Serge P. Troeber

Bio: Serge P. Troeber is an academic researcher. The author has contributed to research in topics: Goethite & Oxide. The author has an hindex of 1, co-authored 1 publications receiving 436 citations.

Reduction of Substituted Nitrobenzenes by Fe(II) in Aqueous Mineral Suspensions.

Abstract: The kinetics of the reduction of 10 monosubstituted nitrobenzenes (NBs) by Fe(II) has been investigated under various experimental conditions in aqueous suspensions of minerals commonly present in soils and sediments. Aqueous solutions of Fe(II) were unreactive. In suspensions of Fe(III)-containing minerals (magnetite, goethite, and lepidocrocite), Fe(II) readily reduced the NBs to the corresponding anilines in a strongly pH-dependent reaction. Our results suggest that on other mineral surfaces (γ-aluminum oxide, amorphous silica, titanium dioxide, and kaolinite) iron (hydr)oxide coatings are indispensable to promote the reduction of NBs by adsorbed Fe(ll). Apparent pseudo-first-order rate constants, k obs , were used to describe the initial kinetics of the NB reduction, covering several half-lives of the compounds. The distinct effect of substituents on k obs and the observed pronounced competition between different NBs indicate that precursor complex formation as well as the (re)generation of reactive surface sites are rate-determining steps in the overall reduction of the NBs. The results of this study demonstrate that Fe(ll) adsorbed on iron (hydr)oxide surfaces or surface coatings may play an important role in the reductive transformation of organic pollutants in subsurface environments. Our findings may also contribute to a better understanding of the various redox processes involved in groundwater remediation techniques based on Fe(0) as the bulk reductant.

Spectroscopic Evidence for Fe(II)−Fe(III) Electron Transfer at the Iron Oxide−Water Interface

Abstract: Using the isotope specificity of 57Fe Mossbauer spectroscopy, we report spectroscopic observations of Fe(II) reacted with oxide surfaces under conditions typical of natural environments (i.e., wet, anoxic, circumneutral pH, and about 1% Fe(II)). Mossbauer spectra of Fe(II) adsorbed to rutile (TiO2) and aluminum oxide (Al2O3) show only Fe(II) species, whereas spectra of Fe(II) reacted with goethite (α-FeOOH), hematite (α-Fe2O3), and ferrihydrite (Fe5HO8) demonstrate electron transfer between the adsorbed Fe(II) and the underlying iron(III) oxide. Electron-transfer induces growth of an Fe(III) layer on the oxide surface that is similar to the bulk oxide. The resulting oxide is capable of reducing nitrobenzene (as expected based on previous studies), but interestingly, the oxide is only reactive when aqueous Fe(II) is present. This finding suggests a novel pathway for the biogeochemical cycling of Fe and also raises important questions regarding the mechanism of contaminant reduction by Fe(II) in the presenc...

Biological Degradation of 2,4,6-Trinitrotoluene

Abstract: Nitroaromatic compounds are xenobiotics that have found multiple applications in the synthesis of foams, pharmaceuticals, pesticides, and explosives. These compounds are toxic and recalcitrant and are degraded relatively slowly in the environment by microorganisms. 2,4,6-Trinitrotoluene (TNT) is the most widely used nitroaromatic compound. Certain strains of Pseudomonas and fungi can use TNT as a nitrogen source through the removal of nitrogen as nitrite from TNT under aerobic conditions and the further reduction of the released nitrite to ammonium, which is incorporated into carbon skeletons. Phanerochaete chrysosporium and other fungi mineralize TNT under ligninolytic conditions by converting it into reduced TNT intermediates, which are excreted to the external milieu, where they are substrates for ligninolytic enzymes. Most if not all aerobic microorganisms reduce TNT to the corresponding amino derivatives via the formation of nitroso and hydroxylamine intermediates. Condensation of the latter compounds yields highly recalcitrant azoxytetranitrotoluenes. Anaerobic microorganisms can also degrade TNT through different pathways. One pathway, found in Desulfovibrio and Clostridium, involves reduction of TNT to triaminotoluene; subsequent steps are still not known. Some Clostridium species may reduce TNT to hydroxylaminodinitrotoluenes, which are then further metabolized. Another pathway has been described in Pseudomonas sp. strain JLR11 and involves nitrite release and further reduction to ammonium, with almost 85% of the N-TNT incorporated as organic N in the cells. It was recently reported that in this strain TNT can serve as a final electron acceptor in respiratory chains and that the reduction of TNT is coupled to ATP synthesis. In this review we also discuss a number of biotechnological applications of bacteria and fungi, including slurry reactors, composting, and land farming, to remove TNT from polluted soils. These treatments have been designed to achieve mineralization or reduction of TNT and immobilization of its amino derivatives on humic material. These approaches are highly efficient in removing TNT, and increasing amounts of research into the potential usefulness of phytoremediation, rhizophytoremediation, and transgenic plants with bacterial genes for TNT removal are being done.

Superoxide radical driving the activation of persulfate by magnetite nanoparticles: Implications for the degradation of PCBs

Abstract: Magnetite nanoparticles (MNPs) are ubiquitous components of the subsurface environment, and increasing attention has been paid to MNPs due to their highly reductive and heterogeneous catalysis reactivity for the degradation of organic contaminants. However, most previous research studies neglected the generation of reactive oxygen species (ROS) by MNPs, which plays an important role in the transformation of contaminants. In this paper, we investigated the activation of persulfate (PS) by MNPs for the degradation of 2,4,4′-CB (PCB28), a selected model compound, and the underlying mechanism was elucidated. The results indicated that the PS can be activated by MNPs efficiently for the degradation of PCB28 at neutral pH. Electron paramagnetic resonance (EPR) technique was used to detect and identify the radical species in these processes. The mechanism of the activation of PS by MNPs was that superoxide radical anion (O2 −) generated by MNPs could activate the PS to produce more sulfate radicals (SO4 −), which favored the degradation of PCB28. The conclusion was further confirmed by quenching studies with the addition of superoxide dismutase (SOD). The effects of Fe(II) and pH on the degradation of PCB28 by PS/MNPs as well as the generation of ROS by MNPs were also studied. Both sorbed Fe(II) on MNPs surface and increased pH led to production of more O2 −, which activated the PS to give more SO4 − to degrade PCB28. In addition, increasing the oxygen concentration in the reaction solution favored the generation of O2 − as well as the degradation of PCB28. The findings of this study provide new insights into the mechanism of heterogeneous catalysis based on MNPs and the reactivity of MNPs toward environmental contaminants.

Activation of Peroxydisulfate on Carbon Nanotubes: Electron-Transfer Mechanism.

Abstract: This study proposed an electrochemical technique for investigating the mechanism of nonradical oxidation of organics with peroxydisulfate (PDS) activated by carbon nanotubes (CNT). The electrochemical property of twelve phenolic compounds (PCs) was evaluated by their half-wave potentials, which were then correlated to their kinetic rate constants in the PDS/CNT system. Integrated with quantitative structure-activity relationships (QSARs), electron paramagnetic resonance (EPR), and radical scavenging tests, the nature of nonradical pathways of phenolic compound oxidation was unveiled to be an electron-transfer regime other than a singlet oxygenation process. The QSARs were established according to their standard electrode potentials, activation energy, and pre-exponential factor. A facile electrochemical analysis method (chronopotentiometry combined with chronoamperometry) was also employed to probe the mechanism, suggesting that PDS was catalyzed initially by CNT to form a CNT surface-confined and -activated PDS (CNT-PDS*) complex with a high redox potential. Then, the CNT-PDS* complex selectively abstracted electrons from the co-adsorbed PCs to initiate the oxidation. Finally, a comparison of PDS/CNT and graphite anodic oxidation under constant potentials was comprehensively analyzed to unveil the relative activity of the nonradical CNT-PDS* complex toward the oxidation of different PCs, which was found to be dependent on the oxidative potentials of the CNT-PDS* complex and the adsorbed organics.