Photolytic and radiolytic oxidation of humic acid.

Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA, CCT La Plata-CONICET/UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, La Plata, Argentina.
Photochemistry and Photobiology (Impact Factor: 2.29). 02/2012; 88(4):810-5. DOI: 10.1111/j.1751-1097.2012.01116.x
Source: PubMed

ABSTRACT The reactions of Br(2)(˙-), Br˙, HO˙ and N(3)˙ with Aldrich humic acid (AHA) were investigated. The Br/Br(2)(˙-) radicals were obtained in flash-photolysis experiments (λ(exc) = 266 nm) performed with NaS(2)O(8) solutions in the presence of bromide ions. HO˙ and N(3)˙ radicals were generated by pulse radiolysis of N(2)O-saturated solutions. From the combination of a bilinear analysis and computer simulations of the absorbance traces, it was possible to obtain information on the rate constants for the reactions of Br(2)(˙-), Br˙, HO˙ and N(3)˙ with AHA and on the intermediate species involved in the mechanism. Evidence for the participation of phenoxyl radicals (λ(max) = 410 nm) is given.

  • [Show abstract] [Hide abstract]
    ABSTRACT: Transformation of dissolved organic matter (DOM) during ozonation results in a higher reduction in trihalomethane formation potential (THMFP) relative to dissolved organic carbon (DOC). This study was conducted to determine the effect of DOM transformation after ozonation on THM formation and to elucidate the difference in THMFP and DOC removal. Changes in DOC, THMFP, reactivities of the hydrophilic and hydrophobic DOC, and phenolic-OH were determined to explain the difference in THMFP and DOC removal after ozonation. Higher reduction in THMFP (24-46%) relative to DOC (10-16%) was obtained and was attributed to the following: transformation of DOM from a more reactive hydrophobic DOC (microg THM produced per mg organic carbon) to a less reactive hydrophilic DOC and to the decrease in the reactivities of both the hydrophobic and hydrophilic DOC after ozonation. The results also showed decrease in phenolic-OH indicating the oxidation of some reactive sites like resorcinol or meta-dihydroxy benzene ring structures, which are prone to chlorine substitution, consequently decreasing the reactivity of the organic carbon to form THM. These changes in DOM led to a significant decrease in THMFP with no remarkable removal in DOC.
    Water Research 07/2001; 35(9):2201-6. · 4.66 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: By monitoring the decay of SO4*- after flash photolysis of aqueous solutions of S2O82- at different pH values, the kinetics of the reaction of SO4*- radicals with gallic acid and the gallate ion was investigated. The bimolecular rate constants for the reactions of the sulfate radicals with gallic acid and the gallate ion were found to be (6.3 +/- 0.7) x 10(8) and (2.9 +/- 0.2) x 10(9) M(-1) s(-1), respectively. On the basis of the oxygen-independent second-order decay kinetics and on their absorption spectra, the organic radicals formed as intermediates of these reactions were assigned to the corresponding phenoxyl radicals. DFT calculations in the gas phase and aqueous solution support formation of the phenoxyl radicals by H abstraction from the phenols to the sulfate radical anion. The observed recombination of the phenoxyl radicals of gallic acid to yield substituted biphenyls and quinones is also supported by the calculations. HPLC/MS product analysis showed formation of one of the predicted quinones.
    The Journal of Physical Chemistry A 03/2008; 112(6):1188-94. · 2.77 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: Reactions of chlorine radicals might play a role in aqueous aerosols where a core of inorganic components containing insulators such as SiO2 and dissolved HUmic-LIke Substances (HULIS) are present. Herein, we report conventional flash photolysis experiments performed to investigate the aqueous phase reactions of silica nanoparticles (NP) and humic acid (HA) with chlorine atoms, Cl*, and dichloride radical anions, Cl2*-. Silica NP and HA may be taken as rough models for the inorganic core and HULIS contained in atmospheric particles, respectively. Both Cl* and Cl2*- were observed to react with the deprotonated silanols on the NP surface with reaction rate constants, k +/- sigma, of (9 +/- 6) x 10(7) M(-1) s(-1) and (7 +/- 4) x 10(5) M(-1) s(-1), respectively. The reaction of Cl* with the surface deprotonated silanols leads to the formation of SiO* defects. HA are also observed to react with Cl* and Cl2*- radicals, with reaction rate constants at pH 4 of (3 +/- 2) x 10(10) M(-1) s(-1) and (1.2 +/- 0.3) x 10(9) M(-1) s(-1), respectively. The high values observed for these constants were discussed in terms of the multifunctional heterogeneous mixture of organic molecules conforming HA.
    Photochemistry and Photobiology 01/2007; 83(4):944-51. · 2.29 Impact Factor


Available from
May 21, 2014