Fenton-like oxidation of 2,4,6-trinitrotoluene using different iron minerals

Degradation of 2,4,6-trinitrotoluene (TNT) was investigated in presence of different oxidants (Fenton's reagent, sodium persulfate, peroxymonosulfate and potassium permanganate) and different iron minerals (ferrihydrite, hematite, goethite, lepidocrocite, magnetite and pyrite) either in aqueous solution or in soil slurry systems. Fenton's reagent was the only oxidant able to degrade TNT in solution (k(app)=0.0348 min(-1)). When using iron oxide as heterogeneous catalyst at pH 3, specific reaction rate constants per surface area were k(surf)=1.47.10(-3) L min(-1) m(-2) and k(surf)=0.177 L min(-1) m(-2) for magnetite and pyrite, respectively while ferric iron minerals were inefficient for TNT degradation. The major asset of iron mineral catalyzed Fenton-like treatment has been the complete oxidation of the pollutant avoiding the accumulation of possible toxic by-products. In soil slurry systems, 38% abatement of the initial TNT concentration (2 g/kg) was reached after 24 h treatment time at neutral pH. Rate limiting steps were the availability of soluble iron at neutral pH together with desorption of the TNT fraction sorbed on the clay mineral surfaces.     

Soil organic matter-hydrogen peroxide dynamics in the treatment of contaminated soils and groundwater using catalyzed H2O2 propagations (modified Fenton's reagent)

The interactions between catalyzed H(2)O(2) propagations (CHP-i.e. modified Fenton's reagent) and soil organic matter (SOM) during the treatment of contaminated soils and groundwater was studied in a well-characterized surface soil. The fate of two fractions of SOM, particulate organic matter (POM) and nonparticulate organic matter (NPOM), during CHP reactions was evaluated using concentrations of hydrogen peroxide from 0.5 to 3M catalyzed by soluble iron (III), an iron (III)-ethylenediamine tetraacetic acid (EDTA) chelate, or naturally-occurring soil minerals. The destruction of total SOM in CHP systems was directly proportional to the hydrogen peroxide dosage, and was significantly greater at pH 3 than at neutral pH; furthermore, SOM destruction occurred predominantly in the NPOM fraction. At pH 3, SOM did not affect hydrogen peroxide decomposition rates or hydroxyl radical activity in CHP reactions. However, at neutral pH, increasing the mass of SOM decreased the hydrogen peroxide decomposition rate and increased the rate of hydroxyl radical generation in CHP systems. These results show that, while CHP reactions destroy some of the organic carbon pools, SOM does not have a significant effect on the CHP treatment of soils and groundwater.     

Fenton's oxidation of pentachlorophenol

The combination of H₂O₂ and Fe(II) (Fenton's reaction) has been demonstrated to rapidly degrade many organics via hydroxyl radicals. However, few studies have related hydroxyl radical generation rates with measured organic chemical degradation data. The goals of this work were to investigate the kinetics, stoichiometry, and intermediates of pentachlorophenol (PCP) degradation in the Fenton's reaction and to develop a mathematical model of this reaction system. Batch reaction experiments were performed to assess both initial transients and steady states, and special attention was given to the analysis of intermediates. Solutions of PCP (55 μM) and Fe(II) (200 μM) were treated with variable levels of H₂O₂ (<850 μM), and the concentrations of these reactants and their products were measured. Partial PCP degradation and near stoichiometric dechlorination were observed at low initial H₂O₂ concentrations. Higher H₂O₂ doses achieved at most 70% dechlorination even though nearly all of the PCP was degraded. The reaction intermediates tetrachlorohydroquinone and dichloromaleic acid accounted for up to 5% of the PCP degraded. Organic carbon mineralization (transformation to CO₂) was not observed. The OH scavenging effects of the PCP-by-products mixture were characterized as a lumped parameter in the reaction kinetics model, which provided reasonable predictions of experimental results at different oxidant concentrations and reaction time.     

Oxidation of p-hydroxybenzoic acid by Fenton's reagent

Fenton's reagent has been shown to be a feasible technique to treat phenolic-type compounds present in a variety of food processing industry wastewaters. A model compound, p-hydroxybenzoic acid was oxidised by continuously pumping two solutions of ferrous iron and hydrogen peroxide. Typical operating variables like reagent feeding concentrations and flowrate, temperature and pH were studied. A mechanism of reactions based on the classical Fenton's chemistry was assumed, and computed concentration profiles of the parent compound, ferrous ion and dihydroxybenzene were compared to experimental results. The model qualitatively predicted the influence of several operating variables, however, calculated results suggested the presence of parallel routes of substrate elimination and/or a initiating rate constant with a higher value. The low efficiency of a well-known hydroxyl radical scavenger (tert-butyl alcohol) also supports the contribution of oxidising species different from the hydroxyl radical to substrate removal. Further evidence of the presence of reactions different from the hydroxyl radical oxidation was observed from comparison of the simultaneous Fenton's or UV/H2O2 oxidations of p-hydroxybenzoic acid, tyrosol and p-coumaric acid.     

Electrochemical generation of the Fenton's reagent: application to atrazine degradation

The degradation of refractory chemicals in water requires chemical oxidation by hydroxyl radicals. Among the systems that may be used to generate OH(o), the Fenton's reagent consists of the mixing of ferrous iron and hydrogen peroxide. Even though this system is very simple, the oxidation of an organic compound is difficult to control and the ferrous iron regeneration is limited. Very recently, electrochemical systems have merged that allow the electrochemical production of ferrous iron and/or hydrogen peroxide, thereby allowing the generation of OH(o). So a simple electro-Fenton system has been used and tested for its efficiency in producing hydroxyl radicals. Atrazine was chosen as a model organic compound as its reaction with OH(o) has been extensively studied. Comparison with the classical Fenton system gives advantage to the electrochemical system, due to a more thorough oxidation of atrazine.     

Displacement of five metals sorbed on kaolinite during treatment with modified Fenton's reagent

The displacement of sorbed metals during the treatment of soils and groundwater with modified Fenton's reagent was investigated using five common metal contaminants (cadmium, copper, lead, nickel, and zinc) and kaolinite as a model sorbent. Modified Fenton's conditions included three H(2)O(2) concentrations (0.9, 1.8, 2.7 M) and two catalysts: soluble iron (III) at pH 3 and iron (III)-NTA chelate at pH 6. Iron (III)-catalyzed Fenton's reactions released significant amounts of zinc, cadmium, and copper. Modified Fenton's reactions catalyzed by iron (III)-NTA released zinc, cadmium, copper, and lead, and resulted in greater amounts of metals release than the iron (III)-catalyzed reactions. Metals release may have been mediated by transient oxygen species, such as superoxide, generated by propagation reactions, which become dominant at the relatively high hydrogen peroxide concentrations used. Metals release from kaolinite was undetectable when sufficiently low hydrogen peroxide concentrations were maintained to minimize propagation reactions. These results indicate that using dilute concentrations of hydrogen peroxide for Fenton's ISCO may minimize potential metals mobility when treating contaminated soils and groundwater containing a mixture of organic and metal contaminants.     

Enhanced Fenton degradation of hydrophobic organics by simultaneous iron and pollutant complexation with cyclodextrins

The effectiveness and selectivity of Fenton degradation of hydrophobic organic compounds (HOCs) can be improved by simultaneous complexation of Fe(2+) and the organic compound with a cyclodextrin or derivatized cyclodextrin. Such selective complexation of a target substrate and a catalytic metal is a crude mimic of enzyme systems. Both beta-cyclodextrin and carboxymethyl-beta-cyclodextrin (CMCD) were able to simultaneously complex Fe(2+) and an aromatic hydrocarbon, such as phenol, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls (PCBs). Degradation of compounds included in cyclodextrins was unaffected by hydroxyl radical scavengers, indicating that the radical was formed at the ternary complex (HOC-cyclodextrin-iron) and in close proximity to the included molecule. Without cyclodextrins, humic acid (HA) decreased degradation efficiency. However, in the presence of CMCD, HA did not inhibit degradation of the target compound. CMCD is capable of removing HOCs from HA binding sites while at the same time complexing Fe(2+). PCBs sorbed to glass were resistant to Fenton degradation, but were significantly degraded using a cyclodextrin modified Fenton system. In all of these systems, the ternary HOC-cyclodextrin-iron complexes effectively direct hydroxyl radical reaction toward the HOC, increasing the efficiency of Fenton degradation. One potential application of such targeted degradation systems is the in situ remediation of hydrophobic organic pollutants in contaminated soil and groundwater or in industrial waste streams.     

Influence of ferrous iron and ph on carbon tetrachloride degradation by Methanosarcina thermophila

The influence of environmental conditions on the biological transformation of a contaminant must be well understood to optimize remediation processes. One factor that impacts the biological transformation of carbon tetrachloride (CT) is elemental iron (Fe0). Previous research has shown that Fe0 increases the methanogenic CT degradation rate by providing H2 for cell growth and dechlorination. As Fe0 oxidizes it also increases the pH and Fe2+ levels, which may also impact the biological transformation of CT. Experiments were performed with Methanosarcina thermophila to investigate the influence of these factors on CT degradation. The transformation of CT and CF was greatly influenced by pH, with the rate of CT and CF degradation increasing with increasing pH. After 6 h, > 90% of the CT had been degraded in the treatments containing cells at a pH of 8.5, whereas only about 51% of the CT had been degraded in similar treatments at a pH of 5.5. Fe2+ did not significantly influence the degradation of CT; however, 60% less CF was formed in systems containing cells+Fe2+ than in systems containing cells only. In addition. Fe2+ promoted rapid transformation of CF when added to treatments containing cells. The product distribution after 9 days in all systems containing cells was very similar, with 98.04 +/- 5.46% (two-sided 95% confidence interval) of the originally fed CT present as soluble products. These results show that pH and Fe2+ influence the degradation of CT and CF, although transiently. Because the residence time of contaminants in Fe0 barriers varies with the thickness of the barrier, it is likely that this influence will be important for some flow-through systems. This implies that a combined Fe0/organism remediation system may have previously unrealized advantages (due to pH and Fe2+ changes).     

Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: effects of sorption, surfactants, and natural organic matter

Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1×cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5×cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.     

Fenton's oxidation of MTBE with zero-valent iron

Methyl tert-butyl ether (MTBE) has become a contaminant of increasing concern in the U.S. Traditional remediation technologies are successful in removing MTBE from contaminated water, but usually transfer the contaminant from the aqueous to another phase. Fenton's oxidation of MTBE provides a promising alternative to traditional remediation techniques in that it may mineralize the contaminant rather than just phase transfer. This bench-scale study investigated the feasibility of Fenton's oxidation of MTBE using zero-valent iron as the source of catalytic ferrous iron. The oxidation reactions were able to degrade over 99% of the MTBE within 10 min, and showed significant generation, and subsequent degradation, of the MTBE oxidation byproduct acetone. Second-order rate constants for MTBE degradation were 1.9 x 10(8) M(-1) s(-1) at pH 7.0 and 4.4 x 10(8) M(-1) s(-1) at pH 4.0. The total organic carbon was reduced by over 86% when a H2O2:MTBE ratio of 220:1 or greater was used.     

Two-phase ozonation of hazardous organics in single and multicomponent systems

The destruction of pentachlorophenol (PCP), oxalic acid, chlorendic acid, and a mixture of pentachlorophenol, 1,3-dichlorobenzene (DCB), and trichloroethylene (TCE) were studied using a two-phase ozonation system. A two-phase ozonation system consists of water containing the pollutant and a second solvent phase which houses the ozone. The solvent phase is an inert fluorinated hydrocarbon (FC40) that is nonpolar and reusable. The solvent phase is desirable because it has a high ozone stability (k = 0.0033 min⁻¹) and an ozone solubility of 120 mg/L at 25°C, 10 times that of water. In addition to an enhanced oxidation rate of PCP, less ozone was utilized. At high pH (10.3), a first-order rate constant of 200 min⁻¹ in the two-phase system was found for PCP degradation compared to k_app = 0.154 min⁻¹ in a single aqueous-phase system. Within 15 s, the concentration of PCP (100 mg/L initially) was degraded more than 90%, and 100% dechlorination was obtained with longer reaction times. This system also demonstrated the ability to selectively oxidize PCP while in the presence of free radical scavengers existing in the water phase. PCP was also successfully oxidized using actual wastwater which contained alkalinity, hardness, many inorganics, and trace hazardous organics. Oxalic acid, an intermediate formed during the degradation of PCP, was also degraded by two-phase ozonation. Preliminary work with chlorendic acid showed that two-phase ozonation was faster than single aqueous-phase ozonation at dechlorinating the compound. TCE and DCB degraded slightly faster when PCP was added to the mxture, possibly due to the production of other radicals during the oxidation of PCP.     

Sonochemical destruction of free and metal-binding ethylenediaminetetraacetic acid

This study focused on the sonochemical degradation of ethylenediaminetetraacetic acid (EDTA) and chromium-EDTA complexes. Degradation of the copper(II)-EDTA complex was also investigated as a comparison metal complex. A 90% degradation of a 150-microM EDTA solution with continuous O2-bubbling was shown for the 20-kHz system in approximately 3 h (kpseudo-first order = 1.22 x 10(-2) min-1) and less than 1 h for the 354-kHz system (kpseudo-first order = 5.42 x 10(-2) min-1). These results are consistent with the higher concentrations of hydrogen peroxide found in the higher frequency system and an expected oxidation of EDTA in bulk solution. The presence of a chelated metal decreased the rate of degradation at both frequencies. Cr(III)-EDTA degraded the slowest, supporting the theory that the extremely slow ligand exchange rate of chromium is the determining factor in how fast degradation by hydroxyl radical can occur. The 354-kHz system showed a 17% decrease in the original 150-microM Cr(III)-EDTA complex after 3 h of sonication. All of the chromium from the degraded EDTA complex existed as a combination of oxidized Cr(VI) and possibly small amounts of a new Cr(III)-organic complex (Cr(III)-Y). The 20-kHz system showed a similar extent of degradation (16%) after 3 h of sonication, despite lower hydroxyl radical production. Fifty percent of the chromium from the degraded EDTA complex was found as free Cr3+ ion, with the remaining 50% existing as both Cr(III)-Y and Cr(VI). Varying degrees of bulk oxidation, near-bubble thermolysis, and perhaps different degradation pathways at the two frequencies are responsible for these differences.     

Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at 20 degrees C

Application of in situ chemical oxidation (ISCO) involves application of oxidants to contaminants such as trichloroethylene (TCE) in soil or groundwater in place. Successful application of ISCO at a hazardous waste site requires understanding the scavenging reactions that could take place at the site to better optimize the oxidation of target contaminants and identification of site conditions where ISCO using persulfate may not be applicable. Additionally, estimation of the oxidant dose at a site would need identification of groundwater constituents such as alkalinity and chlorides that may scavenge radicals and therefore use up the oxidant that is targeted for the contaminant(s). The objective of this study was to investigate the influence of various levels of chloride and carbonates on persulfate oxidation of TCE at 20 degrees C under controlled conditions in a laboratory. Based on the results of the laboratory experiments, both chloride and alkalinity were shown to have scavenging effects on the rate of oxidation of TCE. It was found that at a neutral pH, persulfate oxidation of TCE was not affected by the presence of bicarbonate/carbonate concentrations within the range of 0-9.20 mM. However, the TCE degradation rate was seen to reduce with an increase in the level of carbonate species and at elevated pHs. TCE degradation in the presence of chlorides revealed no effect on the degradation rate especially at chloride levels below 0.2 M. However, at chloride levels greater than 0.2 M, TCE degradation rate was seen to reduce with an increase in the chloride ion concentration. Prior to application of persulfate as an oxidant, a site should be screened for the presence of scavengers to evaluate the potential of meeting target cleanup goals within a desirable timeframe at the site.     

The role of hydroxyl radicals for the decomposition of p-hydroxy phenylacetic acid in aqueous solutions

The chemical decomposition of p-hydroxyphenylacetic acid, a priority phenolic pollutant present in wastewaters from some agro-industrial plants, is studied by means of a single photochemical process produced by a polychromatic UV radiation and by hydroxyl radicals generated by the combination of UV radiation plus hydrogen peroxide and by the Fenton's reagent (hydrogen peroxide plus ferrous salts). Batch experiments were conducted to establish the degradation levels obtained and the quantum yields in the single photodecomposition process. An improvement in the decomposition of the phenolic acid in the combined UV/H2O2 oxidation is observed, due to the generation of OH radicals, and the contribution of the radical reaction to the global process is determined. In the Fenton's reagent oxidation, the effects of the operating variables (H2O2 and Fe2+ initial concentrations, pH, type of buffer used) are established and the rate constant for the reaction of p-hydroxyphenylacetic acid with OH radicals is evaluated from a kinetic model, its value being 7.02 x 10(8) M-1 s-1 at 20 degrees C.     

Mineralization of salicylic acid in acidic aqueous medium by electrochemical advanced oxidation processes using platinum and boron-doped diamond as anode and cathodically generated hydrogen peroxide

Solutions containing 164 mg L(-1) salicylic acid of pH 3.0 have been degraded by electrochemical advanced oxidation processes such as anodic oxidation, anodic oxidation with electrogenerated H(2)O(2), electro-Fenton, photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Their oxidation power has been comparatively studied in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and a graphite or O(2)-diffusion cathode. In the three latter procedures, 0.5mM Fe(2+) is added to the solution to form hydroxyl radical (()OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the O(2)-diffusion cathode. Total mineralization is attained for all methods with BDD and for photoelectro-Fenton and solar photoelectro-Fenton with Pt. The poor decontamination achieved in anodic oxidation and electro-Fenton with Pt is explained by the slow removal of most pollutants by ()OH formed from water oxidation at the Pt anode in comparison to their quick destruction with ()OH produced at BDD. ()OH generated from Fenton's reaction oxidizes rapidly all aromatic pollutants, but it cannot destroy final Fe(III)-oxalate complexes. Solar photoelectro-Fenton treatments always yield quicker degradation rate due to the very fast photodecarboxylation of these complexes by UVA irradiation supplied by solar light. The effect of current density on the degradation rate, efficiency and energy cost of all methods is examined. The salicylic acid decay always follows a pseudo-first-order kinetics. 2,3-Dihydroxybenzoic, 2,5-dihydroxybenzoic, 2,6-dihydroxybenzoic, alpha-ketoglutaric, glycolic, glyoxylic, maleic, fumaric, malic, tartronic and oxalic acids are detected as oxidation products. A general reaction sequence for salicylic acid mineralization considering all these intermediates is proposed.     

Abiotic reduction of dinitroaniline herbicides

The importance of abiotic reductive transformations as a sink for four dinitroaniline herbicides (trifluralin, pendimethalin, nitralin, and isopropalin) has been evaluated. Using reductants representative of abiotic reductants found in natural systems, the results of this study indicate that nitro groups present on the dinitroaniline herbicides can be reduced by surface-bound Fe(II) species in goethite suspensions or by hydroquinone moieties such as (mercapto)juglone in a hydrogen sulfide solution. Aqueous iron species are also effective at pH values above 7.0. The reaction in aqueous Fe(II) and in Fe(II)/goethite systems is strongly pH dependent, with rates increasing with increasing pH. Montmorillonite clay, however, is not effective in mediating the reduction of dinitroaniline herbicides in the presence of Fe(II). Because the selected dinitroaniline herbicides have a mixture of electron withdrawing and electron donating groups, linear free energy relationships were developed for the H(2)S/(mercapto)juglone and Fe(II)/goethite systems. Anilines resulting from reduction of the nitro group as well as cyclization products (benzimidazoles) were observed in the degradation of trifluralin. Only one aniline product was observed for pendimethalin.     

Degradation of TCE,Cr(VI), sulfate,and nitrate mixtures by granular iron in flow-through columns under different microbial conditions

Flow-through aquifer columns packed with a middle layer of granular iron (Fe0) were used to study the applicability and limitations of bio-enhanced Fe0 barriers for the treatment of contaminant mixtures in groundwater. Concentration profiles along the columns showed extensive degradation of hexavalent chromium Cr(VI), nitrate, sulfate, and trichloroethene (TCE), mainly in the Fe0 layer. One column was bioaugmented with Shevanella algae BRY, an iron-reducing bacterium that could enhance Fe0 reactivity by reductive dissolution of passivating iron oxides. This strain did not enhance Cr(VI), which was rapidly reduced by iron, leaving little room for improvement by microbial participation. Nevertheless, BRY-enhanced nitrate removal (from 15% to 80%), partly because this strain has a wide range of electron acceptors, including nitrate. Sulfate was removed (55%) only in a column that was bioaugmented with a mixed culture containing sulfate-reducing bacteria. Apparently, these bacteria used H2 (produced by Fe0 corrosion) as electron donor to respire sulfate. Most of the TCE was degraded in the zone containing Fe0 (50-70%), and bioaugmentation with BRY slightly increased the removal efficiency to about 80%. Microbial colonization of the Fe0 surface was confirmed by scanning electron microscopy.     

The mechanisms of rate enhancing and quenching of trichloroethene photodecay in the presence of sensitizer and hydrogen sources

The reaction mechanisms and rates of trichloroethene (TCE) photodecay in the presence of photosensitizer (acetone, ACE) and hydrogen sources (surfactant and triethylamine, TEA) were investigated. Quantum yields of TCE photodecay in solution with surfactant Brij 35 and optimal ACE dosage are about 25 times higher than in Brij 35 alone. However, with an excess ACE dosage, ACE will act as a light barrier and attenuate the light intensity available for TCE photodegradation. TCE photodegradation follows a two-stage kinetics, in which a lag-phase is followed by a fast decay. The lag-phase distribution depends on initial pH levels and ACE concentrations. The overall TCE removal was found to be higher at high pH level, suggesting that free radical reaction is dominant at high pH levels. The use of additional hydrogen source (TEA) in the reaction can further accelerate the reaction, but overdosing of TEA would quench the reaction. The possible reaction mechanisms of TCE photodecay involving ACE and TEA were proposed, and rateenhancing and rate-quenching models at low and high TEA concentrations respectively were derived based on the proposed mechanism, they were found useful for predicting the TEC decay quantum yields.     

Reductive dehalogenation of chlorinated ethenes with elemental iron: the role of microorganisms

Trichloroethene (TCE) transformation and the product distribution in an aqueous medium containing zero-valent iron (Fe(0)) was investigated in the presence of an anaerobic mixed culture to assess the potential role of microorganisms in permeable iron barriers. The presence of the culture increased the rate of TCE disappearance and changed the product distribution. Rapid formation and degradation of cis-dichloroethene (cis-DCE) was observed in reactors containing cells plus Fe(0) or H2 as a bulk reducing agent. High levels of vinyl chloride (VC) were formed and very similar profiles were obtained in the Fe(0) plus cell and H2 plus cell reactors, but not in Fe(0)-only reactors. The similar trends observed in Fe(0)-cell and H2-cell reactors suggest that most cis-DCE and VC in the Fe(0)-cell reactors were produced and transformed biologically rather than abiotically. Accumulation of methane in the Fe(0)-cell system indicates that hydrogen gas generated during anaerobic iron corrosion could support a methanogenic culture. Digital confocal images showed that the microorganisms were able to colonize the iron surface. The results suggest that potential development of dechlorinating populations in Fe(0) barriers may alter the TCE reduction pathway and produce VC, which would have significant impact on the performance of Fe(0) barriers.     

Degradation of atrazine in aqueous medium by electrocatalytically generated hydroxyl radicals. A kinetic and mechanistic study

Oxidative degradation of atrazine by hydroxyl radicals (OH) was studied in aqueous medium. OH were formed in situ from electrochemically generating Fenton's reagent by an indirect electrochemical advanced oxidation process. Identification and evolution of seven main aromatic metabolites and four short-chain carboxylic acids were performed by using liquid chromatography analyses. Total organic carbon (TOC) and ionic chromatography were used in order to evaluate the mineralization efficiency of treated aqueous solutions. A high mineralization rate of 82% (never reported until now) was obtained. The oxidative degradation of cyanuric acid, the ultimate product of atrazine degradation, was highlighted for the first time. The absolute rate constant of the reaction between atrazine and hydroxyl radicals was evaluated by competition kinetics method as (2.54 ± 0.22) × 10⁹ M⁻¹ s⁻¹. Considering all oxidation reaction intermediates and end products a general reaction sequence for atrazine degradation by hydroxyl radicals was proposed.