Hydroxyl radical formation in aqueous reactions (pH 3-8) of iron(II) with hydrogen peroxide: the photo-Fenton reaction

1992 ◽  
Vol 26 (2) ◽  
pp. 313-319 ◽  
Author(s):  
Richard G. Zepp ◽  
Bruce C. Faust ◽  
Juerg Hoigne
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Fenton Reaction ◽  
Radical Formation ◽  
Aqueous Reactions

scholarly journals Superoxide dismutase enhances the formation of hydroxyl radicals in the reaction of 3-hydroxyanthranilic acid with molecular oxygen

1988 ◽  
Vol 251 (3) ◽  
pp. 893-899 ◽  
Author(s):  
H Iwahashi ◽  
T Ishii ◽  
R Sugata ◽  
R Kido
Keyword(s):  
Hydrogen Peroxide ◽  
Superoxide Dismutase ◽  
Hydroxyl Radical ◽  
Molecular Oxygen ◽  
Hydroxyl Radicals ◽  
Fenton Reaction ◽  
Potassium Phosphate ◽  
Radical Formation ◽  
Superoxide Anions ◽  
Hydroxyanthranilic Acid

Superoxide dismutase (SOD) enhanced the formation of hydroxyl radicals, which were detected by using the e.s.r. spin-trapping technique, in a reaction mixture containing 3-hydroxyanthranilic acid (or p-aminophenol), Fe3+ ions, EDTA and potassium phosphate buffer, pH 7.4. The hydroxyl-radical formation enhanced by SOD was inhibited by catalase and desferrioxamine, and stimulated by EDTA and diethylenetriaminepenta-acetic acid, suggesting that both hydrogen peroxide and iron ions participate in the reaction. The hydroxyl-radical formation enhanced by SOD may be considered to proceed via the following steps. First, 3-hydroxyanthranilic acid is spontaneously auto-oxidized in a process that requires molecular oxygen and yields superoxide anions and anthranilyl radicals. This reaction seems to be reversible. Secondly, the superoxide anions formed in the first step are dismuted by SOD to generate hydrogen peroxide and molecular oxygen, and hence the equilibrium in the first step is displaced in favour of the formation of superoxide anions. Thirdly, hydroxyl radicals are generated from hydrogen peroxide through the Fenton reaction. In this Fenton reaction Fe2+ ions are available since Fe3+ ions are readily reduced by 3-hydroxyanthranilic acid. The superoxide anions do not seem to participate in the reduction of Fe3+ ions, since superoxide anions are rapidly dismuted by SOD present in the reaction mixture.

A Systematic DFT Study of Two Elementary Steps Involving Hydrogen Peroxide and the Hydroxyl Radical in the Fenton Reaction

2018 ◽  
Author(s):  
Danilo Carmona ◽  
David Contreras ◽  
Oscar A. Douglas-Gallardo ◽  
Stefan Vogt-Geisse ◽  
Pablo Jaque ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Ab Initio ◽  
Fenton Reaction ◽  
Basis Set ◽  
Basis Sets ◽  
Dft Methods ◽  
Elementary Steps ◽  
Oxygen Oxygen ◽  
Complete Basis Set

The Fenton reaction plays a central role in many chemical and biological processes and has various applications as e.g. water remediation. The reaction consists of the iron-catalyzed homolytic cleavage of the oxygen-oxygen bond in the hydrogen peroxide molecule and the reduction of the hydroxyl radical. Here, we study these two elementary steps with high-level ab-initio calculations at the complete basis set limit and address the performance of different DFT methods following a specific classification based on the Jacob´s ladder in combination with various Pople's basis sets. Ab-initio calculations at the complete basis set limit are in agreement to experimental reference data and identified a significant contribution of the electron correlation energy to the bond dissociation energy (BDE) of the oxygen-oxygen bond in hydrogen peroxide and the electron affinity (EA) of the hydroxyl radical. The studied DFT methods were able to reproduce the ab-initio reference values, although no functional was particularly better for both reactions. The inclusion of HF exchange in the DFT functionals lead in most cases to larger deviations, which might be related to the poor description of the two reactions by the HF method. Considering the computational cost, DFT methods provide better BDE and EA values than HF and post--HF methods with an almost MP2 or CCSD level of accuracy. However, no systematic general prediction of the error based on the employed functional could be established and no systematic improvement with increasing the size in the Pople's basis set was found, although for BDE values certain systematic basis set dependence was observed. Moreover, the quality of the hydrogen peroxide, hydroxyl radical and hydroxyl anion structures obtained from these functionals was compared to experimental reference data. In general, bond lengths were well reproduced and the error in the angles were between one and two degrees with some systematic trend with the basis sets. From our results we conclude that DFT methods present a computationally less expensive alternative to describe the two elementary steps of the Fenton reaction. However, choice of approximated functionals and basis sets must be carefully done and the provided benchmark allows a systematic validation of the electronic structure method to be employed

Removal of Tributyltin in Shipyard Waters: Characterization and Treatment to Meet Low Parts per Trillion Levels

2003 ◽  
Vol 19 (03) ◽  
pp. 179-186
Author(s):  
Gary C. Schafran ◽  
R. Prasad ◽  
F. H. Thorn ◽  
R. Michael Ewing ◽  
J. Soles
Keyword(s):  
Hydrogen Peroxide ◽  
Activated Carbon ◽  
Hydroxyl Radical ◽  
Ultraviolet Irradiation ◽  
Treatment Plant ◽  
Full Scale ◽  
Radical Formation ◽  
Estuarine Waters ◽  
Treatment Conditions ◽  
Made In

Removal of tributyltin (TBT) from shipyard waters has been conducted in Virginia shipyards for over 2.5 years and has resulted in a 99% reduction of TBT discharged to coastal-estuarine waters. This has been achieved by conventional coagulation clarification for particulate TBT removal and removal of dissolved TBT using activated carbon. Although advances have been made in the understanding of TBT removal under various treatment conditions, TBT removal with the existing full-scale treatment plant to levels that would comply with a 50 parts per trillion (pptr) discharge limit are not possible. Results from study efforts that are currently ongoing suggest that the 50 pptr limit might be reached using ultraviolet irradiation or ozonation and that both processes would be substantially improved with the addition of hydrogen peroxide to promote hydroxyl radical formation.

Hydroxyl radical formation from bacteria-assisted Fenton chemistry at neutral pH under environmentally relevant conditions

2016 ◽  
Vol 13 (4) ◽  
pp. 757 ◽  
Author(s):  
Jarod N. Grossman ◽  
Tara F. Kahan
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Natural Waters ◽  
Shewanella Oneidensis ◽  
Radical Formation ◽  
Production Rates ◽  
Fenton Chemistry ◽  
Iron Reducing Bacteria ◽  
Neutral Ph ◽  
Reducing Bacteria

Environmental contextReactions in natural waters such as lakes and streams are thought to be extremely slow in the absence of sunlight (e.g. at night). We demonstrate that in the presence of iron, hydrogen peroxide and certain bacteria (all of which are common in natural waters), certain reactions may occur surprisingly quickly. These findings will help us predict the fate of many compounds, including pollutants, in natural waters at night. AbstractDark Fenton chemistry is an important source of hydroxyl radicals (OH•) in natural waters in the absence of sunlight. Hydroxyl radical production by this process is very slow in many bodies of water, owing to slow reduction and low solubility of FeIII at neutral and near-neutral pH. We have investigated the effects of the iron-reducing bacteria Shewanella oneidensis (SO) on OH• production rates from Fenton chemistry at environmentally relevant hydrogen peroxide (H2O2) and iron concentrations at neutral pH. In the presence of 2.0 × 10–4M H2O2, OH• production rates increased from 1.3 × 10–10 to 2.0 × 10–10Ms–1 in the presence of 7.0 × 106cellsmL–1 SO when iron (at a concentration of 100μM) was in the form of FeII, and from 3.6 × 10–11 to 2.2 × 10–10Ms–1 when iron was in the form of FeIII. This represents rate increases of factors of 1.5 and 6 respectively. We measured OH• production rates at a range of H2O2 concentrations and SO cell densities. Production rates depended linearly on both variables. We also demonstrate that bacteria-assisted Fenton chemistry can result in rapid degradation of aromatic pollutants such as anthracene. Our results suggest that iron-reducing bacteria such as SO may be important contributors to radical formation in dark natural waters.

Analysis of a complex produced in the Fenton oxidation process

2014 ◽  
Vol 69 (5) ◽  
pp. 1115-1119 ◽  
Author(s):  
Chang Wang ◽  
Siyue Zhang ◽  
Sakai Yuji ◽  
Zongpeng Zhang
Keyword(s):  
Hydrogen Peroxide ◽  
Complex Formation ◽  
Hydroxyl Radical ◽  
Fenton Reaction ◽  
Oxidation Process ◽  
Fenton Oxidation ◽  
Radical Theory ◽  
Uv Visible ◽  
Iron Based ◽  
Fenton Oxidation Process

The absorbances of different concentrations of Fe2+, Fe3+ and H2O2 were investigated by UV-visible spectrophotometry without separating the substances. The law of complex formation was studied by considering changes in the UV-vis spectra of mixtures of these three substances. The results show that upon eliminating the influence of the substrate, an iron-based complex was present in the Fenton reaction, which exhibited substantial absorbance from 190 to 500 nm. Therefore, the presence of an unknown complex in the Fenton oxidation process was verified and its concentration varied with a change in the concentration of hydrogen peroxide. This study provides a strong foundation for further studies into the mechanism of traditional hydroxyl radical theory of the Fenton reaction.

Effect of amino acids on X-ray-induced hydrogen peroxide and hydroxyl radical formation in water and 8-oxoguanine in DNA

2008 ◽  
Vol 73 (4) ◽  
pp. 470-478 ◽  
Author(s):  
I. N. Shtarkman ◽  
S. V. Gudkov ◽  
A. V. Chernikov ◽  
V. I. Bruskov
Keyword(s):  
Amino Acids ◽  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Radical Formation ◽  
X Ray
Sign in / Sign up

Export Citation Format

Share Document