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Surfactant-modified bentonite clays: preparation, characterization, and atrazine removal

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Abstract

Bentonite clay was modified using quaternary ammonium cations, viz. phenyltrimethylammonium (PTMA), hexadecyltrimethylammonium (HDTMA), trioctylmethylammonium (TOMA) [100 % of cation exchange capacity of clay], and stearylkonium (SK) [100 % (SK-I) and 250 % (SK-II) of cation exchange capacity of clay]. The organoclays were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, and scanning electron microscopy (SEM). Atrazine adsorption on modified clays was studied using a batch method. Bentonite clay was a poor adsorbent of atrazine as 9.4 % adsorption was observed at 1 μg mL−1 atrazine concentration. Modification of clay by PTMA cation did not improve atrazine adsorption capacity. However, atrazine adsorption in HDTMA-, TOMA-, and SK-bentonites varied between 49 and 72.4 % and data fitted well to the Freundlich adsorption isotherm (R > 0.96). Adsorption of atrazine in organoclays was nonlinear and slope (1/n) values were <1. The product of Freundlich adsorption constants, K f(1/n) in HDTMA-, TOMA-, and SK-I-bentonites was 239.2, 302.4, and 256.6, respectively, while increasing the SK cation loading in the clay (SK-II) decreased atrazine adsorption [K f(1/n) − 196.4]. Desorption of atrazine from organoclays showed hysteresis and TOMA- and SK-I-bentonites were the best organoclays to retain the adsorbed atrazine. Organoclays showed better atrazine removal from wastewater than an aqueous solution. The synthesized organoclays may find application in soil and water decontamination and as a carrier for atrazine-controlled released formulations.

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References

  • Abate G, Masini JC (2005) Sorption of atrazine, propazine, deethylatrazine, deisopropylatrazine and hydroxyatrazine on organovermiculite. J Braz Chem Soc 16:936–943

    Article  CAS  Google Scholar 

  • Akçay G, Yurdakoç MK (1999) Nonyl- and dodecylamines intercalated bentonite and illite from Turkey. Turk J Chem 23:105–113

    Google Scholar 

  • Borisover M, Graber ER, Bercovich F, Gerstl Z (2001) Suitability of dye-clay complexes for removal of non-ionic organic compounds from aqueous solution. Chemosphere 44:1033–1040

    Article  CAS  Google Scholar 

  • Boyd SA, Jaynes WF, Ross BS (1991) Immobilization of organic contaminants by organo-clays: application to soil restoration and hazardous waste contaminants. In: Baker RA (ed) Organic substances and sediments in water, vol 1, CRC Press. Boca Raton, FL, pp 181–200

    Google Scholar 

  • Celis R, Hermosín MC, Carrizosa MJ, Cornejo J (2002) Inorganic and organic clays as carriers for controlled release of herbicide hexazinone. J Agril Food Chem 50:2324–2330

    Article  CAS  Google Scholar 

  • El-Nahhal Y, Nir S, Polubesova T, Margulies L, Rubin B (1998) Movement of metolachlor in soil: effect of new organoclay formulations. Pest Sci 55:857–864

    Article  Google Scholar 

  • El-Nahhal Y, Nir S, Polubesova T, Margulies L, Rubin B (1999) Leaching, phytotoxicity and weed control of new formulations of alachlor. J Agril Food Chem 42:1223–1227

    Google Scholar 

  • El-Nahhal Y, Nir S, Serban C, Rabinovitch O, Rubin B (2000) Montmorillonite-phenyltrimethylammonium yields environmentally improved formulations of hydrophobic herbicides. J Agril Food Chem 48:4791–4801

    Article  CAS  Google Scholar 

  • Farmer VC (1974) The layer silicates. In: Farmer VC (ed) The infrared spectra of minerals, Mineralogical Society Monograph 4. London, pp 331–363

  • Gaynor JD, Mactavish DC, Findlay WI (1995) Atrazine and metolachlor loss in surface and subsurface runoff from three tillage treatments in corn. J Environ Qual 24:246–256

    Article  CAS  Google Scholar 

  • Giles CH, McEvans TH, Nakhwa SN, Smith D (1960) Studies in adsorption. Part XI: a system of classification of adsorption isotherms and its use in diagnosis of desorption mechanism and measurement of specific surface areas of solids. J Chem Soc 3:3973–3993

    Article  Google Scholar 

  • Gilliom RJ (2007) Pesticides in U.S. streams and groundwater. Environ Sci Technol 41:3408–3414

    Article  CAS  Google Scholar 

  • Groisman L, Rav-Acha C, Gerstl Z, Mingelgrin U (2004) Sorption of organic compounds of varying hydrophobicities from water and industrial wastewater by long- and short-chain organoclays. Appl Clay Sci 24:159–166

  • Hermosín MC, Calderon MJ, Aguer JP, Cornejo J (2001) Organoclays for controlled release of the herbicide fenuron. Pest Manag Sci 57:803–809

    Article  Google Scholar 

  • Jackson ML (1967) Soil chemical analysis. Prentice Hall Inc., New Delhi, India

    Google Scholar 

  • Keeney DR, Nelson DW (1989) Nitrogen inorganic forms. In: Page AL (ed) Methods of soil analysis, part 2: chemical and microbiological properties. Soil Science Society of America and American Society of Agronomy, Madison, WI, pp 643–698

    Google Scholar 

  • Li Z, Alessi D, Allen L (2002) Influence of quaternary ammonium on sorption of selected metal cations onto clinoptilolite zeolite. J Environ Qual 31:1106–1114

    Article  CAS  Google Scholar 

  • Mishael YG, Undabeytia T, Rabinovitz O, Rubin B, Nir S (2002) Slow-release formulations of sulfometuron incorporated in micelles adsorbed on montmorillonite. J Agril Food Chem 50:2864–2869

    Article  CAS  Google Scholar 

  • Poinke HB, Glotfelty DE, Lucas AD, Urban JB (1998) Pesticide contamination of groundwater in the Mahantango Creek Watershed. J Environ Qual 7:76–84

    Google Scholar 

  • Sánchez-Camazano M, Sánchez-Martín MJ (1994) Organo-clays as adsorbents for azinphosmethyl and dichlorvos in aqueous medium. Water Air Soil Pollut 74:19–28

    Article  Google Scholar 

  • Sánchez-Martín MJ, Rodriguez-Cruz MS, Andrades MS, Sánchez-Camazano M (2006) Efficiency of different clay minerals modified with a cationic surfactant in the adsorption of pesticides: influence of clay type and pesticide hydrophobicity. Appl Clay Sci 31:216–228

    Article  Google Scholar 

  • Trigo C, Koskinen WC, Celis R, Sadowsky MJ, Hermosín MC, Cornejo J (2010) Bioavailability of organoclay formulations of atrazine in soils. J Agril Food Chem 58:11857–11863

    Article  CAS  Google Scholar 

  • Undabeytia T, Nir S, Rubin B (2000) Organo-clay formulation of the hydrophobic herbicide norflurazon yield reduced leaching. J Agril Food Chem 48:4767–4773

    Article  CAS  Google Scholar 

  • Undabeytia T, Nir S, Sánchez-Verdejo T, Villaverde J, Maqueda C, Morillo E (2008) A clay-vesicle system for water purification from organic pollutants. Water Res 42:1211–1219

    Article  CAS  Google Scholar 

  • USDHHS, United States Department of Health and Human Services (2003) Toxicological profile for atrazine. Public Health Service, Agency for Toxic Substances and Disease Registry (ATDSR), Atlanta, GA. http://www.atsdr.cdc.gov/ToxProfiles/tp153.pdf. Accessed 21 March 2014

  • USEPA, United States Environment Protection Agency (2009) National primary drinking water regulations. EPA 816-F-09-004, May 2009. http://www.epa.gov/safewater/consumer/pdf/mcl.pdf. Accessed 21 March 2014

  • USEPA, United States Environmental Protection Agency (2006) Decision documents for atrazine. Washington D.C., USA. http://www.epa.gov/oppsrrd1/REDs/atrazine_combined_docs.pdf. Accessed 7 February 2013

  • Wang Q, Yang W, Liu W (1999) Adsorption of acetanilide herbicides on soils and its correlation with soil properties. Pestic Sci 55:1103–1108

    Article  CAS  Google Scholar 

  • Zhang ZZ, Sparks DL, Scrivner SC (1993) Sorption and desorption of quaternary amine cations on clays. Environ Sci Technol 27:1625–1631

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Anirban Dutta was supported by INSPIRE Fellowship from the Department of Science and Technology (DST), Government of India, New Delhi, India.

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Correspondence to Neera Singh.

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Responsible editor: Philippe Garrigues

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Dutta, A., Singh, N. Surfactant-modified bentonite clays: preparation, characterization, and atrazine removal. Environ Sci Pollut Res 22, 3876–3885 (2015). https://doi.org/10.1007/s11356-014-3656-3

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