The complete destruction of separate mixtures of 1.1 mM 4-chlorophenol (aqueous) and 0.61 mM pentachlorophenol (aqueous slurry) take place in the presence of 0.5 g of iron particles in 10 mL of 0.32 mM ethylenediaminetetraacetic acid (EDTA) under ambient air under room temperature conditions. Under this reaction condition, the time required to reach complete disappearance to the detection limit of GC-FID for each compound was 4 h for 4-chlorophenol and 70 h for pentachlorophenol. Electrospray ionization mass spectral (ESI-MS) analysis of the 4-chlorophenol reaction mixture after its complete disappearance indicated non-chlorinated, primarily low molecular weight products; however, Clfrom 4-chlorophenol was not detected due to adsorption onto the iron or its corrosion products. Radical trap and control experiments suggest that the mechanism for destruction initiates with dioxygen activation, leading to the formation of reactive oxygen species (ROS) and ultimately ring opening of the phenolic compounds. This is the first example of an abiotic system capable of the complete destruction of an organic pollutant under room temperature and pressure conditions through dioxygen activation chemistry.

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The acid dissociation and ferric stability constants for complexation by the flavonoids 3-hydroxyflavone (flavonol), 5,7-dihydroxyflavone (chrysin), and 3',4'-dihydroxyflavone in 50:50 (v/v) ethanol/water are determined by pH potentiometric and spectrophotometric titrations and the linear least-squares curve-fitting program Hyperquad. Over the entire range of pH and reagent concentrations spanning the titration experiments, the stoichiometry for iron-flavonoid complex formation was 1:1 for all three flavonoids examined. The three flavonoids were chosen for their hydroxy substitution pattern, with each possessing one of the three most commonly suggested sites for metal binding by the flavonoids. On the basis of the calculated stability constants, the intraflavonoid-binding site competition is illustrated as a function of pH via speciation curves. The curves indicate that the binding site comprised of the 3',4'-hydroxy substitutions, the catecholic site, is most influential for ferric complexation at the physiological pH of 7.4. The possibility for antioxidant activity by flavonoid chelation of ferric iron in the presence of other competitive physiological complexing agents is demonstrated through additional speciation calculations.

The organophosphorus insecticide malathion was selected as an analog for the chemical nerve agent, VX. Degradation of 0.44 mM malathion in a 10 mL aqueous solution containing 0.50 g granular zero valent iron (ZVI) under ambient air and pressure was complete after 4 h to the detection limit of GC-FID. The degradation kinetics demonstrate the system to be pseudo-first-order with respect to malathion disappearance with a rate constant of 0.92 h 21 . The only non-polar organic intermediates detected were diethyl succinate and malaoxon, of which malaoxon is degraded to below the limit of detection of the GC-FID after 12 h. Electrospray ionization mass spectral analyses show the final reaction products to be low molecular weight carboxylic acids (propionic, oxalic and iminodiacetic acid).