not result in complete removal of the ion and exhibited favorable sorption as evidenced by Freundlich 1/n values ranging from 0.803 to 1.194; Freundlich constants (Kf) ranged from 8 ng/L to 575 ng/L. Denatonium ion sorption to peroxide treated bentonite appeared to depend on pH while hectorite sorption of denatonium ions was independent of hydrogen ion concentrations. For powdered activated carbon adsorption, as pH increased denatonium ion sorption decreased. Overall, the work demonstrates that denatonium can be effectively removed from water via activated carbon or clay mineral sorption.

Cite this paper: Crosson, G. , Crosson, K. , Thorpe, S. , MacPherson, L. , Murdock, M. and Smith, B. (2014) Activated Carbon and Clay Minerals for the Sorptive Removal of Denatonium Ions from Denatonium Benzoate Solutions. Journal of Water Resource and Protection, 6, 793-803. doi: 10.4236/jwarp.2014.68075.

[1]   Sparks, D.L. (1995) Environmental Soil Chemistry. 4th Edition, Academic Press, San Diego.

[2]   Association, C.S.P. (2013) Making Antifreeze and Engine Coolant Unpalatable to Humans and Animals.

[3]   Henderson, M.C., Neumann, C.M. and Buhler, D.R. (1998) Analysis of Denatonium Benzoate in Oregon Consumer Products by HPLC. Chemosphere, 36, 203-210.

[4]   Reddy, C.M. and Quinn, J.G. (1997) Environmental Chemistry of Benzothiazoles Derived from Rubber. Environmental Science & Technology, 31, 2847-2853.

[5]   H.R. 2567 (2006) The Antifreeze Bittering Act of 2005. Energy and Commerce, 2nd Edition, Government Printing Office, Washington DC, 155.

[6]   Brownawell, B.J., Chen, H., Collier, J.M. and Westall, J.C. (1990) Adsorption of Organic Cations to Natural Materials. Environmental Science & Technology, 24, 1234-1241.

[7]   Zhang, Z.Z., Sparks, D.L. and Scrivner, N.C. (1993) Sorption and Desorption of Quaternary Amine Cations on Clays. Environmental Science & Technology, 27, 1625-1631.

[8]   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.

[9]   Xu, S. and Boyd, S.A. (1995) Alternative Model for Cationic Surfactant Adsorption by Layer Silicates. Environmental Science & Technology, 29, 3022-3028.

[10]   Wang, C., Ding, Y., Teppen, B.J., Boyd, S.A., Song, C. and Li, H. (2009) Role of Interlayer Hydration in Lincomycin Sorption by Smectite Clays. Environmental Science & Technology, 43, 6171-6176.

[11]   Parette, R., Cannon, F.S. and Weeks, K. (2005) Removing Low Ppb Level Perchlorate, RDX, and HMX from Groundwater with Cetyltrimethylammonium Chloride (CTAC) Pre-Loaded Activated Carbon. Water Research, 39, 4683-4692.

[12]   De Oliveira, M.F., Johnston, C.T., Premachandra, G.S., Teppen, B.J., Li, H., Laird, D.A., Zhu, D.Q. and Boyd, S.A. (2005) Spectroscopic Study of Carbaryl Sorption on Smectite from Aqueous Suspension. Environmental Science & Technology, 39, 9123-9129.

[13]   Agus, E., Lim, M.H., Zhang, L. and Sedlak, D.L. (2011) Odorous Compounds in Municipal Wastewater Effluent and Potable Water Reuse Systems. Environmental Science & Technology, 45, 9347-9355.

[14]   Chen, W.F., Parette, R. and Cannon, F.S. (2012) Pilot-Scale Studies of Arsenic Removal with Granular Activated Carbon and Zero-Valent Iron. Environmental Engineering Science, 29, 897-901.

[15]   Basar, C.A., Karagunduz, A., Cakici, A. and Keskinler, B. (2004) Removal of Surfactants by Powdered Activated Carbon and Microfiltration. Water Research, 38, 2117-2124.

[16]   Adachi, A., Kamide, M., Kawafune, R., Miki, N. and Kobayashi, T. (1990) Removal Efficiency of Anionic and Nonionic Surfactants from Chemical Waste-Water by a Treatment-Plant Using Activated Carbon Adsorption and Coagulation Precipitation Processes. Environmental Technology, 11, 133-140.

[17]   Oen, A.M.P., Beckingham, B., Ghosh, U., Krusa, M.E., Luthy, R.G., Hartnik, T., Henriksen, T. and Cornelissen, G. (2011) Sorption of Organic Compounds to Fresh and Field-Aged Activated Carbons in Soils and Sediments. Environmental Science & Technology, 46, 810-817.

[18]   Kupryianchyk, D., Rakowska, M.I., Roessink, I., Reichman, E.P., Grotenhuis, J.T.C. and Koelmans, A.A. (2013) In Situ Treatment with Activated Carbon Reduces Bioaccumulation in Aquatic Food Chains. Environmental Science & Technology, 47, 4563-4571.

[19]   Li, X. and Brownawell, B.J. (2010) Quaternary Ammonium Compounds in Urban Estuarine Sediment Environments— A Class of Contaminants in Need of Increased Attention? Environmental Science & Technology, 44, 7561-7568.

[20]   Li, X.L. and Brownawell, B.J. (2009) Analysis of Quaternary Ammonium Compounds in Estuarine Sediments by LC-ToF-MS: Very High Positive Mass Defects of Alkylamine Ions as Powerful Diagnostic Tools for Identification and Structural Elucidation. Analytical Chemistry, 81, 7926-7935.

[21]   Crosson, G. and Sandmann, E. (2013) Kinetic Study of Denatonium Sorption to Smectite Clay Minerals. Environmental Engineering Science, 30, 311-316.

[22]   Ma, J., Yu, F., Zhou, L., Jin, L., Yang, M.X., Luan, J.S., Tang, Y.H., Fan, H.B., Yuan, Z.W. and Chen, J.H. (2012) Enhanced Adsorptive Removal of Methyl Orange and Methylene Blue from Aqueous Solution by Alkali-Activated Multiwalled Carbon Nanotubes. ACS Applied Materials & Interfaces, 4, 5749-5760.

[23]   Ho, Y.S., Malarvizhi, R. and Sulochana, N. (2009) Equilibrium Isotherm Studies of Methylene Blue Adsorption onto Activated Carbon Prepared from Delonix Regia Pods. Journal of Environmental Protection Science, 3, 111-116.

[24]   Raposo, F., De La Rubia, M.A. and Borja, R. (2009) Methylene Blue Number as Useful Indicator to Evaluate the Adsorptive Capacity of Granular Activated Carbon in Batch Mode: Influence of Adsorbate/Adsorbent Mass Ratio and Particle Size. Journal of Hazardous Materials, 165, 291-299.

[25]   Arslanoglu, F.N., Kar, F. and Arslan, N. (2005) Adsorption of Dark Coloured Compounds from Peach Pulp by Using Granular Activated Carbon. Journal of Food Engineering, 68, 409-417.

[26]   Kumar, K.V. and Sivanesan, S. (2006) Isotherm Parameters for Basic Dyes onto Activated Carbon: Comparison of Linear and Non-Linear Method. Journal of Hazardous Materials, 129, 147-150.

[27]   Mittal, A., Krishnan, L. and Gupta, V.K. (2005) Removal and Recovery of Malachite Green from Wastewater Using an Agricultural Waste Material, De-Oiled Soya. Separation and Purification Technology, 43, 125-133.

[28]   Itodo, A.U., Itodo, H.U. and Gafar, M.K. (2010) Estimation of Specific Surface Area Using Langmuir Isotherm Method. Journal of Applied Science and Environmental Management, 14, 141-145.

[29]   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 & Technology, 38, 5393-5399.

[30]   Li, H., Teppen, B.J., Laird, D.A., Johnston, C.T. and Boyd, S.A. (2006) Effects of Increasing Potassium Chloride and Calcium Chloride Ionic Strength on Pesticide Sorption by Potassium- and Calcium-Smectite. Soil Science Society of America Journal, 70, 1889-1895.

[31]   Hower, W.F. (1970) Adsorption of Surfactants on Montmorillonite. Clays and Clay Minerals, 18, 97-105.

[32]   Bohmer, M.R. and Koopal, L.K. (1992) Adsorption of Ionic Surfactants on Variable-Charge Surfaces. 1. Charge Effects and Structure of the Adsorbed Layer. Langmuir, 8, 2649-2659.

[33]   Pendleton, P. and Wu, S.H. (2003) Kinetics of Dodecanoic Acid Adsorption from Caustic Solution by Activated Carbon. Journal of Colloid and Interface Science, 266, 245-250.

[34]   Gao, J.P., Maguhn, J., Spitzauer, P. and Kettrup, A. (1998) Sorption of Pesticides in the Sediment of the Teufelsweiher Pond (Southern Germany). I: Equilibrium Assessments, Effect of Organic Carbon Content and pH. Water Research, 32, 1662-1672.

[35]   Mermut, A.R. and Cano, A.F. (2001) Baseline Studies of The Clay Minerals Society Source Clays: Chemical Analyses of Major Elements. Clays and Clay Minerals, 49, 381-386.

[36]   Chattopadhyay, S. and Traina, S.J. (1999) Spectroscopic Study of Sorption of Nitrogen Heterocyclic Compounds on Phyllosilicates. Langmuir, 15, 1634-1639.