title: Micellar catalyzed degradation of fenitrothion, an organophosphorus pesticide, in solution and soils.
abstract: We report on a study of the decomposition of fenitrothion (an organophosphorus pesticide that is a persistent contaminant in soils and groundwater) as catalyzed by cetyltrimethylammonium (CTA+) micelles. The CTA micelles were associated with two types of counterions: (1) inert counterions (e.g. CTABr) and (2) reactive counterions (e.g. CTAOH). The reactive counterion surfactants used were hydroxide anion (HO-) as a normal nucleophile and hydroperoxide anion (HOO-) and the anion of pyruvaldehyde oxime (MINA-) as two alpha-nucleophiles. The reactivity order followed: CTABr < CTAOH < CTAMINA << CTAOOH. Treatment of the rate data using the Pseudo-Phase Ion Exchange (PPIE) model of micellar catalysis showed the ratio k2M/k2w to be less than unity for all the surfactants employed. Rather than arising from a "true catalysis", we attributed the observed rate enhancements to a "concentration effect", where both pesticide and nucleophile were incorporated into the small micellar phase volume. Furthermore, the CTAOOH/CTAOH pair gave an alpha-effect of 57, showing that the alpha-effect can play an important role in micellar systems. We further investigated the effectiveness of reactive counterion surfactants in decontaminating selected environmental solids that were spiked with 27 ppb fenitrothion. The solids were as follows: the clay mineral montmorillonite and SO-1 and S0-2 soils (obtained from the Canadian Certified Reference Materials Project). The reactive counterion surfactant solutions significantly enhanced the rate of fenitrothion degradation in the spiked solids over that obtained when the spiked solid was placed in contact with either 0.02 M KOH or water. The rate enhancements followed the order CTAOOH >> CTAMINA approximately CTAOH > KOH >> water. We conclude that reactive counterion surfactants, especially with alpha-nucleophiles, hold great potential in terms of remediating soils contaminated by toxic organophosphorus esters.
authors.affiliation: Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada.
authors.forename: Vimal K
authors.initials: VK
authors.lastname: Balakrishnan
authors.forename: Erwin
authors.initials: E
authors.lastname: Buncel
authors.forename: Gary W
authors.initials: GW
authors.lastname: Vanloon
mesh_terms: D002384:Catalysis; D002593:Cetrimonium Compounds / Q000737:chemistry; D005278:Fenitrothion / Q000032:analysis*; D006861:Hydrogen Peroxide / Q000737:chemistry; D007700:Kinetics; D008823:Micelles; D008956:Models, Chemical; D010575:Pesticides / Q000032:analysis*; D011765:Pyruvaldehyde / Q000737:chemistry; D012037:Refuse Disposal / Q000379:methods*; D012989:Soil Pollutants / Q000032:analysis*; D012996:Solutions; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D002593:Cetrimonium Compounds; D008823:Micelles; D010575:Pesticides; D012989:Soil Pollutants; D012996:Solutions; D014874:Water Pollutants, Chemical; D011765:Pyruvaldehyde; D006861:Hydrogen Peroxide; D005278:Fenitrothion