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

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.

2003 ◽  
Vol 19 (03) ◽  
pp. 179-186
Author(s):  
Gary C. Schafran ◽  
R. Prasad ◽  
F. H. Thorn ◽  
R. Michael Ewing ◽  
J. Soles

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.


2003 ◽  
Vol 69 (10) ◽  
pp. 6025-6031 ◽  
Author(s):  
Elisa Varela ◽  
Ming Tien

ABSTRACT The redox cycle of 2,5-dimethoxybenzoquinone (2,5-DMBQ) is proposed as a source of reducing equivalent for the regeneration of Fe2+ and H2O2 in brown rot fungal decay of wood. Oxalate has also been proposed to be the physiological iron reductant. We characterized the effect of pH and oxalate on the 2,5-DMBQ-driven Fenton chemistry and on Fe3+ reduction and oxidation. Hydroxyl radical formation was assessed by lipid peroxidation. We found that hydroquinone (2,5-DMHQ) is very stable in the absence of iron at pH 2 to 4, the pH of degraded wood. 2,5-DMHQ readily reduces Fe3+ at a rate constant of 4.5 × 103 M−1s−1 at pH 4.0. Fe2+ is also very stable at a low pH. H2O2 generation results from the autoxidation of the semiquinone radical and was observed only when 2,5-DMHQ was incubated with Fe3+. Consistent with this conclusion, lipid peroxidation occurred only in incubation mixtures containing both 2,5-DMHQ and Fe3+. Catalase and hydroxyl radical scavengers were effective inhibitors of lipid peroxidation, whereas superoxide dismutase caused no inhibition. At a low concentration of oxalate (50 μM), ferric ion reduction and lipid peroxidation are enhanced. Thus, the enhancement of both ferric ion reduction and lipid peroxidation may be due to oxalate increasing the solubility of the ferric ion. Increasing the oxalate concentration such that the oxalate/ferric ion ratio favored formation of the 2:1 and 3:1 complexes resulted in inhibition of iron reduction and lipid peroxidation. Our results confirm that hydroxyl radical formation occurs via the 2,5-DMBQ redox cycle.


2008 ◽  
Vol 73 (4) ◽  
pp. 470-478 ◽  
Author(s):  
I. N. Shtarkman ◽  
S. V. Gudkov ◽  
A. V. Chernikov ◽  
V. I. Bruskov

1988 ◽  
Vol 251 (3) ◽  
pp. 893-899 ◽  
Author(s):  
H Iwahashi ◽  
T Ishii ◽  
R Sugata ◽  
R Kido

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.


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