Efficient use of Fe metal as an electron transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron M?ssbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.     

Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn

Groundwater and wastewater contaminated with chlorinated organic compounds (COCs) can be treated with zero-valent metals. The practicality of this treatment method depends on the reduction rates of the target compounds and their byproducts. In this study, nano-scale Fe and Fe/Ni particles were synthesized so that they could be used to rapidly degrade carbon tetrachloride (CT) and chloroform (CF). Their BET surface areas were around two orders higher than those of commercial micro-scale Fe and Zn particles. Batch reduction experiments carried out with a metal loading of 2.5 gl(-1) showed that complete reduction of CT by the nano-scale Fe/Ni and Fe particles could be achieved within 20 min and 60 min, respectively. With the commercial micro-scale Fe and Zn particles applied at 125 gl(-1), complete CT reduction could only be achieved after 4h and 1.5h, respectively. Reductions of CT and CF with the nano-scale particles followed pseudo-first-order kinetics, and the specific reaction rate constants with the nano-scale Fe/Ni particles were 2-8 times higher than those of the nano-scale Fe particles. CT was degraded through hydrogenolysis to CF, and subsequently via both complete reduction pathway to methane and hydrogenolysis pathway to dichloromethane (DCM). Significantly more methane was generated with the use of the nano-scale Fe/Ni particles than with the nano-scale Fe particles. While the commercial Zn particles were more reactive than the commercial Fe particles, they failed to transform CT directly into methane, causing accumulation of DCM in the aqueous phase.     

Sonolysis of alkylphenols in aqueous solution with Fe(II) and Fe(III)

The sonolytic degradation of alkylphenols (APs), such as butylphenol, pentylphenol, octylphenol, and nonylphenol (NP), in water was investigated at a sound frequency of 200 kHz with an acoustic intensity of 6 W cm(-2) under argon, oxygen, and air atmospheres. The sonolytic degradation rate of the APs under the conditions of the present study depended upon their alkyl chain length. The decrease in the degradation rate by the radical scavenging effect was in the range of about 48-82% for APs in the presence of 3 mM 2-methyl-2-propanol. The free radicals play a significant role in the sonolytic degradation process of the APs. In the presence of Fe(II) and Fe(III), the pseudo-first-order rate constants for the sonolytic degradation of 30 microM NP as a function of the concentration of Fe(II) and Fe(III) were estimated under argon and oxygen. The maximum rate constants were observed at 50 microM Fe(II) (0.139 +/- 0.008 min(-1)) and 100 microM Fe(III) (0.103 +/- 0.001 min(-1)) under oxygen. The total organic carbon concentration (TOC) was investigated under same conditions. TOC decreased in the range of about 50-70% during the sonication in the presence of Fe(II) and Fe(III) under argon and oxygen. The sonochemical effects by the addition of Fe(II) and Fe(III) as catalyst during the sonication under the proper atmosphere result in a remarkable enhancement of degradation and mineralization.     

Comparison of hematite/Fe(II) systems with cement/Fe(II) systems in reductively dechlorinating trichloroethylene

Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons are unknown. This study initially evaluated reactivities of potential reactive agents of cement/Fe(II) systems such as hematite (alpha-Fe(2)O(3)), goethite (alpha-FeOOH), lepidocrocite (gamma-FeOOH), akaganeite (beta-FeOOH), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12)), Friedel's salt (Ca(4)Al(2)Cl(2)(OH)(12)), and hydrocalumite (Ca(2)Al(OH)(6)(OH).3H(2)O) in reductively dechlorinating trichloroethylene (TCE) in the presence of Fe(II). It was found that a hematite/Fe(II) system shows TCE degradation characteristics similar to those of cement/Fe(II) systems in terms of degradation kinetics, Fe(II) dose dependence, and final products distribution. It was therefore suspected that Fe(III)-containing phases of cement hydrates in cement/Fe(II) systems behaved similarly to the hematite. CaO, which was initially introduced as a pH buffer, was observed to participate in or catalyze the formation of reactive reductants in the hematite/Fe(II) system, because its addition enhanced the reactivities of hematite/Fe(II) systems. From the SEM (scanning electron microscope) and XRD (X-ray diffraction) analyses that were carried out on the solids from hematite/Fe(II) suspensions, it was discovered that a sulfate green rust with a hexagonal-plate structure was probably a reactive reductant for TCE. However, SEM analyses conducted on a cement/Fe(II) system showed that hexagonal-plate crystals, which were presumed to be sulfate green rusts, were much less abundant in the cement/Fe(II) than in the hematite/Fe(II) systems. It was not possible to identify any crystalline minerals in the cement/Fe(II) system by using XRD analysis, probably because of the complexity of the cement hydrates. These observations suggest that major reactive reductants of cement/Fe(II) systems may differ from those of hematite/Fe(II) systems.     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

Potential application of highly reactive Fe(0)/Fe3O4 composites for the reduction of Cr(VI) environmental contaminants

We describe the use of highly reactive Fe(0)/Fe3O4 composites for the reduction of Cr(VI) species in aqueous medium. The composites were prepared by simple mechanical alloying of metallic iron and magnetite in different proportions, i.e. Fe(0) 25, 50, 75 and 90wt%. While after 3h of reaction pure Fe(0) and pure Fe3O4 showed only a low reduction efficiency of 15% and 25% Cr(VI) conversion, respectively, the composites, in particular Fe(0)(25wt%)/Fe3O4, showed a remarkable activity with ca. 65% Cr(VI) conversion. Kinetic experiments showed a high reaction rate during the first 3h, which subsequently decreased strongly, probably due to a pH increase from 6 to 8. Experiments with composites based on Fe(0)/alpha-Fe2O3, Fe(0)/gamma-Fe2O3 and Fe(0)/FeOOH showed very low activities, suggesting that Fe(oct)2+ in the magnetite structure plays an important role in the reaction. Scanning and high resolution electron microscopies and M?ssbauer spectra (transmission and conversion electron M?ssbauer spectroscopy) indicated that the mechanical alloying process promotes a strong interaction and interface between the metallic and oxide phases, with the Fe(0) particles completely covered by Fe3O4 particles. The high efficiency of the composite Fe(0)/Fe3O4 for Cr(VI) reduction is discussed in terms of a special mechanism where an electron is transferred from Fe(0) to magnetite to reduce Fe(oct)3+ to Fe(oct)2+, which is active for Cr(VI) reduction.     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

Catalytic dechlorination kinetics of p-dichlorobenzene over Pd/Fe catalysts

p-Dichlorobenzene (p-DCB) was dechlorinated using Pd/Fe bimetallic catalytic reductants synthesized by chemical deposition. Batch experiments demonstrated that the Pd/Fe bimetallic particles could effectively dechlorinate p-DCB, p-DCB and its intermediate chlorobenzene were removed completely at a Pd loading of 0.02% (weight ratio of Pd to Fe) and Pd/Fe power to solution ratio about 4g 75 ml-1 in 90 min. Dechlorination was affected by various factors such as the reaction temperature, pH, Pd loading percentage over Fe and the introduction of Pd/Fe catalysts et al. Chlorobenzene represents partially stable dechlorinated intermediates in the generation of benzene and part of p-DCB was dechlorinated to benzene indirectly on the surface of Pd/Fe. The dechlorination of p-DCB took place on the surface of the Pd/Fe bimetallic particles in a pseudo-first-order reaction, the activation energy of the dechlorination reaction was determined to be 80.0 kJ mol-1 at the temperature range of 287-313 K.     

Effects of pH, Fe, and Cd on the uptake of Fe2+ and Cd2+ by rice

The rhizosphere plays an important role in altering cadmium (Cd) solubility in paddy soils and Cd accumulation in rice. However, more studies are needed to elucidate the mechanism controlling rice Cd solubility and bioavailability under different rhizosphere conditions to explain the discrepancy of previous studies. A rice culture with nutrient solution and vermiculite was conducted to assess the effects of pH, Eh, and iron (Fe) concentration on Cd, Fe fractions on the vermiculite/root surface and their uptake by rice. The solution pH was set from 4.5 to 7.5, with additions of Fe (30 and 50 mg L^?1) and Cd (0.5 and 0.9 mg L^?1). At pH 5.5, the Eh in the rice rhizosphere was higher whereas transpiration, Cd²⁺, and Fe²⁺ adsorption on the vermiculite/root surface and accumulation in rice were lower than the other pH treatments. Cadmium addition had no impact on pH and Eh in rice rhizosphere while Fe addition decreased pH and increased Eh significantly. Compared with control, Fe addition resulted in the decrease of rhizosphere Cd, Fe solubility and bioavailability. Higher redox potential in the rice rhizosphere resulted in the decline of transpiration, Cd, and Fe accumulation in the rice tissues, suggesting that the transfer of two elements from soil to rice was depressed when the rhizosphere was more oxidized.     

Relation of enhanced Pb solubility to Fe partitioning in soils

It is well documented that Pb solubility may be related to Fe chemistry in soils and enhanced Pb solubility may occur under certain reducing conditions; however, quantification of such relationships is unavailable. Based on metal classification, Pb (II) and Fe (II) are similar in some chemical characteristics. Thus, competition between Pb and Fe for ligands in soils may be important in determining Pb solubility. In this paper, Pb solubility was examined in a sandy soil after spiking with Pb and incubating for 40 days under water-flooded or non-water-flooded conditions. Solution chemistry in soil columns was adjusted using different concentrations of NaCl, CaCl(2) and deionized water of varying pH before incubation. The results showed that Pb solubility in the soil was not correlated well with pH, dissolved organic C or aqueous Fe concentrations. However, an index of Fe partition behavior using the ratio of aqueous Fe to sorbed Fe was related to Pb solubility. Enhanced Pb solubility occurred only when the index was < approximately 2 kg l(-1). The index can be a simple measure of Fe's ability to compete with Pb for ligands in solution. The ability of Fe to compete with Pb decreases as the index decreases and as the ratio approached its minimum, substantial increases in Pb solubility will be expected. In general, the index was not sensitive to changes in solution chemistry. A similar trend was observed using one data set published in the literature.     

Influence of pH,EDTA/Fe(II) ratio,and microbial culture on Fe(II)-mediated autotrophic denitrification

Environmental Science and Pollution Research - Fe(II)-mediated autotrophic denitrification with four different microbial cultures under different pH and EDTA/Fe(II) conditions was investigated in...     

Dechlorination of pentachloroethane by commercial Fe and ferruginous smectite

Short-term experiments were conducted to investigate the effect of a commercial Fe and an iron-bearing clay mineral, ferruginuous smectite (SWa-1), on the degradation of pentachloroethane (PCA). After 3 h of contact time, SWa-1 catalyzed PCA dehydrochlorination to tetrachloroethene (PCE, 65% conversion), whereas commercial Fe promoted PCA stepwise dechlorination via dehydrochlorination (approximately 40% conversion) and subsequent PCE hydrogenolysis to trichloroethene (TCE). The addition of unaltered SWa-1 to commercial Fe led to a complete inhibition on TCE production, whereas the addition of reduced SWa-1 barely resulted in a 30% decrease.     

Comparative study of the oxidation of atrazine and acetone by H2O2/UV, Fe(III)/UV, Fe(iii)/H2O2/UV and Fe(II) or Fe(III)/H2O2

In this study, the rates of degradation of organic compounds by several AOPs (H₂O₂/UV, Fe(III)/UV, Fe(III)/H₂O₂/UV, Fe(II)/H₂O₂ and Fe(III)/H₂O₂) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]_o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H₂O₂/UV. Photo-Fenton process (Fe(III)/H₂O₂/UV) was found to be more efficient than H₂O₂/UV and Fe(II)/H₂O₂ for the mineralization of acetone ([Acetone]_o = 1 mM).     

Dechlorination of trichloroethylene by a steel converter slag amended with Fe(II)

This study aims to assess the feasibility of using slag, byproduct from iron and steel making industries, as a new reactive material for dechlorination reactions and to investigate dechlorination chemistries of the systems containing the slag and Fe(II). Initially, screening experiments were conducted to evaluate various systems containing slags with or without Fe(II). A combination of the steel converter slag and Fe(II) showed a potential to be developed as a reactive material to treat chlorinated organics. Further kinetic studies with the steel converter slag/Fe(II) systems revealed that the dechlorination capacity of the slag/Fe(II) system is comparable to that of zero-valent iron and generally higher than the cement/Fe(II) system. The slag/Fe(II) system can substantially dechlorinate trichloroethylene (TCE) in the neutral pH region, although the dechlorination rate was greatest in the pH region between 12 and 13. TCE reductions in the slag/Fe(II) system were observed to occur through reductive beta-elimination pathways that produce primarily acetylene and no chlorinated intermediates such as vinyl chloride. These results demonstrate that the steel converter slag with Fe(II) has sound characteristics for an alternative reactive medium for subsurface remediation.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Biodegradation of nonylphenol polyethoxylates under Fe(III)-reducing conditions

Biodegradation behavior of nonylphenol polyethoxylates (NPEOs) under Fe(III)-reducing conditions was investigated. The study demonstrated that NPEOs could be rapidly biodegraded under Fe(III)-reducing conditions. Almost 60% of the total NPEOs were removed within three days and the maximum biodegradation rate was 34.95+/-0.84 microM d(-1). NPEOs were degraded via sequential removal of ether units under Fe(III)-reducing conditions. No nonylphenol polyethoxy-carboxylates (NPECs) were formed in this process. This ether removal process was coupled to Fe(III) reduction. Nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) slightly accumulated in the anaerobic biodegradation process. The accumulation of these estrogenic metabolites led to a significant increase in the estrogenic activity during the biodegradation period. The calculated estrogenic activity reached its top on day 14 when the total concentration of these estrogenic metabolites was maximal. This is the first report of the primary biodegradation behavior of NPEOs under Fe(III)-reducing conditions. These findings are of major environmental importance in terms of the environmental behavior of NPEO contaminants in natural environment.     

Mineralisation of Monuron photoinduced by Fe(III) in aqueous solution

The degradation of Monuron (3-(4-chlorophenyl)-1,1-dimethylurea) photoinduced by Fe(III) in aqueous solution has been investigated. The rate of degradation depends on the concentration of Fe(OH)2+, the most photoreactive species in terms of *OH radical formation. These *OH radicals are able to degrade Monuron until total mineralisation. The primordial role of the speciation of Fe(III)-hydroxy complex in aqueous solution, for the efficiency of the elimination of pollutant, was shown and explained in detail. The formation of Fe(II) in the irradiated solution was monitored and correlated with the total organic carbon evolution. Degradation photoproducts were identified and a mechanism of degradation is proposed.     

Oxidation of [Fe(CN)6]4- and reduction of [Fe(CN)6]3- in VUV-irradiated aqueous solutions

Vacuum ultraviolet (VUV) photolysis is one of the straightforward alternatives method among the advanced oxidation processes (AOPs) for the elimination of pollutants from water and air. The VUV photolysis of water produces hydroxyl radicals and hydrogen atoms, which have widely different oxidation and reduction abilities. In this work the oxidation and reduction properties of VUV-irradiated solutions were compared by investigating the reduction of [Fe(CN)6]3- and the oxidation of [Fe(CN)6]4-. The rate of oxidation of [Fe(CN)6]3- was found to be practically the same as the reduction rate of [Fe(CN)6]4- in the irradiated oxygen-free solutions under identical conditions. Dissolved oxygen strongly influences the redox properties of this system.     

废弃核桃壳粉对模拟微污染水中总铁的静态吸附特性研究

采用废弃核桃壳粉对总铁质量浓度约为3 mg/L的模拟微污染水进行了静态吸附实验研究.结果表明,采用产地为新疆、粒径为1.6～2.5 mm的废弃核桃壳粉1.0 g、水样初始pH为7.0、吸附时间为240 min时,总铁去除率可以达到92.69%.吸附后,水样中总铁浓度满足<生活饮用水卫生标准>(GB 5749-2006)...     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10^{? 3} h^{? 1} to 7.0 × 10^{? 3} h^{? 1}. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.