Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).     

Removing nitric oxide from flue gas using iron(II) citrate chelate absorption with microbial regeneration

The addition of metal chelates such as Fe(II)EDTA or Fe(II)Cit to wet flue gas desulfurization systems has been shown to increase the amount of NO(x) absorption from gas streams containing SO(2). This paper attempts to demonstrate the advantage of not only using Fe(II)Cit chelate to absorb nitrogen oxides from flue gas but also the advantage gained from adding microorganisms to the system. Two distinct classes of microorganisms are needed: denitrifying and iron-reducing bacteria. The presence of oxygen in flue gas will affect the absorption efficiency of NO by Fe(II)Cit chelate. The oxidation of Fe(II) can be slowed with the help of bacteria in two ways: bacteria can serve to directly reduce Fe(III) to Fe(II) or they can serve to keep levels of dissolved oxygen in the solution low. As a result, after NO absorption, Fe(II)(Cit)NO will be reduced by denitrifying bacteria to Fe(II)Cit while Fe(III) is reduced by anaerobic bacteria back to Fe(II). Our experiments have shown that the implementation of our protocol allowed for an NO reduction rate constant increase from standard levels of 0.0222-0.100 m Mh(-1) with inlet NO changed from 250 to 1000 ppm. We have also found that total Fe concentration tends to decrease after prolonged periods of operation due to the loss of some Fe to the formation of Fe(OH)(3) that settles together with the sludge at the bottom of bioreactor tank.     

Kinetics of chemoheterotrophic microbially mediated reduction of ferric EDTA and the nitrosyl adduct of ferrous EDTA for the treatment and regeneration of spent nitric oxide scrubber liquor.

Biomass from a prototype reactor was used to investigate the kinetics of chemoheterotrophic reduction of solutions of ferric ethylenediaminetetraacetic acid (EDTA) and solutions containing the nitrosyl adduct of ferrous EDTA using ethanol as the primary electron donor and carbon source. A series of batch experiments were conducted using biomass extracted from the scrubber solution treatment and regeneration stage of a prototype iron EDTA-based unit process for the absorption of nitric oxide with subsequent biological treatment. Using a linear-sweep voltammetric method for analysis of the ferric EDTA concentration, iron-reducing bacteria were found to behave according to the Monod kinetic model, at initial concentrations up to 2.16 g chemical oxygen demand (COD) as ethanol per liter, with a half-velocity constant of 0.532 g COD as ethanol/L and a maximum specific utilization rate of 0.127 mol/L of ferric ethylenediamine-tetraacetic acid [Fe(III)EDTA]*(g volatile suspended solids [VSS]/L)d(-1). Based on batch analyses, biomass yield and endogenous decay values of iron-reducing bacteria were estimated to be 0.055 g VSS/g COD and 0.017 L/d, respectively. An average of 1.64 times the theoretical (stoichiometric) demand of ethanol was used to complete reduction reactions. Kinetics of the reduction of the nitrosyl adduct of ferrous EDTA are summarized by the following kinetic constants: half-velocity constant (Ks) of 0.39 g COD/L, maximum specific utilization rate (k) of 0.2 mol/L [NO x Fe(II)EDTA(2-)](g VSS/L)d(-1), and inhibition constant (K(I)) of 0.33 g COD/L, as applied to the modified Monod kinetic expression described herein. Based on batch analyses, the biomass yield of nitrosyl-adduct-reducing bacteria was estimated to be 0.259 g VSS/g COD, endogenous decay was experimentally determined to be 0.0569 L/d, and an average of 1.26 times the stoichiometric demand of ethanol was used to complete reduction reactions.     

Light-induced disappearance of nitrite in the presence of iron (III)

Understanding of rapid disappearance of nitrite in natural waters and its impact on nitrogen natural cycling has remained limited. We found that NO2- disappeared rapidly in pH 3.2 aqueous Fe(III) solutions both in sunlight and in 356 nm light. Quantum yields of the NO2- loss at 356 nm were 0.049-0.14 for initial levels of 10-80 microns NO2- and 200 microns Fe(III). The NO2- loss (at 356 nm) followed apparent first-order kinetics. The rate constants were 1.3 x 10(-3) (40 microns NO2-) and 4.1 x 10(-4) s-1 (80 microns NO2-) for 100 microns Fe(III), and 2.3 x 10(-3) (40 microns NO2-) and 7.5 x 10(-4) s-1 (80 microns NO2(-1)) for 200 microns Fe(III) (t1/2 = 8.7, 27.9, 5.1, and 15.3 min, respectively). The rate constants were directly proportional to [Fe(III)]0 and inversely proportional to [NO2-]0. Agreement between the rate constants obtained experimentally and those calculated mechanistically supports the hypothesis that NO2- was oxidized to NO2 by .OH radicals from photolysis of FeOH2+ complexes, and at high [NO2-]0 (e.g., 80 microns) relative to [Fe(III)]0, hydrolysis of NO2 or N2O4 to form NO3- and NO2- could be significant. This study showed that light and Fe(III)-induced oxidation of NO2- (rate = approximately 10(-1)-10(-2) microns s-1) was more rapid than its direct photolysis (rate = approximately 10(-4) microns s-1), and the photolysis could be a significant source of .OH radicals only in cases where the Fe(III) level is much lower than the NO2- level ([Fe(III)]/[NO2-] < 1/80). This study suggests that the light and Fe(III)-induced oxidation of NO2- would be one potential important pathway responsible for the rapid transformation of NO2- in acidic surface waters, especially those affected by acid-mine drainage or volcanic activities. This study also may be of interest for modeling certain acidic atmospheric water environments.     

Geochemical and microbiological processes contributing to the transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in contaminated aquifer material

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a potential human carcinogen, and its contamination of subsurface environments is a significant threat to public health. This study investigated abiotic and biological degradation of RDX in contaminated aquifer material. Anoxic batch systems were started with and without pre-aeration of aquifer material to distinguish initial biological RDX reduction from abiotic RDX reduction. Aerating the sediment eliminated chemical reductants in the native aquifer sediment, primarily Fe(II) sorbed to mineral surfaces. RDX (50 μM) was completely reduced and transformed to ring cleavage products when excess concentrations (2 mM) of acetate or lactate were provided as the electron donor for aerated sediment. RDX was reduced concurrently with Fe(III) when acetate was provided, while RDX, Fe(III), and sulfate were reduced simultaneously with lactate amendment. Betaproteobacteria were the dominant microorganisms associated with RDX and Fe(III)/sulfate reduction. In particular, Rhodoferax spp. increased from 21% to 35% and from 28% to 60% after biostimulation by acetate and lactate, respectively. Rarefaction analyses demonstrated that microbial diversity decreased in electron-donor-amended systems with active RDX degradation. Although significant amounts of Fe(III) and/or sulfate were reduced after biostimulation, solid-phase reactive minerals such as magnetite or ferrous sulfides were not observed, suggesting that RDX reduction in the aquifer sediment is due to Fe(II) adsorbed to solid surfaces as a result of Fe(III)-reducing microbial activity. These results suggest that both biotic and abiotic processes play an important role in RDX reduction under in situ conditions.     

络合吸收结合生物转化去除氮氧化物技术

介绍了络合吸收结合生物转化处理NOx 技术的基本原理和目前的研究进展情况 ,并分析了该技术处理氮氧化物存在的问题和未来发展方向     

Simultaneous oxidation of EDTA and reduction of metal ions in mixed Cu(II)/Fe(III)-EDTA system by TiO2 photocatalysis

Both the photooxidation of EDTA and the photoreduction of metal ions in metal-EDTA systems were investigated. EDTA oxidation by TiO(2) photocatalysis occurred sequentially as Cu(II)-EDTA>Cu(II)/Fe(III)-EDTA>Fe(III)-EDTA. For Cu(II)-EDTA, EDTA was completely decomposed after only 60min of irradiation. The rate of EDTA decomposition was directly correlated with the initial Cu(II) concentration in the case of a mixed Cu(II)/Fe(III)-EDTA system. The metal ions in a single metal-EDTA complex were removed following significant decomposition of EDTA. For a mixed Cu(II)/Fe(III)-EDTA system, however, no copper was removed whereas almost all of the iron was removed. The iron and copper species deposited on the TiO(2) surface were identified via EPR and XPS as mixed FeO/Fe(3)O(4) and Cu(0)/Cu(2)O, respectively.     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

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.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Effect of biogenic iron species and copper ions on the reduction of carbon tetrachloride under iron-reducing conditions

In this study, the cell-mediated and abiotic reduction of carbon tetrachloride (CCl(4)) by biogenic iron species produced from the reductive dissolution of ferrihydrite in the presence of Geobacter sulfurreducens and copper ions (Cu(II)) were investigated. 9,10-Anthraquinone-2,6-disulfonate (AQDS), serving as a surrogate of natural organic matters and an electron shuttling compound, was added to enhance the efficiency of biological reduction of the solid Fe(III) minerals. G. sulfurreducens drove the reduction of CCl(4), primarily through the formation of biogenic surface-bound iron species produced from the reductive dissolution of ferrihydrite, in the presence of 10microM AQDS. The pseudo-first-order rate constant (k(obsCT)) for CCl(4) transformation in the presence of ferrihydrite was 3.0 times higher than that resulting from the use of G. sulfurreducens alone. Addition of 0.5mM Cu(II) slightly inhibited both the growth of G. sulfurreducens and the production of biogenic Fe(II). However, the k(obsCT) values for CCl(4) transformation in ferrihydrite suspensions containing G. sulfurreducens and 0.3-0.5mM Cu(II) were 2.1-4.2 times higher than that observed in the absence of Cu(II). X-Ray powder diffraction analysis indicated that the added Cu(II) reacted with the biogenic Fe(II) ions to produce catalytic cuprous ions (Cu(I)) and secondary iron oxide minerals such as magnetite and goethite, resulting in accelerating the chemical transformation efficiency and rate of CCl(4) under iron-reducing conditions.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.     

Effects of copper and palladium on the reduction of bromate by Fe(0)

Bromate reduction by Fe(0) with incorporation of copper or palladium was investigated in batch tests. The incorporation of copper led to an increase in the rate of bromate reduction, while incorporation of palladium did not show any effect on bromate reduction by Fe(0), regardless of the bimetal application techniques (either simultaneous addition of Cu(II) or Pd(IV) into the Fe-BrO3- reaction system or using copper or palladium amended iron for bromate removal). Surface analyses by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) techniques indicated that aqueous Cu(II) was reduced and incorporated into the iron surface to form Cu2O and Cu(0). Among these two species, pure Cu(0) is not an active electron donor to the bromate reduction reaction, as shown by there being no reduction from using Cu(0) powders alone and no enhancement by Fe(0) when physically mixed with Cu(0). Although it has been proposed in the literature that the enhancement of adsorption also contributes to the enhancement of chemical reduction, this is not the case here because adsorption decreased when Cu increased. The enhanced bromate reduction rate in the presence of copper observed here is most likely the result of the newly formed active Cu(I). The presence of PdO was evidenced by XPS but yielded no enhancement in bromate reduction. Finally, the Cu2O present on the iron surface because of copper impurities in commercially available iron was found to be involved in the bromate reduction and to accelerate the reduction rate.     

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.     

Bio-reduction of arsenate using a hydrogen-based membrane biofilm reactor

Arsenate (As(V)) is a carcinogen and a significant problem in groundwater in many parts of the world. Since As(III) is generally more mobile and more toxic than As(V), the reduction of As(V) to As(III) is not a conventional treatment goal. However, reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation or complexation with sulfide or by adsorption to Fe(II)-based solids. A promising approach for reducing oxidized contaminants is the H2-based membrane biofilm reactor (MBfR). In the case of arsenate, the MBfR allows bio-reduction of As(V) to As(III) and sulfate to sulfide, thereby giving the potential for As removal, such as by precipitation of As2S3(s) or formation of Fe(II)-based solids. When As(V) was added to a denitrifying MBfR, As(V) was reduced immediately to As(III). Decreasing the influent sulfate loading increased As(V) reduction for a fixed H2 pressure. A series of short-term experiments elaborated on how As(V) loading, nitrate and sulfate loadings, and H2 pressure controlled As(V) reduction. Lower nitrate loading and increased As(V) loading increased the extent of As(V) reduction, but increased H2 pressure did not increase As(V) reduction. As(V) reduction was sensitive to sulfate loading, with a maximum As(V)-removal percentage and flux with no addition of sulfate. As(III) could be precipitated with sulfide or adsorbed to Fe(II) solids, which was verified by scanning electron microscopy and energy dispersive X-ray analysis.     

Reduction of Ag(I), Au(III), Cu(II), and Hg(II) by Fe(II)/Fe(III) hydroxysulfate green rust

Green rusts are mixed Fe(II)/Fe(III) hydroxides that are found in many suboxic environments where they are believed to play a central role in the biogeochemical cycling of iron. X-ray absorption fine structure analysis of hydroxysulfate green rust suspensions spiked with aqueous solutions of AgCH(3)COO, AuCl(n)(OH)(4-n), CuCl(2), or HgCl(2) showed that Ag(I), Au(III), Cu(II), and Hg(II) were readily reduced to Ag(0), Au(0), Cu(0), and Hg(0). Imaging of the resulting solids from the Ag(I)-, Au(III)-, and Cu(II)-amended green rust suspensions by transmission electron microscopy indicated the formation of submicron-sized particles of Ag(0), Au(0), and Cu(0). The facile reduction of Ag(I), Au(III), Cu(II), and Hg(II) to Ag(0), Au(0), Cu(0), and Hg(0), respectively, by green rust suggests that the presence of green rusts in suboxic soils and sediments can have a significant impact on the biogeochemistry of silver, gold, copper, and mercury, particularly with respect to their mobility.     

Effect of N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) on Cr(VI) reduction by Fe(II)

The complexation of Fe(II) with organic ligand results in the decrease of redox potential, and enhances the reduction ability of Fe(II). An important example is the use of Fe(II)-organic complexes to accelerate Cr(VI) reduction. Dissolved O(2) and light can potentially affect Cr(VI) reduction; however, these two factors have not been adequately evaluated. A batch technique was used to investigate the Cr(VI) reduction as influenced by the light and dissolved O(2) using N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) and Fe(II) solutions. The oxidation of Fe(II) by dissolved O(2) was rapid in the presence of HEDTA at low pH; nonetheless, the oxidation proceeded slowly when HEDTA was absent. Although Cr(VI) could be reduced by free Fe(II) at low pH, the reaction was considerably slower than that of systems involving HEDTA. The enhancement of Cr(VI) reduction by Fe(II) in the presence of high concentrations of HEDTA was achieved as a result of two processes. First, HEDTA acted as a ligand for expediting electron transfer between Fe(II) and Cr(VI). Secondly, HEDTA served as a reductant for Cr(VI) under illumination.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.     

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).