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.     

Kinetics of Nitrate Reduction by Iron at Near Neutral pH

Although considerable research has been conducted on nitrate reduction by zerovalent iron (ZVI), the process kinetics at near neutral pH has not been studied thoroughly. In this study, a kinetic model with a double-Langmuir-adsorption formulation was developed to represent site saturation effects of aqueous Fe2+ and NO3? on nitrate reduction in a ZVI system at near neutral pH. Both an analytical solution and a numerical solution of the proposed model were developed. The kinetic parameters were evaluated based on batch experiments with two types of ZVI. Sensitivity analysis indicates that it is rather difficult and unreliable to estimate the parameters of the proposed multivariable nonlinear kinetic model from a single test curve. A better strategy is to obtain reliable parameters by designing specific experiments to target one parameter each time. The results indicate that, although the values of the kinetic parameters might change with different types of iron powder, the kinetic model can fit the experimental data very well, and therefore is consistent with the proposed mechanism.     

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.     

Competitive Effects of Trichloroethylene on Cr(VI) Removal by Zero-Valent Iron

Eleven columns were set up under various groundwater geochemistry conditions to investigate the competitive effect of trichloroethylene (TCE) on hexavalent chromium [Cr(VI)] removal by zero-valent iron (Fe0). They were found to be electron competitors in the redox reactions. In the presence of TCE, the Cr(VI) removal capacities of Fe0 were decreased by about 40% when compared with their respective Cr(VI) removal capacities with identical groundwater geochemistry but without TCE. The specific reaction rate constant (kSA) of TCE was decreased by about 50% when Cr(VI) was singly applied. The kSA of TCE was further decreased by 75% in the presence of both Cr(VI) and carbonate. However, there was no apparent effect on the kSA of TCE when Cr(VI), hardness and carbonate were all present. It revealed that TCE was a stronger electron competitor of Cr(VI) and the degradation of TCE became more favorable when both hardness and carbonate were present. This suggests that the passivated precipitates formed on the Fe0 surface in the presence of both hardness and carbonate may significantly affect the Cr(VI) removal by Fe0 but has insignificant effect on the TCE removal.     

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.     

Evaluation for Biological Reduction of Nitrate and Perchlorate in Brine Water Using the Hydrogen-Based Membrane Biofilm Reactor

Whereas ion exchange is an attractive technology for treating perchlorate and nitrate in drinking water, a major disadvantage is that the resin must be regenerated using a brine, producing wastes with high concentrations of nitrate, perchlorate, and salt. This study investigates the potential for simultaneous nitrate and perchlorate reductions in high-salt conditions using the H2-based membrane biofilm reactor (MBfR). The autotrophic biological reductions produce harmless N2 and Cl?, making the brine safe for reuse or disposal. A very high-strength brine ( ～ 15% salt) from a commercial ion-exchange membrane, Purolite, supported biofilm accumulation and allowed slow reduction rates for nitrate and perchlorate. Reduction rates increased significantly when the Purolite brine was diluted by 50% or more. A synthetic high-strength salt medium containing nitrate, perchlorate, or both supported more rapid reduction rates for as high as 20?g/L ( ～ 2%) NaCl, while 40?g/L NaCl slowed reduction by 40% or more, confirming that the microorganisms in the MBfR were inhibited by high salt content. An increase of H2 pressure gave higher fluxes for 20?g/L NaCl, demonstrating that H2 availability controlled the reduction kinetics when the system was not salt-inhibited.     

Chemistry of Modified Fenton’s Reagent (Catalyzed H2O2 Propagations–CHP) for In Situ Soil and Groundwater Remediation

The use of modified Fenton’s reagent, or catalyzed H2O2 propagations (CHP), has become increasingly popular for the in situ and ex situ treatment of surface soils and the in situ remediation of the subsurface. The process is based on the catalyzed decomposition of hydrogen peroxide by soluble iron, iron chelates, or iron minerals to generate the strong oxidant hydroxyl radical as well as other reactive oxygen species. Some of these species function as reductants and nucleophiles and may be responsible for the enhanced treatment of sorbed and nonaqueous phase liquid (NAPL) contaminants that is sometimes observed in the field. This paper serves as a review of the process chemistry of CHP; the goal is to provide researchers and practitioners with fundamental concepts that will aid in applying the CHP process to soil and groundwater contamination. Although the importance of well placement and the method of reagent injection must be considered in CHP remediation, understanding and promoting the most effective process chemistry is essential to successful soil and groundwater remediation.     

Bromate Formation by Ozone-VUV in Comparison with Ozone and Ozone-UV: Effects of pH, Ozone Dose, and VUV Power

The formation of bromate by ozone–vacuum ultraviolet (VUV) (185+254??nm) process in comparison with ozone and ozone-ultraviolet (UV) (254?nm) processes of coagulated and softened water was studied. The effects of pH (7, 9, and 11), ozone dosage (1, 2, and 4?mg O3/mg C), and VUV power (30, 60, and 120?W) were investigated. Bromate concentrations formed by the ozone-VUV process were up to four and six times less than those by the ozone and ozone-UV processes, respectively. Among the variables studied, ozone dosage had the most effect on bromate formation by the ozone-VUV process. Approximately 64 and 213% increases of bromate concentration were observed when the ozone dosage was increased from 1 to 2 and 4?mg O3/mg C with VUV power of 120?W at pH 7. The bromate formation also increased as VUV power and pH increased. Hydroxyl radical exposure had a positive relationship with ozone dosage and bromate formation. Results further indicated that it might be difficult to achieve the drinking water standard for bromate and high organic matter removal concurrently.     

Remediation of TCE-Contaminated Groundwater in a Sandy Aquifer Using Pulsed Air Sparging: Laboratory and Numerical Studies

The objective of this study was to investigate, through laboratory and numerical investigations, the effectiveness of a pulsed air sparging system for remediation of groundwater contaminated with trichloroethylene (TCE) in a sandy aquifer. In laboratory experiments, air was pulsed into TCE source zone on a daily basis in order to remediate TCE-contaminated groundwater. Most dissolved TCE was removed at the end of experiments although its concentrations fluctuated due to the air pulsing. The measured gaseous phase TCE concentration increased whereas the aqueous phase TCE concentration decreased during air sparging pulses. Experimental data were assessed by using a numerical code STOMP (subsurface transport over multiphases) with some modification based on the TCE dissolution kinetics. The unmeasured residual TCE mass was predicted through numerical simulations. Results show that aqueous concentrations for TCE are still much higher than the maximum contaminant level in spite of successful removal of 95% of residual TCE. It may imply that it would be more appropriate to apply air sparging combined with other remediation technologies such as bioremediation for remediation of TCE-contaminated groundwater.     

湿法炼锌常规工艺铁的浸出及沉铁pH值的研究

对锌焙砂中铁的物相组成和不同温度下各种铁氧化物酸溶平衡pH值进行了探讨,并根据锌焙砂浸出小型试验和扩大试验铁浸出率结果,研究得出了在湿法炼锌常规工艺浸出过程中,二价铁浸出反应是浸铁的主要化学反应的结论。同时计算了Fe3+在不同浓度下的水解平衡pH值,结果表明,当Fe3+浓度范围在5.6~0.00056 g.L-1时,相应的pH值在1.867~3.20之间。生产现场测定证实了所计算的pH值与生产实际相符合,表明计算结果对生产具有指导作用。     

Synergistic Effect of N and Ni2+ on Nanotitania in Photocatalytic Reduction of CO2

Nitrogen and nickel codoped nanotitania (N-Ni/TiO2) photocatalysts for producing methanol by photocatalytic reduction of CO2 were prepared by an improved sol-gol method. The catalysts were characterized by XRD, HRTEM, DES, FTIR, TG-DSC, and UV-Vis, respectively. The experimental results indicated that nano-N-Ni/TiO2 had better properties than the pure nanotitania (TiO2), N doped titania (N/TiO2), and Ni2+ doped titania (Ni/TiO2), considering their performance of photoresponse and photocatalytic reduction of CO2. The methanol yield could reach 482.0μmol/g-cat under optimal conditions. Additionally, the synergetic effect of N and Ni2+ on nano-TiO2 in photocatalytic reduction of CO2 was explained, and the mechanism of photocatalytic reduction CO2 on N-Ni/TiO2 catalyst was proposed.     

河南省舞阳铁矿田太古代古地史及铁矿的形成过程研究

分析了舞阳铁矿地质概况,追溯了舞阳铁矿田太古代古地史和赵案庄式铁矿、铁山庙式铁矿的形成过程以及变质作用,氧化作用对矿床的改造作用过程。     

CO气氛下MgO对Fe2O3还原时金属铁析出微观行为的影响

利用高温光学体视显微镜和高温热台研究MgO对CO还原Fe2O3中铁晶须成核、生长的影响,并结合SEM、EDS、TG、红外光谱等,从微观角度揭示MgO对还原过程气固界面上金属铁的析出形态的影响机理。结果表明,掺入MgO能有效改变氧化铁还原后析出铁的形态,抑制了铁晶须成核和生长;当掺入质量分数超过2%时,还原后金属铁全部以层状晶析出,无铁晶须形成。     

Speciation of the Fe(II)–Fe(III)–H2SO4–H2O system at 25 and 50 °C

This work presents theoretical and experimental results on the speciation of the Fe(II)–Fe(III)–H₂SO₄–H₂O system in concentrated solutions (up to 2.2 m H₂SO₄ and 1.3 m Fe). The aim was to study the chemical equilibria of iron at 25 and 50 °C in synthetic aqueous sulphuric acid solutions that contain dissolved ferric and ferrous ion species. Raman spectroscopy, volumetric titration and conductivity measurements have been carried out in order to study the presence of specific ions and to characterize the ionic equilibrium. A thermochemical equilibrium model incorporating an extended Debye–Hückel relationship was used to calculate the activities of ionic species in solution. Model calculations were compared with experimental results. Model simulations indicate that anions, cations and neutral complexes coexisted in the studied system, where the dominant species were HSO₄⁻, H⁺, Fe²⁺ and FeH(SO₄)₂⁰. This indicated that these solutions showed a high buffer capacity due to the existence of bisulphate ions (HSO₄⁻), which presented the highest concentration. A decrease in the concentration of H⁺ and Fe³⁺ took place with increasing temperature due to the formation of complex species. Standard equilibrium constants for the formation of FeH(SO₄)₂⁰ were obtained in this work: log K_f⁰ = 8.1 ± 0.3 at 25 °C and 10.0 ± 0.3 at 50 °C.     

合金元素对Sm2（Fe,M）17Ny磁性的影响

采用机械破碎与氢破碎和氮气-固相反应法制得了Sm₂(Fe,M)₁₇N_y化合物粉末及粉末压结体,研究了金属钐含量、过渡元素(M=Co、Cr、V、Mn、Zr、Si、Ga)部分取代铁时对Sm₂(Fe_1-xM_x)₁₇N_y粉末压结体磁性能的影响。结果表明:铬、镓能显著提高粉末的矫顽力。Sm₂(Fe_0.017Ga_0.983)₁₇N_y粉末压结体的矫顽力达到iHc=2000kA/m。     

Effects of Magnetic Annealing on Magnetic Properties in Nd4Fe76Co3(Hf1-xGax)B16 Alloy

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Impact of Initial pH and Linoleic Acid (C18:2) on Hydrogen Production by a Mesophilic Anaerobic Mixed Culture

Hydrogen production from glucose using a mixed anaerobic culture was assessed under batch conditions by adjusting the initial pH and adding linoleic acid (LA). At an initial pH of 5.0, hydrogen (1.9?mol?H2?mol?1 glucose) was detected after the first glucose injection in the controls (no LA added). At the latter initial pH and in cultures fed 2,000?mg?l?1 LA, the yield reached a maximum of 2.4?mol?H2?mol?1 glucose when glucose was injected again. Hydrogen was detected after the second glucose injection in cultures with the initial pH adjusted to 5.0 and 6.0. In cultures receiving LA and adjusted to pH 7.6, the hydrogen yield reached 1.4?mol?H2?mol?1 glucose when glucose was injected again. Acetate, propionate, and butyrate were detected under all conditions; however, the quantities were variable and dependent on the conditions examined. In comparison to the amount of volatile fatty acids produced, relatively low quantities of alcohols (ethanol, i-propanol, n-butanol, and i-butanol) were detected during the initial lag phase of 96?to?120?h.     

国外铁矿粉烧结理论与技术的进展(二)

近年来,国外在铁矿粉烧结理论研究和技术方面取得了长足的进步,尤其体现在烧结过程相图的发展、烧结SFCA理论的完善、预还原烧结的开发、镶嵌式烧结的设计、高温特性研究的不断深入、烧结模拟技术的发展等方面,本文对此进行了简要介绍。     

Effects of Cd2+, Pb2+ and CH3Hg+ on high voltage-activated calcium currents in pheochromocytoma (PC12) cells: potency, reversibility, interactions with extracellular Ca2+ and mechanisms of block

The present study attempted to determine the relationship between affective disposition and the favorability of letters of reference. We hypothesized that individuals with positive dispositions would write more favorable letters than would individuals with less positive or neutral dispositions. In addition, we also hypothesized that length of letter would partly mediate the relationship between affective disposition and letter favorability. To test these hypotheses, two studies were conducted. In order to present letter writers with a controlled stimulus, Study 1 entailed having 110 undergraduate students write letters of reference for two hypothetical job candidates in a laboratory setting. In order to test the generalizability of the laboratory study, Study 2 involved 95 faculty members who submitted three recent letters of reference they had written. Results showed that affective disposition was related to the favorability of letters of reference in both studies. Results also revealed that length of letter partly mediated the relationship between affective disposition and letter favorability. Copyright 1998 Academic Press.