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.     

Dechlorination of trichloroethylene formed from 1,1,2,2-tetrachloroethane by dehydrochlorination in Portland cement slurry including Fe(II)

Transformation of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) by Fe(II) in 10% cement slurries was characterized using a batch reactor system. 1,1,2,2-TeCA was completely converted to trichloroethylene (TCE) within 1h in all experiments, even in controls with cement that did not include Fe(II). Therefore, complete degradation of 1,1,2,2-TeCA depends on the behavior of TCE. The half-life of TCE was observed to be 15d when concentrations of Fe(II) and 1,1,2,2-TeCA were 98mM and 0.245mM, respectively. The kinetics of TCE removal was observed to be dependent on Fe(II) dose, pH and initial substrate concentration. Pseudo-first-order rate constants linearly increased with Fe(II) dose up to 198mM when initial target concentration was 0.245mM. Pseudo-first-order kinetics generally described the degradation reactions of TCE at a specific initial concentration, but a modified Langmuir-Hinshelwood model was necessary to describe the degradation kinetics of TCE over a wide range of initial concentrations. A surface reaction of TCE on active solids, which were formed from Fe(II) and products of cement hydration appears to control observed TCE degradation kinetics.     

Enhanced effect of HAH on citric acid-chelated Fe(II)-catalyzed percarbonate for trichloroethene degradation

This work demonstrates the impact of hydroxylamine hydrochloride (HAH) addition on enhancing the degradation of trichloroethene (TCE) by the citric acid (CA)-chelated Fe(II)-catalyzed percarbonate (SPC) system. The results of a series of batch-reactor experiments show that TCE removal with HAH addition was increased from approximately 57 to 79% for a CA concentration of 0.1 mM and from 89 to 99.6% for a 0.5 mM concentration. Free-radical probe tests elucidated the existence of hydroxyl radical (HO^•) and superoxide anion radical (O₂ ^•-) in both CA/Fe(II)/SPC and HAH/CA/Fe(II)/SPC systems. However, higher removal rates of radical probe compounds were observed in the HAH/CA/Fe(II)/SPC system, indicating that HAH addition enhanced the generation of both free radicals. In addition, increased contribution of O₂ ^•- in the HAH/CA/Fe(II)/SPC system compared to the CA/Fe(II)/SPC system was verified by free-radical scavengers tests. Complete TCE dechlorination was confirmed based on the total mass balance of the released Cl⁻ species. Lower concentrations of formic acid were produced in the later stages of the reaction for the HAH/CA/Fe(II)/SPC system, suggesting that HAH addition favors complete TCE mineralization. Studies of the impact of selected groundwater matrix constituents indicate that TCE removal in the HAH/CA/Fe(II)/SPC system is slightly affected by initial solution pH, with higher removal rates under acidic and near neutral conditions. Although HCO₃ ⁻ was observed to have an adverse impact on TCE removal for the HAH/CA/Fe(II)/SPC system, the addition of HAH reduced its inhibitory effect compared to the CA/Fe(II)/SPC system. Finally, TCE removal in actual groundwater was much significant with the addition of HAH to the CA/Fe(II)/SPC system. The study results indicate that HAH amendment has potential to enhance effective remediation of TCE-contaminated groundwater.

     

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).     

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.     

Reductive dechlorination of chlorinated methanes in cement slurries containing Fe(II)

Degradative solidification/stabilization (DS/S) is a novel remediation technology that combines chemical degradation with conventional solidification/stabilization. The applicability of the Fe(II)-based DS/S to treating chlorinated alkanes was tested by characterizing degradation reactions of carbon tetrachloride (CT) and its daughter products in cement slurries containing Fe(II). Degradation kinetics of CT and chloroform (CF) were generally very rapid with reaction rates comparable to rates that can be obtained with zero-valent iron. Dechlorination reactions of CT proceeded primarily via a hydrogenolysis pathway, which yielded CF and methylene chloride (MC) as major products and chloromethane and methane as minor products. However, reaction pathways other than hydrogenolysis also appeared to be important at very high pH conditions. MC apparently was resistant to dechlorination reactions over a period of about two months. Kinetics of CT and CF transformation were strongly dependent on pH with an optimal value around 13, which was higher than found previously for PCE. When the initial CF concentration varied between 0.01 and 1 mM, and the Fe(II) dose was 104 mM, pseudo-first-order kinetics generally described the degradation reactions of CF. However, there was also some indication of substrate saturation kinetics in these experiments. This suggests that a saturation model would better describe the kinetics in systems with higher concentration of substrates or lower concentration of the reactive surfaces.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.     

Influence of iron-bearing phyllosilicates on the dechlorination kinetics of 1,1,1-trichloroethane in Fe(II)/cement slurries

This study examines the effect of iron-bearing phyllosilicates on dechlorination rates of chlorinated aliphatic hydrocarbons (CAHs) in iron-based degradative solidification/stabilization (DS/S-Fe(II)). Laboratory batch experiments were conducted to evaluate dechlorination rates of 1,1,1-trichloroethane (1,1,1-TCA) in a mixture solution of Fe(II), cement and three different iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite). A first-order rate model was generally used to describe the dechlorination kinetics and the rate constants were dependent on soil mineral type (biotite, vermiculite, and montmorillonite), Fe(II) dose, and the mass ratio of cement to soil mineral. The pseudo-first-order rate constant for montmorillonite was lower than that for biotite and vermiculite by factors of 11-27 when the mass ratio of cement to phyllosilicates was fixed at one. The presence of biotite and vermiculite increase and the presence of montmorillonite decrease the degradation rate that would be observed in their absence. The effect of cement/mineral ratio on rate constants with three different soil minerals indicates that biotite was more reactive than the other two phyllosilicates. This may be due to high accessible natural Fe(II) content in biotite. Montmorillonite appears to inhibit dechlorination by either inactivating Fe(II) by ion exchange or by physically blocking active sites on cement hydration products.     

Thermodynamics of metal cation binding by a solid soil-derived humic acid: binding of Fe(III), Pb(II), and Cu(II)

Metal binding and release by solid humic acids (HAs) in soils and sediments can affect metal mobility and bioavailability. Isotherms for tight binding of Fe(III), Pb(II) and Cu(II) by a solid humic acid at pH2.0 fit the Langmuir binding model. Low pH was chosen to protonate the HA carboxylate groups and avoid metal cation hydrolysis. Binding of Fe(III), Pb(II) and Cu(II) occurs in one detectable step labeled A. Site capacities nu(A) are temperature-independent from 10.0 to 40.0 degrees C and point to binding by charge-neutralization to form solid complexes M(OOC-R)(n)(s), where n appears to be 2 for Pb(II) and 3 for Fe(III). Thermodynamic data pairs (DeltaH(A), DeltaS(A)) for metal binding are linearly correlated with previous data for Ca(II), Co(II) and Mg(II) binding by solid HAs.     

Abiotic reductive dechlorination of chlorinated ethylenes by soil

Abiotic reductive dechlorination of chlorinated ethylenes by soil in anaerobic environments was characterized to improve knowledge of the behavior of chlorinated ethylenes in natural systems, including systems modified to promote attenuation of contaminants. Target organics in the soil suspension reached sorption equilibrium in 2 days and the sorption isotherm of target organics was properly described by the linear sorption model. A modified Langmuir-Hinshelwood model was developed to describe the kinetics of reductive dechlorination of target organics by soil. The rate constants for the reductive dechlorination of chlorinated ethylenes at the reactive surfaces of reduced soils were found in the range between 0.055 (+/- 8.9%) and 2.60 (+/- 3.2%) day(-1). The main transformation products in reduced soil suspensions were C2 hydrocarbons. No chlorinated intermediates were observed at concentrations above detection limits. Five cycles of reduction of the soil followed by oxidation of the soil with trichloroethylene (TCE) did not affect the removal of TCE. The removal was affected by the reductants used and increased in the order: Fe(II) < dithionite < Fe(II) + dithionite.     

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.     

Photochemically induced formation of the "Al13" tridecameric polycation in the presence of Fe(III) and organic acids

We found that light-induced Fe(III) reduction associated with the oxidation of a simple hydroxy-carboxylic acid (lactate) caused the formation of the AlO4Al12(OH)24(H2O)12 polycation ("Al13"). Initial conditions were a lactate:Al:Fe ratio of 1:0.76:0.11 in a partially neutralized solution. Base was added rapidly and no Al13 was detected in samples kept in the dark. With exposure to light, Fe(III) reduction was rapid and Fe(II) reached a maximum within 1 day. After the maximum, steady-state Fe(II) declined from 54% to 43% over eight days. During this same time period, the lactate concentration fell to 2% of the original, pH rose from 4.05 to 4.46, and the Al13 detectable by 27Al NMR increased to 2.3 mmol l(-1) (51% of the total solution Al). The formation of Al13 is attributed to the pH rise resulting from the removal of the organic acid buffer. Similar photo-induced chemical changes occur in natural waters and may promote the formation of Al13, conditions permitting.     

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.     

Degradation of polychlorinated dibenzo-p-dioxins in aqueous solution by Fe(II)/H2O2/UV system

The photodegradation of polychlorinated dibenzo-p-dioxins (PCDDs), which include tetra- to octa-CDDs (TeCDD, PeCDD, HxCDD, HpCDD and OCDD), was carried out in the presence of Fe(II) and H2O2 mixed reagent. The degradation efficiency was strongly influenced by UV irradiation, and the initial concentrations of H2O2 and Fe(II). An initial TeCDD concentration of 10 ng l(-1) was completely degraded within 20 min under the optimum conditions. All PCDDs tested were successfully degraded by Fe(II)/H2O2/UV treatment and complete degradation of TeCDD, PeCDD and HxCDD was achieved within 120 min. PCDD photodegradation rates decreased with the number of chlorine atoms. The degradation process of TeCDD by this system seems to be initiated by an oxidative reaction (OH* radical attack) because less chlorinated DDs as intermediate products were not detected. From the Frontier electron density calculation, the first OH* radical attack positions on TeCDD were found to be four C atoms neighboring two O atoms. The decomposition of TeCDD gave 4,5-dichlorocatechol as an intermediate product. A TeCDD degradation scheme was proposed based on the identified intermediate and the values of Frontier electron density. Based on these results, Fe(II)/H2O2/UV system could be useful technology for the treatment of wastewater containing persistent pollutants such as dioxins and polychlorinated biphenyls.     

Formation of leadhillite and calcium lead silicate hydrate (C-Pb-S-H) in the solidification/stabilization of lead contaminants

In this study, we have investigated the structure of Pb-doped solidified waste forms (SWF) for assessment of lead fixation. A large quantity of lead precipitates produced during the S/S, based upon the results of cement-water solution analysis, X-ray diffraction and electron probe microanalysis/electron dispersive spectroscopy investigations, have been shown to be principally leadhillite (lead carbonate sulfate hydroxide, Pb(4)SO(4)(CO(3))(2)(OH)(2)), lead carbonate hydroxide hydrate (3PbCO(3).2Pb(OH)(2).H(2)O) and two other unidentified lead salts. In the long curing, the lead species dissolved from the lead precipitates are fixed into the cement matrix, forming a gelling calcium lead silicate hydrate during cement-based solidification. On leaching the lead precipitates such as leadhillite were markedly dissolved/released and some dissolved lead species were adsorbed to silicate-rich surface of leached SWF with the subsequent formation of mainly amorphous gel of calcium lead silicate hydrate.     

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...     

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.     

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.     

Dechlorination of chlorinated hydrocarbons by bimetallic Ni/Fe immobilized on polyethylene glycol-grafted microfiltration membranes under anoxic conditions

In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE > PCE > CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol⁻¹, showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.