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ABSTRACT: The chiral signature of the antidepressant venlafaxine was used in this study to gain insight into biological attenuation processes and to differentiate abiotic and biotic transformation processes in water. Laboratory scale experiments revealed that sorption and phototransformation processes were not enantioselective while venlafaxine was enantioselectively biotransformed into O-desmethylvenlafaxine. The enantiomeric fraction (EF) variations of venlafaxine appeared to be proportional to its microbial fractional conversion. Enantioselective biotransformation of venlafaxine was also investigated in a eutrophic French river. Venlafaxine was found to be racemic at the output of the main wastewater treatment plant discharging into the river, independently of the sampling date during the year. An analysis of EF variations might provide evidence of biodegradation along a 30km river stretch.
Chemosphere 11/2012; · 3.21 Impact Factor
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ABSTRACT: Bioaccumulation is essential for gaining insight into the impact of exposure to organic micropollutants in aquatic fauna. Data are currently available on the bioaccumulation of persistent organic pollutants, but there is very little documentation on the bioaccumulation of pharmaceuticals and personal care products (PPCPs). The bioconcentration of selected PPCPs was studied in marine mussels (Mytilus galloprovincialis). The selected PPCPs were two organic UV filters, i.e., 2-ethylhexyl-4-trimethoxycinnamate (EHMC) and octocrylene (OC), and two benzodiazepines (BZP), i.e., diazepam (DZP) and tetrazepam (TZP). Laboratory experiments were performed in which M. galloprovincialis was exposed to these compounds either directly from water, for the less lipophilic substances (BZP) or via spiked food for lipophilic UV filters. M. galloprovincialis uptook and eliminated BZP following first-order kinetics. The biological half-life (t (1/2)) of TZP was 1.4 days, resulting in a bioconcentration factor of 64 and 99 mL g(-1) dry weight (dw), respectively, for 2.3 and 14.5 mu g L-1 of exposure, while the biological half-life (t (1/2)) of DZP was 0.4 days, resulting in a bioconcentration factor of 51 mL g(-1) dw for 13.2 mu g L-1 of exposure. The uptake of UV filter was rapid in mussels, followed by elimination within 24 h. EHMC increased from 15 to 138 ng g(-1) dw in 1 h and decreased to 25 ng g(-1) after 24 h for 11.9 mu g L-1 exposure. OC reached 839 ng g(-1) dw after 1 h and decreased to 33 ng g(-1) after 24 h for 11.6 mu g L-1 exposure. However, EHMC and OC were slightly accumulated in 48 h, i.e., 38 and 60 ng g(-1) dw, respectively.
Environmental Science and Pollution Research 08/2012; 19(7):2561-2569. · 2.65 Impact Factor
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ABSTRACT: It is shown here that carbamazepine (CBZ) would undergo direct photolysis and reaction with (•)OH as the main phototransformation pathways in surface waters. Environmental lifetimes are expected to vary from a few weeks to several months, and predictions are in good agreement with available field data. Acridine (I) and 10,11-dihydro-10,11-trans-dihydroxy-CBZ (V) are the main quantified phototransformation intermediates upon direct photolysis and (•)OH reaction, respectively. The photochemical yield of mutagenic I from CBZ is in the 3-3.5% range, and it is similar for both direct photolysis and (•)OH reaction: it would undergo limited variation with environmental conditions. In contrast, the yield of V would vary in the 4-8.5% range depending on the conditions, because V is formed from CBZ by (•)OH (9.0% yield) more effectively than upon direct photolysis (1.4% yield). Other important photointermediates, mostly formed from CBZ upon (•)OH reaction, are an aromatic-ring-dihydroxylated CBZ (VI) and N,N-bis(2-carboxyphenyl)urea (VII). Compounds VI and VII are formed by photochemistry and are not reported as human metabolites; thus, they could be used as tracers of CBZ phototransformation in surface waters. Interestingly, VI has recently been detected in river water.
Environmental Science & Technology 07/2012; 46(15):8164-73. · 4.80 Impact Factor
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ABSTRACT: The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals
are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting
alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from
peroxymonosulfate/CoII are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H2O2/FeII) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO4
·− with carbamazepine is 1.92·109M−1s−1. In laboratory grade water and in real urban wastewater, SO4
·− yielded a faster degradation of carbamazepine compared to HO· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly
oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban
wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may
represent an interesting alternative in advanced oxidation processes.
KeywordsPeroxymonosulfate–Sulfate radical–Carbamazepine–Advanced oxidation technology–Kinetic–Second-order rate constant
Environmental Chemistry Letters 04/2012; 9(3):347-353. · 1.88 Impact Factor
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ABSTRACT: Transformation of the pharmaceutical oxcarbazepine (OXC), a keto analogue of carbamazepine (CBZ) was investigated under different water disinfection processes (ozonation, chlorination and UV irradiation) to compare its persistence, toxicity and degradation pathways with those of CBZ. Analysis by LC-ion trap-MS(n) allowed for the identification of up to thirteen transformation products (TPs). The major abundant and persistent TPs (10,11-dihydro-10,11-trans-dihydroxy-carbamazepine (DiOH-CBZ), acridine (ACIN) and 1-(2-benzaldehyde)-(1H, 3H)-quinazoline-2,4-dione (BQD)) were identical to those previously reported during water treatment of CBZ. Only one new compound arising from an intramolecular cyclisation reaction was identified during UV irradiation. OXC reacted quickly with hydroxyl radical and relatively rapidly with free chlorine while slow reaction rates were recorded in presence of ozone and upon UV irradiation. An increase of the acute toxicity of UV irradiated solutions, monitored by a Daphnia magna bioassay, was recorded, probably due to the accumulation of ACIN. The formation of ACIN is of concern due to the carcinogenic properties of this chemical. ACIN was also generated during the direct UV photo transformation of DiOH-CBZ and 10-hydroxy-10,11-dihydro-carbamazepine (OH-CBZ), two metabolites of OXC and CBZ widely detected in water resources. Analysis of tap water samples revealed the occurrence at ng/L levels of the major TPs detected under laboratory scale experiments, except ACIN.
Water Research 02/2011; 45(4):1587-96. · 4.86 Impact Factor
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ABSTRACT: This study was aimed at investigating which processes cause acidic herbicides (e.g., bentazone, MCPA and dichlorprop) to rapidly disappear in the lagoons of the Rhône delta, which are peculiar brackish and shallow aquatic environments. The use of the model MASAS (Modeling of Anthropogenic Substances in Aquatic Systems) revealed that sorption, sedimentation, volatilization, flushing and abiotic hydrolysis had a minor role in the attenuation of the investigated herbicides. Laboratory scale biodegradation and photodegradation studies were conducted to better assess the significance of these two processes in the natural attenuation of herbicides in brackish (lagoons) waters with respect to fresh waters (canals draining paddy fields). Herbicide biodegradation rates were significantly lower in lagoon water than in canal water. Consequently, photodegradation was the main dissipation route of all investigated herbicides. The contribution of indirect photolysis was relevant for MCPA and dichlorprop while direct photolysis dominated for bentazone removal. There is a need to further investigate the identity of phototransformation products of herbicides in lagoons.
Science of The Total Environment 11/2010; 409(3):582-7. · 3.29 Impact Factor
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ABSTRACT: This work is an attempt to establish if aromatic nitration processes are always associated with an increase of genotoxicity. We determined the mutagenic and genotoxic effects of Benzene (B), Nitrobenzene (NB), Phenol (P), 2-Nitrophenol (2-NP), 2,4-Dinitrophenol (2,4-DNP), Pyrene (Py), 1-Nitropyrene (1-NPy), 1,3-Dinitropyrene (1,3-DNPy), 1,6-Dinitropyrene (1,6-DNPy), and 1,8-Dinitropyrene (1,8-DNPy). The mutagenic activities were evaluated with umuC test in presence and in absence of metabolic activation with S9 mix. Then, we used both cytokinesis-blocked micronucleus (CBMN) assay, in combination with fluorescent in situ hybridization (FISH) of human pan-centromeric DNA probes on human lymphocytes in order to evaluate the genotoxic effects. Analysis of all results shows that nitro polycyclic aromatic hydrocarbons (PAHs) are definitely environmental genotoxic/mutagenic hazards and confirms that environmental aromatic nitration reactions lead to an increase in genotoxicity and mutagenicity properties. Particularly 1-NPy and 1,8-DNPy can be considered as human potential carcinogens. They seem to be significant markers of the genotoxicity, mutagenicity, and potential carcinogenicity of complex PAHs mixtures present in traffic emission and industrial environment. In prevention of environmental carcinogenic risk 1-NPy and 1,8-DNPy must therefore be systematically analyzed in environmental complex mixtures in association with combined umuC test, CBMN assay, and FISH on cultured human lymphocytes. © 2010 Wiley Periodicals, Inc. Environ Toxicol, 2012.
Environmental Toxicology 08/2010; 27(6):321-31. · 2.41 Impact Factor
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ABSTRACT: This work is an attempt to investigate the chemical stability of 1,N2-propano-2'-deoxyguanosine (pdG-HNE) and 1,N2-etheno-2'-deoxyguanosine (epsilondG) DNA adducts against hydrolysis and upon oxidation reactions. It includes both kinetic issues together with proposed degradation pathways. While both chemicals are stable in the 3.5-9 pH range, the results suggest that pdG-HNE adduct is less prone to in vitro oxidative transformation than epsilondG adduct. EpsilondG and pdG-HNE behave differently upon hydroxyl radical and one electron oxidation reactions. The exocyclic ring of epsilondG is mainly affected by oxidative processes leading to the regeneration of 2'-deoxyguanosine (dG) while the integrity of the exocyclic ring is preserved for pdG-HNE. Consequently, pdG-HNE might be a better biomarker than epsilondG for monitoring oxidative stress during environmental or occupational exposures to chemicals. Understanding the in vitro routes of etheno and propano DNA adduct degradation would probably help to guide the development of analytical methodologies for the reliable detection of these endogenous adducts.
Chemosphere 08/2010; 80(9):1081-7. · 3.21 Impact Factor
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ABSTRACT: This paper reports a simple model to describe the formation and reactivity of hydroxyl radicals in the whole column of surface freshwater systems. The model is based on empirical irradiation data and it is a function of the water chemical composition (the photochemically significant parameters Non-Purgeable Organic Carbon–NPOC–, nitrate, nitrite, carbonate and bicarbonate), the water body conformation, and the water absorption spectrum in a simplified Lambert-Beer approach. The purpose is to derive the lifetime of dissolved molecules, due to the reaction with •OH, on the basis of their second-order rate constants with the hydroxyl radical. It is also proposed a simplified (and approximated) approach to simulate the absorption spectrum of water when the latter is not available, based on the value of the NPOC. Such a simulation can be useful when the model is adopted to describe a degradation scenario for a certain compound, without a direct link to a definite ecosystem. The model was applied to the lifetime of various pesticides in surface water bodies, and it is suggested that the lifetime of a given compound can be very variable in different systems, even more than the lifetime of different compounds in the same water body. The variations of the chemical composition and of the depth of the water column are the main reasons for the reported finding.
International Journal of Environmental Analytical Chemistry 03/2010; 90(Nos. 3–6):260-275. · 1.16 Impact Factor
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Environmental Modelling and Software. 01/2010; 25:1837-1844.
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ABSTRACT: This paper describes the reactive photo-induced species (RPS) hydroxyl radical (HO*), singlet oxygen ((1)O(2)) and chromophoric dissolved organic matter triplet state ((3)CDOM*) in fresh water (Canal Fumemorte) and estuarine water (Vaccarès), sampled in the Camargue region, southern France. Experiments were conducted with a medium-pressure Hg lamp in a glass photoreactor (lambda > 290 nm, 220 W m(-2) irradiance between 290 and 400 nm). Steady-state concentration and initial production rate of RPS were determined for HO* and for (1)O(2). HO* and (1)O(2) were indirectly identified in the presence of benzene and furfuryl alcohol, respectively, as specific probes. The steady-state measured concentration of HO* was (1.72 +/- 0.01) x 10(-16) M and (9.41 +/- 0.12) x 10(-17) M for Vaccarès and Canal waters samples, respectively, and the respective concentrations of (1)O(2) was (2.06 +/- 0.22) x 10(-13) M and (5.44 +/- 0.04) x 10(-14) M. The interference of (3)CDOM* or other species in the determination of (1)O(2) with furfuryl alcohol, and of (1)O(2) in the quantification of (3)CDOM* with 2,4,6-trimethylphenol was also quantitatively assessed. We developed a kinetic model describing the solar photo-transformation of xenobiotic organic compounds induced by the three different photooxidants HO*, (1)O(2) and (3)CDOM*.
Photochemical and Photobiological Sciences 01/2010; 9(1):78-86. · 2.58 Impact Factor
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ABSTRACT: This work is an attempt to elucidate the quantitative significance of acetaminophen (APAP) nitration in nitrifying activated sludge and to propose a reaction mechanism for this process. The link between nitrification and nitration of APAP was investigated at different scales. Results from field studies showed the occurrence of 3-nitro-APAP and to a lesser extent 3-chloro-5-nitro-APAP at concentration levels in the 50-300 ng/L range in effluents of a full scale wastewater treatment plant (WWTP) operated with nitrogen removal, whereas 3-hydroxy-APAP was eliminated after the nitrification step. Batch experiments with nitrifying activated sludge confirmed APAP transformation by nitration and suggested that nitrifying bacteria may play a role in this transformation process through the release of reactive nitrogen species. In vitro assays provided evidence that nitration through the production of nitrous acid is a very unlikely pathway. In contrast, nitric oxide (*NO) produced by nitrifying bacteria is probably involved in APAP nitration through the formation of peroxynitrite in presence of superoxide anion. The production of 3-nitro-APAP would only account for a few percents of the total transformation rate of APAP in WWTPs. The production of nitrated derivatives is highly relevant because of the potential ecotoxicological risks of these compounds.
Environmental Science and Technology 12/2009; 44(1):284-9. · 5.23 Impact Factor
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ABSTRACT: Photochemical processes can decontaminate the aqueous environment from xenobiotics, but they also produce secondary pollutants. This paper presents field and laboratory evidence of the transformation of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (2N4CP).
Field monitoring of 4CP and 2N4CP was carried out by solid phase extraction coupled with liquid chromatography-multiple reaction monitoring mass spectrometry. Laboratory irradiation experiments were carried out under a UV-Vis lamp, and the time evolution of the compounds of interest was followed by liquid chromatography.
The purpose of this study was elucidating the pathways leading to 2N4CP from 4CP in paddy field water.
The field monitoring results suggest that 4CP can be transformed into 2N4CP in the paddy field water of the Rhône delta (Southern France). The laboratory study indicates that the transformation can take place via photonitration by (*)NO(2). The nitration process is inhibited by bicarbonate, possibly due to basification that favours the occurrence of the 4-chlorophenolate. The latter could consume (*)NO(2) without being nitrated. Photonitration in the presence of bicarbonate could account for the observed transformation in the field.
Photonitration of 4CP to 2N4CP by (*)NO(2) could account for the observed interconversion of the two compounds in paddy fields. The results are of concern because 2N4CP is biorecalcitrant and toxic.
Bicarbonate can modulate the photonitration of 4CP into 2N4CP, which can be very significant in bicarbonate-poor waters.
Environmental Science and Pollution Research 11/2009; 17(5):1063-9. · 2.65 Impact Factor
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ABSTRACT: The phototransformation of clarithromycin and roxithromycin, two human-used macrolide (MLs) antibiotics was investigated in surface waters. Photolysis kinetic data suggest that degradation in water would occur via the direct photolysis of the Fe(III)-MLs complexes. Hydroxyl radicals, singlet oxygen and other photooxidants generated from nitrate ions and from excited chromophores present in humic acids appeared to have only a very limited impact on the overall degradation of MLs under the adopted UV-vis irradiation conditions. A photolysis model applied to the Fe(III)-clarithromycin complex in river water showed that a half-life of 40 days was predicted under clear-sky irradiation in November, 26 days in February, and 10 in May. Direct photolysis could have a limited impact on the environmental concentrations of MLs in rivers, due to a too short water residence time but might be important in shallow lakes and lagoons. Photoinduced degradation of MLs mainly implied changes in the structure of the aglycone, probably leading to their detoxification because the pseudoerythromycin derivatives have very little antimicrobial activity.
Water Research 03/2009; 43(7):1959-67. · 4.86 Impact Factor
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ABSTRACT: The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity.
Environmental pollution (Barking, Essex: 1987) 01/2009; 157(4):1317-22. · 3.43 Impact Factor
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ABSTRACT: Bicarbonate enhances the transformation of phenol upon irradiation of hematite, and phenol nitration upon irradiation of both nitrate and nitrite. Hematite under irradiation is able to oxidise the carbonate ion to the CO3-. radical, which in turn oxidises phenol to the phenoxyl radical faster compared to the direct photo-oxidation of phenol by hematite. The formation of CO3-. from hematite and carbonate under irradiation is supported by the detection of 3,3'-dityrosine from tyrosine, added as a probe for CO3-.. It is shown that Fe(III) might be an important photochemical source of CO3-. in Fe-rich waters, e.g. waters that contain more than 1 mg L(-1) Fe. The enhancement by bicarbonate of phenol nitration upon nitrate irradiation is probably accounted for by an increased photogeneration rate of nitrogen dioxide. The process could lead to enhanced phenol photonitration by nitrate in waters rich of inorganic carbon (>10 mM bicarbonate). Bicarbonate also increases the transformation and nitration rates of phenol upon nitrite photolysis. The effect is due to the combination of basification that enhances phenol nitrosation and nitration, and of peculiar bicarbonate chemistry. It is shown that bicarbonate-enhanced phenol nitration upon nitrite photolysis could be a significant photonitration pathway, leading to the generation of toxic nitrated compounds in natural waters in which the scavenging of hydroxyl radicals by nitrite is competitive with that of Dissolved Organic Matter (DOM).
Photochemical and Photobiological Sciences 01/2009; 8(1):91-100. · 2.58 Impact Factor
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ABSTRACT: A field monitoring campaign for pesticides and their transformation intermediates was carried out in the Rhône delta (Southern France). It was evidenced the following transformation sequence: MCPA-->4-chloro-2-methylphenol (CMP)-->4-chloro-2-methyl-6-nitrophenol (CMNP). Interestingly CMP disappeared about as quickly as MCPA, while CMNP was environmentally more persistent than the parent molecules. This is very relevant to the environmental risk associated with the occurrence of these compounds, because the nitration of chlorophenols reduces their acute toxicity but the nitroderivatives could have more marked long-term effects, associated with their genotoxicity. Irradiation experiments suggested that the photonitration of CMP into CMNP involves nitrogen dioxide, generated from the photolysis of nitrate and from the photooxidation of nitrite by ()OH. The photochemistry of Fe(III) species could also play a significant role, but its contribution is still difficult to be quantified. Another important intermediate of CMP transformation is methylnitrophenol (MNP), produced via a dechlorination/nitration pathway, with ortho-cresol as the most likely reaction intermediate.
Chemosphere 11/2008; 74(4):599-604. · 3.21 Impact Factor
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ABSTRACT: A field study on the runoff of pesticides was conducted during the cultivation period in 2004 on a hydraulically isolated rice farm of 120 ha surface with one central water outlet. Four pesticides were studied: Alphamethrin, MCPA, Oxadiazon, and Pretilachlor. Alphamethrin concentrations in runoff never exceeded 0.001 microg L(-1). The three other pesticides were found in concentrations between 5.2 and 28.2 microg L(-1) in the runoff water shortly after the application and decreased thereafter. The data for MCPA compared reasonably well with predictions by an analytical runoff model, accounting for volatilization, degradation, leaching to groundwater, and sorption to soil. The runoff model estimated that runoff accounted for as much as 18-42% of mass loss for MCPA. Less runoff is observed and predicted for Oxadiazon and Pretilachlor. It was concluded that runoff from rice paddies carries important loads of dissolved pesticides to the wetlands in the Ile de Camargue, and that the model can be used to predict this runoff.
Environmental Pollution 03/2008; 151(3):486-93. · 3.75 Impact Factor
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ABSTRACT: 2,4-Dichlorophenol (2,4-DCP) and 2,6-dichlorophenol (2,6-DCP) undergo oxidation, nitrosation and nitration in the presence of nitrate under UV irradiation. Nitration is favoured under acidic conditions, most likely because HNO(2) is formed on nitrate photolysis. The most likely photonitration pathway is the reaction between radiation-excited dichlorophenols (DCP*) and HNO(2). HNO(2) is also able to nitrate DCP in the dark with elevated yields. Irradiation also causes DCP direct photolysis, which is more efficient for the dichlorophenolate anions. The photolysis of the dichlorophenols and that of the dichlorophenolates also produce different intermediates, by dechlorination in the former and ring contraction in the latter case.
Chemosphere 12/2007; 69(10):1548-54. · 3.21 Impact Factor
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ABSTRACT: 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.
Science of The Total Environment 11/2007; 385(1-3):242-51. · 3.29 Impact Factor
