An in situ study of the role of surface films on granular iron in the permeable iron wall technology

Permeable walls of granular iron are a new technology developed for the treatment of groundwater contaminated with dissolved chlorinated solvents. Degradation ofthe chlorinated solvents involves a charge transfer process in which they are reductively dechlorinated, and the iron is oxidized. The iron used in the walls is an impure commercial material that is covered with a passive layer of Fe2O3, formed as a result of a high-temperature oxidation process used in the production of iron. Understanding the behaviour of this layer upon contact with solution is important, because Fe2O3 inhibits mechanisms involved in contaminant reduction, including electron transfer and catalytic hydrogenation. Using a glass column specially designed to allow for in situ Raman spectroscopic and open circuit potential measurements, the passive layer of Fe2O3 was observed to be largely removed from the commercial product, Connelly iron, upon contact with Millipore water and with a solution of Millipore water containing 1.5 mg/l trichloroethylene (TCE). It has been previously shown that Fe2O3 is removed from iron surfaces upon contact with solution by an autoreduction reaction; however, prior to this work, the reaction has not been shown to occur on the impure commercial iron products used in permeable granular iron walls. The rate of removal was sufficiently rapid such that the initial presence of Fe2O3 at the iron surface would have no consequence with respect to the performance of an in situ wall. Subsequent to the removal of Fe2O3 layer, magnetite and green rust formed at the iron surface as a result of corrosion in both the Millipore water and the solution containing TCE. The formation of these two species, rather than higher valency iron oxides and oxyhydroxides, is significant for the technology. The former can interfere with contaminant degradation because they inhibit electron transfer and catalytic hydrogenation. Magnetite and green rust, in contrast, will not inhibit the mechanisms involved in contaminant reduction, and hence their formation is beneficial to the long-term performance of the iron material.     

The effect of silica on the degradation of organohalides in granular iron columns

Dissolved silica species are naturally occurring, ubiquitous groundwater constituents with corrosion-inhibiting properties. Their influence on the performance and longevity of iron-based permeable reactive barriers for treatment of organohalides was investigated through long-term column studies using Connelly iron as the reactive medium. Addition of dissolved silica (0.5 mM) to the column feed solution led to a reduction in iron reactivity of 65% for trichloroethylene (TCE), 74% for 1,1,2-trichloroethane (1,1,2-TCA), and 93% for 1,1,1-trichloroethane (1,1,1-TCA), compared to columns operated under silica-free conditions. Even though silica adsorption was a gradual process, the inhibitory effect was evident within the first week, with subsequent decreases in reactivity over 288 days being relatively minor. Lower concentrations of dissolved silica species (0.2 mM) led to a lesser decrease (70%) in iron reactivity toward 1,1,1-TCA. The presence of dissolved silica species produced a shift in TCE product distribution toward the more highly chlorinated product cis-dichloroethylene (cis-DCE), although it did not appear to alter products originating from the trichloroethanes. The major corrosion products identified were magnetite (Fe3O4) or maghemite (gamma-Fe2O3) and carbonate green rust ([Fe4(2+)Fe(2)3+(OH)12][CO(3).2H2O]). Iron carbonate hydroxide (Fe(II)1.8Fe(III)0.2(OH)2.2CO3) was only found in the silica-free column, indicating that silica may hinder its formation. A comparison with columns operated under the same conditions, but using Master Builder iron as the reactive matrix, showed that Connelly iron is initially less reactive, but performs better than Master Builder iron over 288 days.     

Effects of water characteristics on nitrate reduction by the Fe0/CO2 process

In this study, CO2 was bubbled into Fe0-contained solution to create an acidic environment favorable to reduction of aqueous nitrate under various water qualities. Results showed that nitrate of 30 mg l(-1) could be removed from solutions almost completely within 30 min under the conditions of 2 g Fe0 l(-1) and CO2 bubbling flow rate of 200 ml min(-1). It was observed from the Fe0/CO2 system that one mole of nitrate reduced by Fe0 led to the formation of 6.6 mol of ferrous ions. The removal of nitrate increases with increasing Fe0 dosage, however, the removal makes no difference as the Fe0 is applied at a relatively higher dosage. In the system with various water qualities, nitrate removal was inhibited significantly in the presence of humic acid. Calcium ions strongly retard nitrate removal, whereas chloride ions promote the reduction of nitrate in a significant way. Sodium ions impose only slight inhibitive effect on nitrate removal. Water molecule in the studied system can be of significance due to its competitive capability of electrons released from Fe0.     

Channel flow and trichloroethylene treatment in a partly iron-filled fracture: experimental and model results

Technical developments have now made it possible to emplace granular zero-valent iron (Fe(0)) in fractured media to create a Fe(0) fracture reactive barrier (Fe(0) FRB) for the treatment of contaminated groundwater. To evaluate this concept, we conducted a laboratory experiment in which trichloroethylene (TCE) contaminated water was flushed through a single uniform fracture created between two sandstone blocks. This fracture was partly filled with what was intended to be a uniform thickness of iron. Partial treatment of TCE by iron demonstrated that the concept of a Fe(0) FRB is practical, but was less than anticipated for an iron layer of uniform thickness. When the experiment was disassembled, evidence of discrete channelised flow was noted and attributed to imperfect placement of the iron. To evaluate the effect of the channel flow, an explicit Channel Model was developed that simplifies this complex flow regime into a conceptualised set of uniform and parallel channels. The mathematical representation of this conceptualisation directly accounts for (i) flow channels and immobile fluid arising from the non-uniform iron placement, (ii) mass transfer from the open fracture to iron and immobile fluid regions, and (iii) degradation in the iron regions. A favourable comparison between laboratory data and the results from the developed mathematical model suggests that the model is capable of representing TCE degradation in fractures with non-uniform iron placement. In order to apply this Channel Model concept to a Fe(0) FRB system, a simplified, or implicit, Lumped Channel Model was developed where the physical and chemical processes in the iron layer and immobile fluid regions are captured by a first-order lumped rate parameter. The performance of this Lumped Channel Model was compared to laboratory data, and benchmarked against the Channel Model. The advantages of the Lumped Channel Model are that the degradation of TCE in the system is represented by a first-order parameter that can be used directly in readily available numerical simulators.     

Iron and organo-bentonite for the reduction and sorption of trichloroethylene

Hybrid barriers using dechlorination and immobilization were studied to remove trichloroethylene (TCE) in this study. Hybrid barriers of iron filings and organo (hexadecyltrimethylammonium, HDTMA)-bentonite were simulated in columns to assess the performance of the hybrid barriers. TCE reduction rate for the mixture of zero valent iron (ZVI) and HDTMA-bentonite was approximately seven times higher than that for ZVI, suggesting the reduction of TCE was accelerated when HDTMA-bentonite was mixed with ZVI. For the column of two separate layers of iron and HDTMA-bentonite, TCE reduction rate was nearly similar to that for ZVI alone, but the partition coefficient (Kd) was 4.5 times higher than that for ZVI only. TCE was immobilized in the first layer with HDTMA-bentonite due to sorption, and then dechlorinated in the second layer with iron filings due to reduction. The HDTMA-bentonite and minimally-desorbed HDTMA from the organo-bentonite are believed to contribute the increase in TCE concentration on iron surface so that more TCE could be available for reduction. Therefore, the incorporation of HDTMA-bentonite into ZVI not only can effectively retard the transport of chlorinated organic contaminants from landfill leachate or oil shock in subsurface environment, also can expedite the reduction rate of TCE.     

Persulfate oxidation of trichloroethylene with and without iron activation in porous media

In situ chemical oxidation with persulfate anion (S2O82*) is a viable technique for remediation of groundwater contaminants such as trichloroethylene (TCE). An accelerated reaction using S2O82* to destroy TCE can be achieved via chemical activation with ferrous ion to generate sulfate radicals (SO4*)(E degrees =2.6 V). The column study presented here simulates persulfate oxidation of TCE in porous media (glass beads and a sandy soil). Initial experiments were conducted to investigate persulfate transport in the absence of TCE in the column. The persulfate flushing exhibited a longer residence time and revealed a moderate persulfate interaction with soils. In TCE treatment experiments, the results indicate that the water or persulfate solution would push dissolved TCE from the column. Therefore, the effluent TCE concentration gradually increased to a maximum when about one pore volume was replaced with the flushing solution in the column. The presence of Fe2+ concentration within the column caused a quick drop in effluent TCE concentration and more TCE degradation was observed. When a TCE solution was flushing through the soil column, breakthrough of TCE concentration in the effluent was relatively slow. In contrast, when the soil column was flushed with a mixed solution of persulfate and TCE, persulfate appeared to preferentially oxidize soil oxidizable matter rather than TCE during transport. Hence, persulfate oxidation of soil organics may possibly reduce the interaction between TCE and soil (e.g., adsorption) and facilitate the transport of TCE through soil columns resulting in faster breakthrough.     

Kinetics of reductive denitrification by nanoscale zero-valent iron

Zero-valent iron powder (Fe0) has been determined to be potentially useful for the removal of nitrate in the water environment. This research is aimed at subjecting the kinetics of denitrification by nanoscale Fe0 to an analysis of factors affecting the chemical denitrification of nitrate. Nanoscale iron particles with a diameter in the range of 1-100 nm, which are characterized by the large BET specific surface area to mass ratio (31.4 m2/g), removed mostly 50, 100, 200, and 400 mg/l of nitrate within a period of 30 min with little intermediates. Compared with microscale (75-150 microm) Fe0, end product is not ammonia but N2 gas. Kinetics analysis from batch studies revealed that the denitrification reaction with nanoscale Fe0 appeared to be a pseudo first-order with respect to substrate and the observed reaction rate constant (k(obs)) varied with iron content at a relatively low degree of application. The effects of mixing intensity (rpm) on the denitrification rate suggest that the denitrification appears to be coupled with oxidative dissolution of iron through a largely mass transport-limited surface reaction (<40 rpm).     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.     

Investigation of gas production and entrapment in granular iron medium

A method for measuring gas entrapment in granular iron (Fe0) was developed and used to estimate the impact of gas production on porosity loss during the treatment of a high NO3- groundwater (up to approximately 10 mM). Over the 400-d study period the trapped gas in laboratory columns was small, with a maximum measured at 1.3% pore volume. Low levels of dissolved H2(g) were measured (up to 0.07+/-0.02 M). Free moving gas bubbles were not observed. Thus, porosity loss, which was determined by tracer tests to be 25-30%, is not accounted for by residual gas trapped in the iron. The removal of aqueous species (i.e., NO3-, Ca, and carbonate alkalinity) indicates that mineral precipitation contributed more significantly to porosity loss than did the trapped gases. Using the stoichiometric reactions between Fe0 and NO3-, an average corrosion rate of 1.7 mmol kg-1 d-1 was derived for the test granular iron. This rate is 10 times greater than Fe0 oxidation by H2O alone, based on H2 gas production. NO3- ion rather than H2O was the major oxidant in the groundwater in the absence of molecular O2. The N-mass balance [e.g., N2g and NH4+ and NO3-] suggests that abiotic reduction of NO3- dominated at the start of Fe0 treatment, whereas N2 production became more important once the microbial activity began. These laboratory results closely predict N2 gas production in a separated large column experiment that was operated for approximately 2 yr in the field, where a maximum of approximately 600 ml d-1 gas volumes was detected, of which 99.5% (v/v) was N2. We conclude that NO3- suppressed the production of H2(g) by competing with water for Fe0 oxidation, especially at the beginning of water treatment when Fe0 is highly reactive. Depends on the groundwater composition, gas venting may be necessary in maintaining PRB performance in the field.     

Field-scale demonstration of induced biogeochemical reductive dechlorination at Dover Air Force Base, Dover, Delaware

Biogeochemical reductive dechlorination (BiRD) is a new remediation approach for chlorinated aliphatic hydrocarbons (CAHs). The approach stimulates common sulfate-reducing soil bacteria, facilitating the geochemical conversion of native iron minerals into iron sulfides. Iron sulfides have the ability to chemically reduce many common CAH compounds including PCE, TCE, DCE, similar to zero valent iron (Fe(0)). Results of a field test at Dover Air Force Base, Dover, Delaware, are given in this paper. BiRD was stimulated by direct injection of Epson salt (MgSO(4).7H(2)O) and sodium (L) lactate (NaC(3)H(5)O(3)) in five injection wells. Sediment was sampled before and 8 months after injection. Significant iron sulfide minerals developed in the sandy aquifer matrix. From ground water analyses, treatment began a few weeks after injection with up to 95% reduction in PCE, TCE, and cDCE in less than 1 year. More complete CAH treatment is likely at a larger scale than this demonstration.     

Longevity of granular iron in groundwater treatment processes: changes in solute transport properties over time

Although progress has been made toward understanding the surface chemistry of granular iron and the mechanisms through which it attenuates groundwater contaminants, potential long-term changes in the solute transport properties of granular iron media have until now received relatively little attention. As part of column investigations of alterations in the reactivity of granular iron, studies using tritiated water (3H(2)O) as a conservative and non-partitioning tracer were periodically conducted to independently isolate transport-related effects on performance from those more directly related to surface reactivity. Hydraulic residence time distributions (HRTDs) within each of six 39-cm columns exposed to bicarbonate solutions were obtained over the course of 1100 days of operation. First moment analyses of the data revealed generally modest increases in mean pore water velocity (v) over time, indicative of decreasing water-filled porosity. Gravimetric measurements provided independent estimates of water-filled porosity that were initially consistent with those obtained from 3H(2)O tracer tests, although at later times, porosities derived from gravimetric measurements deviated from the tracer test results owing to mineral precipitation. The combination of gravimetric measurements and 3H(2)O tracer studies furnished estimates of precipitated mineral mass; depending on the assumed identity of the predominant mineral phase(s), the porosity decrease associated with solute precipitation amounted to 6-24% of the initial porosity. The accumulation of mineral and gas phases led to the formation of regions of immobile water and increased spreading of the tracer pulse. Application of a dual-region transport model to the 3H(2)O breakthrough curves revealed that the immobile water-filled region increased from initially negligible values to amounts ranging between 3% and 14% of the total porosity in later periods of operation. For the aged columns, mobile-immobile mass transfer coefficients (k(mt)) were generally in the range of 0.1-1.0 day(-1) and reflected a slow exchange of 3H(2)O between the two regions. Additional model calculations incorporating sorption and reaction suggest that although changes in HRTD can have an appreciable effect on trichloroethylene (TCE) transformation, the effect is likely to be minor relative to that stemming from passivation of the granular iron surface.     

The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers

Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.     

Observation of trapped gas during electrical resistance heating of trichloroethylene under passive venting conditions

A two-dimensional experiment employing a heterogeneous sand pack incorporating two pools of trichloroethylene (TCE) was performed to assess the efficacy of electrical resistance heating (ERH) under passive venting conditions. Temperature monitoring displayed the existence of a TCE-water co-boiling plateau at 73.4°C, followed by continued heating to 100°C. A 5cm thick gas accumulation formed beneath a fine-grained capillary barrier during and after co-boiling. The capillary barrier did not desaturate during the course of the experiment; the only pathway for gas escape being through perforated wells traversing the barrier. The thickness of the accumulation was dictated by the entry pressure of the perforated well. The theoretical maximum TCE soil concentration within the region of gas accumulation, following gas collapse, was estimated to be 888mg/kg. Post-heating soil sampling revealed TCE concentrations in this region ranging from 27mg/kg to 96.7mg/kg, indicating removal of aqueous and gas phase TCE following co-boiling as a result of subsequent boiling of water. The equilibrium concentrations of TCE in water corresponding to the range of post-treatment concentrations in soil (6.11mg/kg to 136mg/kg) are calculated to range from 19.8mg/l to 440mg/l. The results of this experiment illustrate the importance of providing gas phase venting during the application of ERH in heterogeneous porous media.     

Bimetallic iron-aluminum particles for dechlorination of carbon tetrachloride

Bimetallic iron-aluminum (Fe/Al) particles were synthesized and tested for their reactivity toward carbon tetrachloride using batch reactors and a flow-through column at near neutral pH. Preparation of bimetallic Fe/Al particles was conducted under acidic conditions under which iron was readily deposited onto the aluminum surface. The SEM image showed clusters of iron on the aluminum surface at the measured Fe:Al molar ratio of about 2:3. Results showed that the presence of zero-valent aluminum successfully prevented the formation of a passive layer at the iron surface and maintained the reactivity of iron. The dechlorination of carbon tetrachloride by bimetallic Fe/Al particles produced chloroform (9%), dichloromethane (17%) and methane (38%). Kinetic analysis suggests that bimetallic Fe/Al particles increased the reactivity toward carbon tetrachloride degradation by a factor of 10 compared to zero-valent iron and possessed a comparable reactivity with nano-sized Fe. The effectiveness of bimetallic Fe/Al particles was further confirmed by the continuous flow column study from which an ageing of bimetallic particles was also observed.     

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3 d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7 d at 25 °C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions.     

Visual determination of nitrite and nitrate in waters by color band formation method

A spot test for aqueous nitrate and nitrite for controlling nitrogen removal performance in small-scale wastewater treatment facilities is proposed. In this method, NO(2)(-) ion in water samples was allowed to react with sulfanilic acid and 1-naphthol to form an anionic azo dye. The resulting colored solution was introduced onto a mini column (similar to a gas detecting tube) packed with PVC particles coated with benzyl cetyl dimethyl ammonium chloride (BCDMA) and biphenyl. The NO(2)(-)-N concentration was determined visually by measuring the color band length (CBL) in the column. The CBL correlates linearly with nitrite concentration in the 4-20 mg-N l(-1) range. The concentration of nitrite+nitrate was determined after reduction to nitrite with zinc. The concentration of NO(3)(-)-N species was calculated by difference. This method was used to visually determine the concentrations of NO(2)(-)-N and (NO(2)(-)+NO(3)(-))-N in domestic wastewater samples with maximum suspended solid (SS) and chemical oxygen demand (COD) concentrations of 114 mg l(-1) and 73.9 mg l(-1), respectively.     

Removal of As,Mn, Mo,Se, U,V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.     

不同阳离子对Fe~0还原硝酸盐的影响

由于水中硝酸盐污染的普遍性、难去除性和对人体健康的潜在危害性而引起人们的广泛关注。通过批实验,考察了不同阳离子(Fe2+、Fe3+和Cu2+)对Fe0还原硝酸盐的影响。结果表明,由于加入阳离子可直接或间接地增加溶液中的Fe2+而都能促进硝酸盐的还原,作用顺序为Fe3+Fe2+Cu2+;Fe2+对硝酸盐的还原具有重要作用,并随着反应的进行,转化为铁氧化物附着在铁表面而降低铁的活性;硝酸盐还原的主要产物为氨氮,亚硝酸盐只在反应初期有少量积累,尤其是加Cu2+的体系中,但随后都很快降低;在所有体系中,检测到的三氮(NO3--N、NO2--N和NH4+-N)之和只占理论总氮的51.5%~82.6%;动力学分析表明,硝酸盐的还原在不加阳离子的体系中更符合一级反应,而加了阳离子的处理更符合Lo-gistic模型。本研究结果阐明了Fe2+对Fe0还原硝酸盐的重要性。     

Isotopic fractionation during reductive dechlorination of trichloroethene by zero-valent iron: influence of surface treatment

During reductive dechlorination of trichloroethene (TCE) by zero-valent iron, stable carbon isotopic values of residual TCE fractionate significantly and can be described by a Rayleigh model. This study investigated the effect of observed reaction rate, surface oxidation and iron type on isotopic fractionation of TCE during reductive dechlorination. Variation of observed reaction rate did not produce significant differences in isotopic fractionation in degradation experiments. However, a small influence on isotopic fractionation was observed for experiments using acid-cleaned electrolytic iron versus experiments using autoclaved electrolytic iron, acid-cleaned Peerless cast iron or autoclaved Peerless cast iron. A consistent isotopic enrichment factor of epsilon = -16.7/1000 was determined for all experiments using cast iron, and for the experiments with autoclaved electrolytic iron. Column experiments using 100% cast iron and a 28% cast iron/72% aquifer matrix mixture also resulted in an enrichment factor of -16.9/1000. The consistency in enrichment factors between batch and column systems suggests that isotopic trends observed in batch systems may be extrapolated to flowing systems such as field sites. The fact that significant isotopic fractionation was observed in all experiments implies that isotopic analysis can provide a direct qualitative indication of whether or not reductive dechlorination of TCE by Fe0 is occurring. This evidence may be useful in answering questions which arise at field sites, such as determining whether TCE observed down-gradient of an iron wall remediation scheme is the result of incomplete degradation within the wall, or of the dissolved TCE plume by passing the wall.