Shikha Garg

Superoxide-mediated formation and charging of silver nanoparticles.

Contemporary studies indicate that reactive oxygen species (ROS) such as superoxide play a key role in the toxicity and behavior of silver nanoparticles (AgNPs). While there have been suggestions that superoxide is able to reduce silver(I) ions with resultant production of AgNPs, no experimental evidence that this process actually occurs has been produced. Here we present definitive experimental evidence for the reduction of silver(I) by superoxide. A second-order rate constant of 64.5 ± 16.3 M(-1)·s(-1) is determined for this reaction in the absence of AgNPs. The overall rate constant, however, increases by at least 4 orders of magnitude in the presence of AgNPs. A model based on electron charging and discharging of AgNPs satisfactorily describes the kinetics of this process. The ability for AgNPs to undergo catalytic cycling provides a pathway for the continual generation of ROS and the regeneration of AgNPs following oxidation.

H2O2-Mediated Oxidation of Zero-Valent Silver and Resultant Interactions among Silver Nanoparticles, Silver Ions, and Reactive Oxygen Species

The H(2)O(2)-mediated oxidation of silver nanoparticles (AgNPs) over a range of pH (3.0-14.0) is investigated here, and an electron charging-discharging model capable of describing the experimental results obtained is developed. AgNPs initially react with H(2)O(2) to form Ag(+) and superoxide, with these products subsequently reacting to reform AgNPs (in-situ-formed AgNPs) via an electron charging-discharging mechanism. Our experimental results show that the AgNP reactivity toward H(2)O(2) varies significantly with pH, with the variation at high pH (>10) due particularly to the differences in the reactivity of H(2)O(2) and its conjugate base HO(2)(-) with AgNPs whereas at lower pH (3-10) the pH dependence of H(2)O(2) decay is accounted for, at least in part, by the pH dependence of the rate of superoxide disproportionation. Our results further demonstrate that the in-situ-formed AgNPs resulting from the superoxide-mediated reduction of Ag(+) have a different size and reactivity compared to those of the citrate-stabilized particles initially present. The turnover frequency for AgNPs varies significantly with pH and is as high as 1776.0 min(-1) at pH 11.0, reducing to 144.2 min(-1) at pH 10.0 and 3.2 min(-1) at pH 3.0.

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron–Natural Organic Matter Interactions

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

Iron uptake by the ichthyotoxic Chattonella marina (Raphidophyceae): impact of superoxide generation

Significant production of superoxide, a known reductant of both inorganic and organically complexed iron(III), occurs in natural systems by both biotic and abiotic pathways. We have investigated the generation of superoxide by Chattonella marina (Subrahman.) Y. Hara et Chihara, a phytoplankton taxon known to produce high levels of this reactive oxygen species, and examined the role of superoxide in the acquisition of iron by this organism. Additionally, a generalized model for iron acquisition by C. marina has been developed, which includes three pathways of iron acquisition from organically complexed iron(III): nondissociative reductive uptake, dissociative reductive uptake, and nonreductive dissociative uptake. The model is shown to be particularly useful in ascertaining the relative importance of these various iron‐uptake pathways as a function of solution parameters including concentration and iron‐binding strength of the organic ligand and superoxide concentration. Our results suggest that superoxide can participate in the C. marina iron‐uptake process when iron is complexed to weak ligands, such as citrate, but plays only a minor role when iron is bound to a strong ligand. It thus appears that facilitation of iron acquisition is not the sole purpose of superoxide production by these organisms.

Production of Reactive Oxygen Species on Photolysis of Dilute Aqueous Quinone Solutions

We have examined the generation of the reactive oxygen species (ROS) superoxide and hydrogen peroxide (H2O2) by irradiation of dilute aqueous solutions of disodium anthraquinone‐2‐6‐disulfonate (AQDS) with simulated sunlight. Irradiating a solution of AQDS in 2 mM NaHCO3 and 0.01 M NaCl produced superoxide and H2O2 at nanomolar concentrations. Experiments in which initial concentrations of dioxygen, H2O2, the superoxide radical trap nitroblue tetrazolium and the electron donor dimethyl sulfoxide were varied suggested that the interaction of solvent water with photo‐excited quinone moieties produces dioxygen‐reducing radicals, and that these are the primary source of ROS in the system. A kinetic model for ROS production is proposed based on our experimental data.

Mechanism and kinetics of dark iron redox transformations in previously photolyzed acidic natural organic matter solutions

Stable organic species produced on irradiation of Suwannee River Fulvic Acid (SRFA) are shown to be important oxidants of Fe(II) in aqueous solutions at acidic pH, with rate constants substantially larger than those for oxygenation of Fe(II) under the same conditions. These Fe(II)-oxidizing species, which are formed during photolysis by superoxide-mediated oxidation of reduced organic moieties that are present intrinsically in SRFA, are long-lived in the dark but prone to rapid oxidation by singlet oxygen ((1)O(2)) under irradiated conditions. The intrinsic reduced organic species are able to reduce Fe(III) at acidic pH. Although the exact identities of the organic Fe(II) oxidant and the organic Fe(III) reductant are unclear, their behavior is consistent with that expected of semiquinone and hydroquinone-like moieties respectively. A kinetic model is developed that adequately describes all aspects of the experimental data obtained, and which is capable of predicting dark Fe(II) oxidation rates and Fe(III) reduction rates in the presence of previously photolyzed natural organic matter.

Oxidative Dissolution of Silver Nanoparticles by Chlorine: Implications to Silver Nanoparticle Fate and Toxicity

The kinetics of oxidative dissolution of silver nanoparticles (AgNPs) by chlorine is investigated in this work, with results showing that AgNPs are oxidized in the presence of chlorine at a much faster rate than observed in the presence of dioxygen and/or hydrogen peroxide. The oxidation of AgNPs by chlorine occurs in air-saturated solution in stoichiometric amounts with 2 mol of AgNPs oxidized for each mole of chlorine added. Dioxygen plays an important role in OCl(-)-mediated AgNP oxidation, especially at lower OCl(-) concentrations, with the mechanism shifting from stoichiometric oxidation of AgNPs by OCl(-) in the presence of dioxygen to catalytic removal of OCl(-) by AgNPs in the absence of dioxygen. These results suggest that the presence of chlorine will mitigate AgNP toxicity by forming less-reactive AgCl(s) following AgNP oxidation, although the disinfection efficiency of OCl(-) may not be significantly impacted by the presence of AgNPs because a chlorine-containing species is formed on OCl(-) decay that has significant oxidizing capacity. Our results further suggest that the antibacterial efficacy of nanosilver particles embedded on fabrics may be negated when treated with detergents containing strong oxidants, such as chlorine.

Iron Redox Transformations in Continuously Photolyzed Acidic Solutions Containing Natural Organic Matter: Kinetic and Mechanistic Insights

In this work, the various pathways contributing to the formation and decay of Fe(II) in photolyzed acidic solutions containing Suwannee River fulvic acid (SRFA) are investigated. Results of experimental and computational studies suggest that ligand to metal charge transfer (LMCT), superoxide-mediated iron reduction and interaction with reduced organic species that are present intrinsically in SRFA each contribute to Fe(III) reduction with LMCT the most likely dominant pathway under these conditions. Fe(II) oxidation occurs as a result of its interaction with a variety of light-generated species including (i) short-lived organic species, (ii) relatively stable semiquinone-like organic species, and (iii) hydroperoxy radicals. While not definitive, a hypothesis that the short-lived organic species are similar to peroxyl radicals appears most consistent with our experimental and modeling results. The semiquinone-like organic species formed during photolysis by superoxide-mediated oxidation of reduced organic moieties are long-lived in the dark but prone to rapid oxidation by singlet oxygen ((1)O2) under irradiated conditions and thus play a minor role in Fe(II) oxidation in the light. A kinetic model is developed that adequately describes all aspects of the experimental data obtained and which is capable of predicting Fe(II) oxidation rates and Fe(III) reduction rates in the presence of natural organic matter and light.

Redox Transformations of Iron in the Presence of Exudate from the Cyanobacterium Microcystis aeruginosa under Conditions Typical of Natural Waters

Interaction of the exudate secreted by a toxic strain of the cyanobacterium Microcystis aeruginosa with Fe(II) and Fe(III) was investigated here under both acidic (pH 4) and alkaline (pH 8) conditions. At the concentrations of iron and exudate used, iron was present as dissolved iron (<0.025 μm) at pH 4 but principally as small (<0.45 μm) iron oxyhydroxide particles at pH 8 with only ∼3-27% present in the dissolved form as a result of iron binding by the organic exudate. The formation of strong Fe(III) exudate and relatively weak Fe(II) exudate complexes alters the reduction potential of the Fe(III)-Fe(II) redox couple, facilitating more-rapid oxidation of Fe(II) at pH 4 and 8 than was the case in the absence of exudate. Our results further show that the organic exudate contains Fe(III)-reducing moieties, resulting in the production of measurable concentrations of Fe(II). However, these reducing moieties are short-lived (with a half-life of 1.9 h) and easily oxidized in air-saturated environments. A kinetic model was developed that adequately describes the redox transformation of Fe in the presence of exudate both at pH 4 and pH 8.

Effects of Good’s Buffers and pH on the Structural Transformation of Zero Valent Iron and the Oxidative Degradation of Contaminants

The presence of Goods buffers caused rapid ZVI corrosion and a dramatic release of Fe(II) leading to the Fe(II)-catalyzed transformation of ferrihydrite to lepidocrocite and/or the direct formation of lepidocrocite from the oxidation of Fe(II) in the pH range 4.0-6.2. In comparison, in the absence of Goods buffers, elution of Fe(II) was insignificant with ferrihydrite being the only Fe(III) oxyhydroxide detected following the oxidative transformation of ZVI. The rapid ZVI corrosion in the presence of Goods buffer is possibly due to either (i) disruption of the Fe oxide surface layer as a result of attack by Goods buffers and/or (ii) interaction of Goods buffer with the outer Fe oxide surface and surface-associated Fe(II)/Fe(III) causing the Fe oxide surface layers to be more porous with both these processes facilitating continuous O2 access to the Fe(0) core and allowing the diffusion of Fe atoms outward. Our results further show that the deprotonated forms of Goods buffers and the surface charge of the Fe oxides formed at the ZVI surface strongly affect the sorption of the target compound (i.e., formate) and hence the oxidation of these compounds via surface-associated Fe(II)-mediated heterogeneous Fenton processes.