Effects of Surface-Bound Fe2+ on Nitrate Reduction and Transformation of Iron Oxide(s) in Zero-Valent Iron Systems at Near-Neutral pH

Nitrate reduction in an iron/nitrate/water system with or without an organic buffer was investigated using multiple batch reactors under strict anoxic conditions. Nitrate reduction was very limited (<10%) at near-neutral pH in the absence of the organic buffer. However, nitrate reduction was greatly enhanced if the system: (1) had a low initial pH ( ～ 2–3); (2) was primed with adequate aqueous Fe2+; or (3) was in the presence of the organic buffer. In Cases (1) and (3), nitrate reduction usually was involved in three stages. The first stage was quick, and H+ ions directly participated in the corrosion of iron grains. The second stage was very slow due to the formation of amorphous oxides on the surface of iron grains, while the third stage was characterized by a rapid nitrate reduction concurrent with the disappearance of aqueous Fe2+. Results indicate that reduction of nitrate by Fe0 will form magnetite; Fe2+ (aq.) can accelerate reduction of nitrate and will be substoichiometrically consumed. Once nitrate is exhausted in the system, no more Fe2+ will be consumed. In the presence of nitrate, Fe2+ (aq) will be adsorbed onto the surface of iron grains or iron oxides; the surface-complexed Fe(II) (extracted by acetate with pH = 4.1) might be oxidized and become structural Fe(III), resulting in a steadily increasing ratio of Fe(III)/Fe(II) in the oxides formed. The transformation of nonstoichiometric amorphous iron oxides into crystalline magnetite, a nonpassive oxide, triggers the rapid nitrate removal thereafter.     

Modeling of Nitrate Adsorption and Reduction in Fe0-Packed Columns through Impulse Loading Tests

A conventional tracer study using Li+ and Cl? was conducted on four Fe0-packed column reactors for nitrate removal. Both Li+ and Cl? showed strong adsorption onto iron media and thus were not ideal tracers for the study. Tests using an impulse loading of nitrate were then innovated to investigate the transport and reduction of nitrate in the reactors. The impulse loading was superposed on a continuous constant feeding of nitrate which generated a steady effluent baseline. A multivariable model incorporating hydraulic dispersion, adsorption/desorption, and reduction of nitrate was developed and numerically solved. Both Langmuir adsorption and linear adsorption isotherms were separately applied to describe nitrate adsorption on the reactive surface. The parameters of the model were estimated by fitting the model with the response curves from the impulse loading tests. These estimated parameters were consistent with previous studies. Specifically, the modeling results suggest a significant adsorption of nitrate by the iron media, causing an evident retardation effect. The research may lead to new methods for studying the fate of contaminants in porous reactive environments.     

Development of a New Zero-Valent Iron Zeolite Material to Reduce Nitrate without Ammonium Release

Previous studies have revealed that the application of zero-valent iron (ZVI) in reducing nitrate is limited by ammonium production and the requirement for adequate pH control. The current study focused on developing a new material potentially applicable in permeable reactive barriers, which can reduce nitrate without ammonium release under unbuffered pH. The new material, referred to as ZanF, is derived from zeolite modified by Fe(II), followed by borohydride reduction. The pseudo-first-order rate constant (kobs) of ZanF in the early period of nitrate reduction was 10 times higher than that of the ZVI used in this study. However, the kobs of ZanF decreased in the reaction period that followed. Even though both ZVI and ZanF produced ammonium as a product of nitrate reduction, ZanF removed it to below detection limits via adsorption, whereas ZVI did not remove it to any significant extent. ZanF maintained its high reactivity even under an initial pH of 6.2 without buffer. The higher ZanF/solution ratio increased the removal rate of ZanF as well as the removal efficiency.     

Cation Effects on Chromium Removal in Permeable Reactive Walls

Permeable reactive walls have proven to be successful in laboratory and pilot-scale field applications. However, the long-term efficacy of reactive permeable walls has not been established due to the novelty of the technology. Also, the impact of common groundwater ions such as calcium and magnesium (i.e., hardness) on permeable reactive walls is unknown. In theory, the ions may react competitively with chromium in solution and/or other materials on the surface of the zero-valent iron. The ions may also form precipitates that could clog the reactive zone over time, resulting in decreased contaminant removal and a shorter wall lifetime. The purpose of this research was to determine the effects of common groundwater ions on permeable reactive walls. A range of calcium and magnesium concentrations was tested in laboratory columns to determine the effect of these ions on removal of a constant chromium concentration (100 mg/L). Results from the laboratory tests indicated that calcium and magnesium had a significant impact on chromium removal. The most dramatic effects were witnessed at hardness levels up to 140 mg/L as CaCO3 where zero-valent iron capacity was reduced by 45%.     

Kinetic studies on the removal of iron and aluminum from recombinant and site-directed mutant N-lobe half transferrins

Kinetic studies have been conducted in pH 7.4 Hepes buffer at 25 degreesC on the removal of Fe(III) and Al(III) from the recombinant N-lobe half molecule of human serum transferrin (Tf/2N) and from the R124A, K206A, and K296A mutants of this protein. The rates of iron removal from Tf/2N by 3-hydroxypyridin-4-one (deferiprone) and nitrilotriacetic acid (NTA) are essentially identical with previous results on N-terminal monoferric transferrin (Tf-FeN). For both Tf/2N and Tf-FeN, iron removal by deferiprone follows simple saturation kinetics, while iron removal by NTA follows simple first-order kinetics. There is some discrepancy between the two proteins with respect to iron removal by PPi, but this may be due to differences in the chloride concentrations among different studies. The addition of Fe(NTA)2 to R124A at ambient bicarbonate concentrations forms the Fe-NTA-Tf ternary complex, but the usual Fe-CO3-Tf complex can be formed by adding ferrous ion in the presence of a larger excess of bicarbonate. This complex releases its iron very rapidly by a mechanism that is first-order with respect to the ligand. This suggests that the first-order component of metal release from transferrin involves the displacement of the synergistic carbonate anion. Since iron removal from K206A and K296A at pH 7.4 is extremely slow, studies have been conducted on the more labile Al3+ complexes of Tf/2N, K206A, and K296A. The removal of Al3+ from Tf/2N by PPi follows the same complex kinetic order with respect to the ligand concentration that is observed for iron removal, while the removal of Al3+ from both K206A and K296A reverts to a simple saturation process. The addition of perchlorate retards the removal of Al3+ from both K206A and K296A, suggesting that these lysine residues are not associated with the allosteric effects of inorganic anions on the rates of metal removal.     

Impact of Solids Formation and Gas Production on the Permeability of ZVI PRBs

The permeability of zero-valent iron permeable reactive barriers (ZVI PRBs) may be reduced by the production of gas and solid precipitates. The reduction in permeability was examined using column experiments, which showed that permeability loss was correlated with influent oxidant concentration. The column containing 100??mg/L nitrate experienced the greatest loss, approximately two orders of magnitude over the course of 200 pore volumes. However, the permeability loss owing to precipitated solids was largely independent of oxidant concentration, accounting for only 24% of the observed loss in the 100??mg/L nitrate column, suggesting that the majority of loss was attributable to gas, not precipitates. Geochemical modeling corroborated these findings, indicating that precipitation of solids in the 100??mg/L nitrate system does not account for more than a 10% permeability reduction. These findings suggest that in field PRBs in which a high reduction in permeability is observed, gas production may be implicated. Design choices that impede gas migration out of ZVI PRBs, such as capping, must be considered in light of the possibility of a high potential for permeability reduction.     

Enhancement of Nitrate Reduction in Fe0-Packed Columns by Selected Cations

Tests were conducted in Fe0-packed columns to investigate the effects of adding selected cations on nitrate removal by Fe0. Due to a rapid passivation of Fe0, only negligible nitrate was reduced in the columns without adding the selected cation. However, adding certain selected cations (Fe2+, Fe3+, or Al3+) in feed solution can significantly enhance nitrate reduction. Extending hydraulic retention time (HRT) increased nitrate removal by the columns, but the increase was not linearly proportional to HRT. Decreases in columns’ hydraulic conductivity (K) were monitored in an 8?month operating period. A modest decrease in K was recorded in the upper and the middle section of the media bed, whereas a significant decrease in K occurred in the inlet section. X-ray diffraction analyses indicate that magnetite (Fe3O4) was the dominant species of the iron corrosion products in the entire height of the column media under anoxic and other test conditions. In the inlet section, however, lepidocrocite and goethite were also identified. Cementation was found to occur only in the inlet section, suggesting that lepidocrocite and goethite, rather than magnetite, might be responsible for the cementation and thereby cause the hydraulic clogging. The magnetite coating would not necessarily cause clogging of the media.     

Evaluation of Granular Surfactant-Modified/Zeolite Zero Valent Iron Pellets As a Reactive Material for Perchloroethylene Reduction

The use of permeable reactive barriers (PRBs) for groundwater remediation is based on two distinct mechanisms: sorption and transformation. With sorption as the main mechanism, contaminants sorb on the PRB materials and are retarded. With transformation as the main mechanism, the contaminants react with the PRB materials and then converted to less toxic or innocuous substances. In this study, we tested surfactant-modified zeolite/zero valent iron (SMZ/ZVI) pellets as a PRB material to retard and degrade perchloroethylene (PCE), utilizing both sorption and transformation processes. Batch PCE kinetic studies showed instantaneous PCE removal from the aqueous phase due to sorption and subsequent removal with time due to reduction. The separation of sorption from reduction can be used to obtain both the PCE distribution coefficient (Kd) and the pseudofirst-order reduction rate constant (μobs) from a single batch experiment. The calculated Kd and μobs values are 3.0 and 0.5?L/kg and 0.14 and 0.05?h?1 for SMZ/ZVI and Z/ZVI pellets, respectively. Column experiments were performed at linear flow velocities of 0.07, 0.14, and 0.20?cm/min. The results were modeled using the one-dimensional advection–dispersion equation with linear sorption and first-order transformation. The Kd values were 2.3±0.4 and 0.5±0.1?L/kg for SMZ/ZVI and Z/ZVI pellets, respectively, in agreement with those of the batch study. The PCE transformation constants varied between 0.077 and 0.199?h?1 for the SMZ/ZVI pellets and between 0.037 and 0.144?h?1 for the Z/ZVI pellets, indicating that an enhanced transformation of PCE occurred with the sorbing SMZ/ZVI pellets. The PCE reduction rates were faster at slower flow rates, indicating that the reduction was not a mass-transfer-limited process.     

Simultaneous Removal of Cd and Cr(VI) Using Fe-Loaded Zeolite

Current research focuses on the simultaneous removal of Cd and Cr(VI) in water by a newly developed material having both abilities of sorption and electrochemical reduction. The material was derived from the zeolite modified by Fe(II) chloride followed by sodium borohydride reduction. The Fe-loaded zeolite simultaneously removed Cd and Cr(VI) to below the detection limit at a fairly rapid rate within 1?h for Cd and within 20?h for Cr(VI), under the pH ranging from slightly acid to around neutral. At high concentration of coexisting Cr(VI), the removal efficiency of Fe-loaded zeolite for Cd slightly decreased due to surface fouling by Cr(III) hydroxide precipitations. On the contrary, the coexisting Cd was found to increase the removal rate of Cr(VI) by Fe-loaded zeolite. From the test results, the Fe-loaded zeolite was found to be a possible alternative in simultaneous removal of Cd and Cr(VI) in the aqueous phase.     

Reduction of Nitrate, Bromate, and Chlorate by Zero Valent Iron (Fe0)

Oxo-anions occur in drinking waters, pose potential health risks, and should be controlled. It may be possible to incorporate zero-valent iron (Fe0) into water treatment processes to remove oxo-anions. Under near neutral pH (～7) and aerobic conditions, the three oxo-anions studied (NO3?, BrO3?, ClO3?) were electrochemically reduced by Fe0 in batch and continuous-flow packed column experiments. Mass balances provided strong evidence that ammonia is the primary reduction by-product from nitrate, chloride from chlorate, and bromide from bromate. Protons were consumed during the reaction, resulting in an increase in pH (i.e., production of hydroxide). Oxo-anion removal rates decreased as follows: BrO3?>ClO3?>NO3?. Differing rates of oxo-anion removal between batch and continuous flow column tests suggested that higher solid (Fe0) to liquid ratios increase oxo-anion electrochemical reduction, and scaling up of batch kinetic data to larger scale must consider the solid–liquid ratios. The atomic structure (atomic radii, electron orbital configuration, electron affinity) of nitrogen, chlorine, and bromine elements of the oxo-anions, and the bond dissociation energy between these elements and oxygen, were good indicators for the relative rates of reduction by Fe0.     

Effect of Metallic Iron Concentration on End-Product Distribution during Metallic Iron-Assisted Autotrophic Denitrification

The main objective of this study was to determine the optimum composition of a reactive porous medium containing sand and metallic iron, to be used for Fe(0)-assisted hydrogenotrophic denitrification. This determination is important to ensure that the end-product distribution after such treatment is acceptable, i.e., ammonia formation due to abiotic nitrate reduction by metallic iron in such media is minimized, while a reasonable rate of biological denitrification is maintained. Based on a previous study it was established that steel wool, with its relatively low specific surface area, exhibited the least propensity to abiotically reduce nitrate. It was also established that to achieve acceptable end-product distribution, the steel wool concentration in the reactive porous media has to be lowered even below the lowest value, i.e., 4.0?g steel wool/m3 of sand, used during that study. It was further hypothesized that to counter any detrimental effect of lower steel wool concentration on biological nitrate removal rate, increase of the retention time in porous media to values higher than 13 days, the maximum value investigated in that study, may be necessary. In the present study, experiments were conducted in batch reactors containing denitrifying microorganisms and various concentrations of steel wool and in semibatch reactors containing sand seeded with denitrifying microorganisms and various concentrations of steel wool. Based on the results of the semibatch experiments, it appears that to achieve acceptable end-product distribution, the steel wool concentration in the reactive porous media has to be maintained around 2.0?g steel wool/m3 sand and the corresponding retention time in the reactive media must be around 26 days.     

Effects of Selected Good’s pH Buffers on Nitrate Reduction by Iron Powder

The effects of three selected Good’s pH buffers on the performance of an Fe0/nitrate/H2O system were evaluated. The Good’s pH buffer itself did not reduce nitrate directly. Nitrate reduction by iron powder at near-neutral pH was negligible in an unbuffered system, but it was greatly enhanced with the presence of the buffer. A significant amount of aqueous Fe2+ (or Fe3+) was released after adding the Good’s pH buffer into the Fe0/H2O system with or without nitrate. In general, the pH of the buffered solution increased from the initial pH ( = ～ 4.6–5.3, depending on buffer’s pKa) to near-neutral pH. After the initial pH hiking, the pH in the system was more or less stable for a period of time ( ～ 5–10?h, usually concurrent with a fairly stable aqueous Fe2+). The pH then drifted to ～ 7.1 to 8.6, depending on the buffer’s initial concentration, the buffer’s pKa, and the consumption of Fe2+ concurrent with nitrate reduction. While a common assumption made by researchers is that Good’s pH buffers do not directly participate in reaction processes involved in contaminant remediation, this study shows that as side effects, the Good’s pH buffer may react with iron powder.     

Mass Transfer Effects on Kinetics of Dibromoethane Reduction by Zero-Valent Iron in Packed-Bed Reactors

Mass transfer effects on the kinetics of 1,2-dibromoethane (EDB) reduction by zero-valent iron (ZVI) in batch reactors, a laboratory scale packed-bed reactor, and a pilot scale packed-bed reactor are described. EDB was debrominated by ZVI to ethylene and bromide. EDB sorption to the cast iron surface was nonlinear and was described by a Langmuir equation. Laboratory scale column studies showed a nonlinear dependence of EDB removal on flow rate and initial EDB concentration. A nonequilibrium model of EDB sorption and reaction dependent on mass transfer was constructed using the laboratory scale data. The model was verified using data from a larger pilot scale packed-bed reactor that was used to remove EDB from contaminated groundwater. The data showed two distinct removal processes, an initial rapid phase dominated by mass transfer followed by a slower phase where surface reactions dominated. The model successfully predicted the transition from mass transfer controlled to surface reaction controlled conditions in the pilot scale data.     

Porous Reactive Walls for the Prevention of Acid Mine Drainage: A Review

Abstract

Laboratory tests and field-scale demonstrations indicate that permeable reactive walls, designed to induce bacterially mediated sulfate reduction within aquifers, have the potential to prevent the discharge of acidic, metal-rich waters. Laboratory batch studies were conducted to determine optimal mixtures of organic materials. Column studies were conducted to evaluate the potential for sulfate reduction and metal sulfide precipitation under dynamic flow conditions at groundwater velocities similar to those observed in the field. These laboratory studies established that sulfate reduction and metal sulfide precipitation mechanisms result in decreases in the concentrations of sulfate and iron and other metals. In the column experiments, sulfate and Fe were removed from synthetic mine drainage water at rates of 500-800 mmol/day/m³. In a pilot-scale field study, test cells installed into an aquifer containing a plume of mine waste-impacted groundwater, induced sulfate reduction and metal-sulfide precipitation. Within a flow path of less than one metre sulfate reduction and metal sulfide precipitation reactions resulted in the removal of iron, and production of alkalinity to the extent that the acid generating potential of the plume water was removed. A full-scale porous reactive wall was installed at the same site in August 1995. Comparing water entering the wall to treated water exiting the wall; sulfate concentrations decrease from 2,400-4,500 mg/L to 200-3,600 mg/L and Fe concentrations decrease from 250- 1,300 mg/L to 1.0 - 40 mg/L. After passing through the reactive wall, groundwater is transformed from acid producing to acid consuming.     

Nitric oxide reduces nontransferrin-bound iron transport in HepG2 cells

Nitric oxide (NO) donors S-nitroso-N-acetylpenicillamine (SNAP) and sodium nitroprusside (SNP) modulate iron regulatory protein (IRP) activity and may, therefore, affect iron uptake through transferrin receptor expression. However, iron also enters the cell as nontransferrin-bound iron (NTBI), and the aim of this study was to evaluate the effects of NO donors on NTBI transport in HepG2 cells, a model of liver physiology. Incubation with SNP and SNAP led to a time- and concentration-dependent reduction in Fe3+ and Fe2+ uptake, thus indicating an effect on the transporter rather than on the reductase. In terms of Fe2+ uptake, no variations in the Michaelis-Menten constant (Km) and a reduction in maximum uptake (Vmax) (50, 33, and 16.6 fmol/microgram protein/min in control, SNP-, and SNAP-treated cells, respectively) were detected, which suggested a decrease in the number of putative NTBI transport protein(s). Gel shift assays showed that IRP activity was reduced by SNP and slightly increased by SNAP. Northern blot analysis of transferrin receptor messenger RNA (mRNA) levels showed variations similar to those observed for IRPs, but both NO donors increased L-ferritin mRNA levels and had no effect on the stimulator of Fe transport (SFT) mRNA. In conclusion, NO donors significantly reduce NTBI transport in HepG2 cells, an effect that seems to be IRP and SFT independent. Moreover, the reduction in NTBI uptake after NO treatment suggests that this form of iron may play a minor role in the increased hepatic iron stores observed in inflammation or that other liver cells are more involved in this pathological condition.     

锌冶炼过程中浸渣加压还原酸浸除铁工艺优化

铁是金属锌产品中主要的杂质元素之一,如何去除是目前锌冶炼生产过程亟须解决的技术难题,湿法锌冶炼中如何除铁已开展了很多研究。介绍了工业上常用的几种湿法锌冶炼工艺流程以及常用的除铁方法,分析了黄钾铁矾法、针铁矿法、赤铁矿法和氧压浸出法等除铁方法的工艺特点以及相应的产品指标,并开展了锌中浸渣加压还原酸浸除铁工艺研究。结果表明：在高温高压条件下,可以同时进行浸锌沉铁,使铁以赤铁矿渣的形式沉淀,达到了浸锌除铁的目的,不需单独设计除铁工序,酸浸液中铁可低于4 g/L,酸度40~50 g/L H2SO4,利用沸腾焙烧炉产出的SO2烟气作为还原剂通入高压釜前段将溶液中Fe3+还原为Fe2+, Fe3+还原率高达94%,将O2通入高压釜中段,对锌中浸渣进行加压酸浸,锌还原浸出率可高达90%。该工艺可以有效解决除铁工艺工序长、设备多、投资大、操作复杂等问题,实现了缩短流程、简化设备、方便操作以及高效安全的生产目的。     

用针铁矿法从锌焙烧烟尘的热酸浸出液中除铁

研究了从锌焙烧烟尘常压热酸浸出液中沉淀针铁矿的过程。试验结果表明,反应时间和空气流量对除铁率的影响不显著,而反应温度和溶液终点pH是除铁过程的主要影响因素。在终点pH3.0、反应温度333 K、反应时间2 h、空气流量0.2 m3/min的条件下,除铁率超过99.5%,溶液中铁浓度可由40g/L降至0.1 g/L以下。     

铁粉矿在HIsarna工艺中预还原行为的研究

通过高温实验与理论分析研究了铁粉矿颗粒在高温下的热分解和熔化行为,以及熔化后气体与熔融粉矿液滴之间的还原动力学.当温度高于FeO熔点且产物层中有FeO生成时,铁粉矿颗粒会出现熔化现象.还原反应前210 ms伴随着剧烈的热分解反应,主要是Fe_2O_3分解成Fe_3O_4.熔化后的铁粉矿颗粒产物层是液态的FeO,颗粒中心是未反应的固态Fe_3O_4,还原反应发生在颗粒表面.Fe~(3+)在产物层中的扩散是还原反应的限制性环节,通过计算得到气体与熔融铁粉矿颗粒还原反应的表观活化能约为141 kJ/mol.     

Development of a Novel Internal Electrolysis System by Iron Connected with Carbon: Treatment of Nitroaromatic Compounds and Case of Engineering Application

The mixture of scrap iron and particle carbon, termed internal electrolysis, has been used in the pretreatment of industrial wastewater to improve the biodegradability. However, the clogging of fillings reduces treatment efficiency, and filling replacement is inconvenient in engineering application. This study developed a novel internal electrolysis system, in which iron and carbon were separately placed and connected with a wire. Results showed that the removal of paranitrophenol by iron was significantly enhanced by the connection of carbon. The removal by iron connected with carbon was approximately equivalent to that by iron contacted with carbon. The removal of nitrobenzene and the production of aniline proved the reduction in nitro to amino group. The sites for contaminant removal were found to be on iron surface rather than on carbon surface. The connection of carbon to iron facilitated the corrosion of iron and led to the formation of more Fe oxyhydroxide and the release of more electrons from iron, both of which attributed to contaminant removal. The engineering application using the novel internal electrolysis demonstrated an average chemical oxygen demand removal of 60% and a significant increase in wastewater biodegradability. This novel internal electrolysis system was preliminarily proved feasible and convenient.     

钢渣负载纳米零价铁-羟基磷灰石(S-FH)的制备及其对锰的吸附性能

通过液相还原法制备钢渣负载纳米零价铁-羟基磷灰石（S-FH）。分析Fe0-HAP被负载前后的微观形貌,研究了pH、S-FH投加量、反应时间和锰的初始浓度对S-FH吸附锰的影响,并借助吸附动力学模型和吸附等温模型对吸附机理作进一步分析。结果表明,在锰溶液初始浓度5 mg/L、pH=5,S-FH用量0.1 g和反应时间300 min条件下,吸附效果最佳。S-FH对锰的吸附过程更符合Freundlich吸附等温线模型（R2>0.98）和准二级动力学模型（R2>0.99）。吸附机理为离子交换、表面络合和溶解-沉淀。