Effects of low pH on nitrate reduction by iron powder

The effect of low pH (2-4.5) on nitrate reduction in an iron/nitrate/water system was investigated through batch experiments conducted in a pH-stat. The results showed that nitrate could be rapidly reduced to ammonium at pH 2-4.5. A black coating, consisted of both Fe(II) and Fe(III), was formed on the surface of iron grains as an iron corrosion product. X-ray diffractometry indicated that the black coating was poorly crystalline, and its spectrum could not be matched with commonly known iron oxides/hydroxides/oxide hydroxides or green rust I/II. The black coating does not inhibit the reactivity of Fe0 (at least at pH < 3). The black coating was unstable and evolved with time into other oxides under certain conditions. A kinetic model incorporating the effects of pH on nitrate reduction and Langmuir adsorption of nitrate was proposed, and the parameters were estimated by nonlinear curve fitting. Based on this model, the two major effects of pH on the kinetics of nitrate reduction are that: (a) H+ ions directly participate in the redox reaction of nitrate reduction following first-order kinetics; and (b) H+ ions affect the nitrate adsorption onto reactive sites.     

Characteristics of nitrate reduction by zero-valent iron powder in the recirculated and CO(2)-bubbled system

In this study, the Fe(0)/CO(2) process was investigated for removing nitrate from aqueous solution under different operating conditions such as CO(2) bubbling rate (0-400 mL/min), Fe(0) dosage (1-6g/L), initial nitrate concentration (6-23 mgN/L), batch mode, and fresh Fe(0) supplementing (0-1g/L). Results show that the bubbling of CO(2) flow rate at 200 mL/min was sufficient for supplying H(+) into solution to create an acidic environment favorable to nitrate reduction reaction. It was found that sigmoidal model equation describes the S-curve behaviors of nitrate reduction, ferrous accumulation and ammonium formation satisfactorily, and the parameter t(1/2) of the proposed model equation serves as a powerful tool for the comparison of nitrate reduction rate. Sustainability test demonstrates that Fe(0) powder began to deteriorate after three batches operation. Concerning the operating modes, the batch mode with the treated solution emptied and freshly refilled outperforms the one, which was operated by retaining the treated solution and spiking concentrated nitrate into it for the next batch treatment. To guarantee satisfactory nitrate removal using the former mode, supplement of appropriate amount of Fe(0) needs to be optimized.     

Zero-valent iron reduction of nitrate in the presence of ultraviolet light,organic matter and hydrogen peroxide

This paper describes the use of metallic iron (Fe(0)) powder for nitrate removal in a well-mixed batch reactor. Important variables explored include Fe(0) dosage (1-3g/L), UV light intensity (64-128 W), and the presence of propanol (20 mg/L as DOC) and H(2)O(2) (100-200 mg/L). Accumulation of ferrous ions released from the Fe(0) surface can be expressed by an S-curve, which involves lag growth phase, exponential phase, rate-declining phase, and saturation phase. The removal of nitrate increases with increasing Fe(0) dosage; however, the removal makes no difference as the Fe(0) dosage is greater than 2 g/L. UV irradiation retards the dissolution of ferrous ion and the removal of nitrate. The species of propanol, which has a functional group of -OH, plays a role of organic inhibitor for Fe(0) corrosion. The presence of H(2)O(2) appears to inactivate all reactions as the Fe(0) of 10 microm was used; the final H(2)O(2) remains intact throughout the entire reaction period, and there were no removal of nitrate and no dissolution of ferrous ion. Surprisingly, with the use of a larger Fe(0) particle size of 150 microm, the H(2)O(2) was seen to decompose rapidly through Fenton reaction. Nevertheless, the rate of ferrous accumulation or nitrate removal is slow.     

Nitrous oxide production kinetics during nitrate reduction in river sediments

A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R_m) ranged between 3.0 and 7.1 μg N g⁻¹ h⁻¹, and affinity constant (K_m) ranged from 7.4 to 30.7 mg N-NO₃⁻ L⁻¹. These values were higher in slurry incubations with an R_m of 37.9 μg N g⁻¹ h⁻¹ and a K_m of 104 mg N-NO₃⁻ L⁻¹. Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4 ng N g⁻¹ h⁻¹ for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates).     

Decreasing ammonium generation using hydrogenotrophic bacteria in the process of nitrate reduction by nanoscale zero-valent iron

An integrated nitrate treatment using nanoscale zero-valent iron (NZVI) and Alcaligenes eutrophus, which is a kind of hydrogenotrophic denitrifying bacteria, was conducted to remove nitrate and decrease ammonium generation. Within 8 days, nitrate was removed completely in the reactors containing NZVI particles plus bacteria while the proportion of ammonium generated was only 33%. That is a lower reduction rate but a smaller proportion of ammonium relative to that in abiotic reactors. It was also found that ammonium generation experienced a biphasic process, involving an increasing period and a stable period. After domestication of the bacteria, the combined NZVI-cell system could remove all nitrate without ammonium released when the refreshed nitrate was introduced. Nitrate reduction and the final product distribution were also studied in batch reactors amended with different initial NZVI contents and biomass concentrations, respectively. Both the nitrate removal rate and the ammonium yield decreased when the initial content of NZVI reduced and the initial biomass concentration increased. However, about 27% of the nitrate was converted to ammonium when excess bacteria (OD₄₂₂ = 0.026) were used, which was higher than that with appropriate amount of bacteria.     

Effects of dissolved oxygen on formation of corrosion products and concomitant oxygen and nitrate reduction in zero-valent iron systems with or without aqueous Fe2+

Batch tests were conducted in zero-valent iron (ZVI or Fe0) systems to investigate oxygen consumption and the effect of dissolved oxygen (DO) on formation of iron corrosion products, nitrate reduction, the reactivity of Fe0, the role Fe2+ (aq) played, and the fate of Fe2+. The study indicates that without augmenting Fe2+ (aq), neither nitrate nor DO could be removed efficiently by Fe0. In the presence of Fe2+ (aq), nitrate and DO could be reduced concomitantly with limited interference with each other. Unlike nitrate reduction, DO removal by Fe0 did not consume Fe2+ (aq). A two-layer structure, with an inner layer of magnetite and an outer layer of lepidocrocite, may be formed in the presence of DO. When DO depleted, the outer lepidocrocite layer was transformed to magnetite. The inner layer of magnetite, even in a substantial thickness, might not impede the Fe0 reactivity as much as the thin interfacial layer between the oxide coating and liquid. Surface-bound Fe2+ may greatly enhance the electron transfer from the Fe0 core to the solid-liquid interface, and thus improve the performance of the Fe0 process.     

Aqueous chlorination of the antibacterial agent trimethoprim: reaction kinetics and pathways

Trimethoprim (TMP), one of the antibacterials most frequently detected in municipal wastewaters and surface waters, reacts readily with free available chlorine (i.e., HOCl) at pH values between 3 and 9 (e.g., the pH-dependent apparent second-order rate constant, k'(app)=5.6 x 10(1)M(-1)s(-1), at pH 7). Solution pH significantly affects the rate of TMP reaction with HOCl. The reaction kinetics in reagent water systems can be well described by a second-order kinetic model incorporating speciation of both reactants and accounting for acid-mediated halogenation of TMP's 3,4,5-trimethoxybenzyl moiety. Studies with the substructure model compounds 2,4-diamino-5-methylpyrimidine and 3,4,5-trimethoxytoluene show that TMP reacts with HOCl primarily via its 3,4,5-trimethoxybenzyl moiety at acidic pH, and with its 2,4-diaminopyrimidinyl moiety at circumneutral and alkaline pH. LC/MS product analyses indicate that the TMP structure is not substantially degraded upon reactions with HOCl. Instead, a wide variety of (multi)chlorinated and hydroxylated products are formed. Experiments with real drinking water and wastewater matrixes confirmed that substantial TMP transformation can be expected for conditions typical of wastewater and drinking water chlorination.     

地下水生物除铁效果及其动力学研究

采用生物滤柱进行了地下水除铁的试验研究。当原水中Fe^2＋的质量浓度为4．3mg／L,pH值为6．4～6．6,水温为23～25℃,DO为1．5mg／L,滤速为8m／h时,出水中Fe^2＋〈0．1mg,／L。通过灭菌试验得出,滤柱对铁的去除主要通过生物氧化完成,而非物理化学作用。通过分析不同高度滤层水中铁的含量研究了生物氧化除铁动力学规律,得出铁含量与空床接触时间之间的函数关系。     

The kinetics of hexavalent chromium reduction by metallic iron

The rate reduction of hexavalent chromium (Cr(VI)) by metallic iron under a range of conditions was studied in batch systems. The chemical variables studied were the Cr(VI) concentration, hydrogen ion concentration and surface area of iron. The influence of ionic strength and mixing rate was also examined. The reaction kinetics were found to be dependent on hydrogen ion concentration, hexavalent chromium concentration and iron surface area and to adhere to the following kinetic expression.

Full-size image (1K)

.The rate constant was evaluated and found to have a value of 5.45 × 10⁻⁵ 1 cm⁻² min⁻¹ over a wide range of conditions.The rate constant was found to increase as mixing rate increased up to a maximum value beyond which the rate was essentially independent of mixing. Increases in ionic strength were found to result in a rapid decrease in the rate constant at ionic strengths below 0.1 M. Further increases in ionic strength had no detectable impact on the rate constant. All rate determination studies were run in the mixing and ionic strength independent regions of these systems.Reaction stoichiometry was found to be, with one exception, independent of environmental conditions. In general, 1.33 mol of iron dissolved for each mol of Cr(VI) reduced. This highly efficient utilization of iron in the reduction suggests that hydrogen generated during iron dissolution may be acting as a reductant for the Cr(VI). The single parameter which influenced the reaction stoichiometry was the initial Cr(VI) concentration. The ratio of Cr(VI) reduced to iron dissolved increased rapidly as the Cr(VI) concentration increased. This observation was taken as being consistant with a surface interaction between the hexavalent chromium and some metastable hydrogen species at the iron surface.     

Appropriate conditions or maximizing catalytic reduction efficiency of nitrate into nitrogen gas in groundwater

This study focused on the appropriate catalyst preparation and operating conditions for maximizing catalytic reduction efficiency of nitrate into nitrogen gas from groundwater. Batch experiments were conducted with prepared Pd and/or Cu catalysts with hydrogen gas supplied under specific operating conditions. It has been found that Pd-Cu combined catalysts prepared at a mass ratio of 4:1 can maximize the nitrate reduction into nitrogen gas. With an increase in the quantity of the catalysts, both nitrite intermediates and ammonia can be kept at a low level. It has also been found that the catalytic activity is mainly affected by the mass ratio of hydrogen gas to nitrate nitrogen, and hydrogen gas gauge pressure. Appropriate operating values of H(2)/NO(3)-N ratio, hydrogen gas gauge pressure, pH, and initial nitrate concentration have been determined to be 44.6g H(2)/g N, 0.15 atm, 5.2 (-), 100 mg x L(-1) for maximizing the catalytic reduction of nitrate from groundwater.     

Nitrate reduction using nanosized zero-valent iron supported by polystyrene resins: role of surface functional groups

To probe the role of host chemistry in formation and properties of the inside nano-zero valent iron (nZVI), we encapsulated nZVI within porous polystyrene resins functionalized with -CH₂Cl and -CH₂N⁺(CH₃)₃ respectively and obtained two hybrid nZVIs denoted Cl-S-ZVI and N-S-ZVI. 14.5% (in Fe mass) of nZVI particles were distributed in N-S within a ring-like region (about 0.10 mm in thickness) of size around ∼5 nm, whereas only 4.0% of nZVI particles were entrapped near the outer surface of Cl-S of size > 20 nm. -CH₂N⁺(CH₃)₃ is more favorable than -CH₂Cl to inhibit nZVI dissolution into Fe²⁺ ions under acidic pH (3.0-5.5). 97.2% of nitrate was converted into ammonium when introducing 0.12 g N-S-ZVI into 50 mL 50 mg N/L nitrate solution, while that for Cl-S-ZVI was 79.8% under identical Fe/N molar ratio. Under pH = 2 of the effectiveness of nZVI was 88.8% for nitrate reduction, whereas that for Cl-S-ZVI was only 14.6% under similar conditions. Nitrate reduction by N-S-ZVI exhibits relatively slower kinetics than Cl-S-ZVI, which may be related to different nZVI distribution of both composites. The coexisting chloride and sulfate co-ions are favorable for the reactivity enhancement of N-S-ZVI whereas slightly unfavorable for Cl-S-ZVI. The results demonstrated that support chemistry plays a significant role in formation and reactivity of the encapsulated nZVI, and may shed new light on design and fabrication of hybrid nZVIs for environmental remediation.     

Arsenic removal from geothermal waters with zero-valent iron--effect of temperature, phosphate and nitrate

Field column studies and laboratory batch experiments were conducted in order to assess the performance of zero-valent iron in removing arsenic from geothermal waters in agricultural regions where phosphates and nitrates were present. A field pilot study demonstrated that iron filings could remove arsenic, phosphate and nitrate from water. In addition, batch studies were performed to evaluate the effect of temperature, phosphate and nitrate on As(III) and As(V) removal rates. All batch experiments were conducted at three temperatures (20, 30 and 40 degrees C). Pseudo-first-order reaction rate constants were calculated for As(III), As(V), phosphate, nitrate and ammonia for all temperatures. As(V) exhibited greater removal rates than As(III). The presence of phosphate and nitrate decreased the rates of arsenic removal. The temperature of the water played a dominant role on the kinetics of arsenic, phosphate and nitrate removal. Nitrate reduction resulted in the formation of nitrite and ammonia. In addition, the activation energy, Eact, and the constant temperature coefficient, theta were determined for each removal process.     

Chlorate and nitrate reduction pathways are separately induced in the perchlorate-respiring bacterium Dechlorosoma sp. KJ and the chlorate-respiring bacterium Pseudomonas sp. PDA

The effect of nitrate on perchlorate and chlorate reduction by perchlorate-respiring bacteria (PRB), and on chlorate reduction by chlorate-respiring bacteria (CRB), is not well understood, particularly with respect to the induction of pathways used to degrade these different chemicals. Based on kinetic data obtained in a series of batch tests, we determined that perchlorate respiratory enzymes were inducible (by chlorate or perchlorate) and separate from those used for denitrification by PRB strain Dechlorosoma sp. KJ. Aerobically grown cultures of KJ had lag times of greater than 0.3-2 days when transferred to a medium containing only perchlorate, chlorate, or nitrate as an electron acceptor. There were no lag times for transfers between identical media. Washed cells reduced very little nitrate (<10%) when grown only on chlorate or perchlorate. When grown on nitrate, they degraded little chlorate or perchlorate. The same lack of activity with these electron acceptors was also observed using cell extracts and methyl viologen as an electron carrier, indicating a lack of reactivity was not due to failure of the chemical to diffuse into the cell. Taken together, these results indicated that enzymes for perchlorate and nitrate reduction are separately expressed in strain KJ. The presence of small amounts of nitrate in contaminated groundwater may actually help to increase rates of perchlorate reduction once the nitrate is completely removed. When strain KJ was pre-grown on nitrate and perchlorate, perchlorate degradation (in the absence of nitrate) was more rapid compared to cells grown only on perchlorate. Pseudomonas sp. PDA was unable to degrade perchlorate or grow using nitrate, and the induction of enzymes necessary for chlorate respiration differed for strains KJ and PDA. While chlorate reductase and chlorite dismutase activity were induced in KJ by chlorate or perchlorate under anaerobic conditions, these two enzymes were constitutively expressed by PDA under anaerobic and aerobic conditions independent of the presence of chlorate. To our knowledge, this is the first report of constitutive expression of both chlorate reductase and chlorite dismutase in a bacterium.     

Chemical reactions between arsenic and zero-valent iron in water

Batch experiments and X-ray photoelectron spectroscopic (XPS) analyses were performed to study the reactions between arsenate [As(V)], arsenite [As(III)] and zero-valent iron [Fe(0)]. The As(III) removal rate was higher than that for As(V) when iron filings (80-120 mesh) were mixed with arsenic solutions purged with nitrogen gas in the pH range of 4-7. XPS spectra of the reacted iron coupons showed the reduction of As(III) to As(0). Soluble As(III) was formed when As(V) reacted with Fe(0) under anoxic conditions. However, no As(0) was detected on the iron coupons after 5 days of reaction in the As(V)-Fe(0) system. The removal of the arsenic species by Fe(0) was attributed to electrochemical reduction of As(III) to sparsely soluble As(0) and adsorption of As(III) and As(V) to iron hydroxides formed on the Fe(0) surface under anoxic conditions. When the solutions were open to atmospheric air, the removal rates of As(V) and As(III) were much higher than under the anoxic conditions, and As(V) removal was faster than As(III). The rapid removal of As(III) and As(V) was caused by adsorption on ferric hydroxides formed readily through oxidation of Fe(0) by dissolved oxygen.     

Fate of As(V)-treated nano zero-valent iron: determination of arsenic desorption potential under varying environmental conditions by phosphate extraction

Nano zero-valent iron (NZVI) offers a promising approach for arsenic remediation, but the spent NZVI with elevated arsenic content could arouse safety concerns. This study investigated the fate of As(V)-treated NZVI (As-NZVI), by examining the desorption potential of As under varying conditions. The desorption kinetics of As from As-NZVI as induced by phosphate was well described by a biphasic rate model. The effects of As(V)/NZVI mass ratio, pH, and aging time on arsenic desorption from As-NZVI by phosphate were investigated. Less arsenic desorption was observed at lower pH or higher As(V)/NZVI mass ratio, where stronger complexes (bidentate) formed between As(V) and NZVI corrosion products as indicated by FTIR analysis. Compared with the fresh As-NZVI, the amount of phosphate-extractable As significantly decreased in As-NZVI aged for 30 or 60 days. The results of the sequential extraction experiments demonstrated that a larger fraction of As was sorbed in the crystalline phases after aging, making it less susceptible to phosphate displacement. However, at pH 9, a slightly higher proportion of phosphate-extractable As was observed in the 60-day sample than in the 30-day sample. XPS results revealed the transformation of As(V) to more easily desorbed As(III) during aging and a higher As(III)/As(V) ratio in the 60-day sample at pH 9, which might have resulted in the higher desorption.     

Abiotic reduction of dinitroaniline herbicides

The importance of abiotic reductive transformations as a sink for four dinitroaniline herbicides (trifluralin, pendimethalin, nitralin, and isopropalin) has been evaluated. Using reductants representative of abiotic reductants found in natural systems, the results of this study indicate that nitro groups present on the dinitroaniline herbicides can be reduced by surface-bound Fe(II) species in goethite suspensions or by hydroquinone moieties such as (mercapto)juglone in a hydrogen sulfide solution. Aqueous iron species are also effective at pH values above 7.0. The reaction in aqueous Fe(II) and in Fe(II)/goethite systems is strongly pH dependent, with rates increasing with increasing pH. Montmorillonite clay, however, is not effective in mediating the reduction of dinitroaniline herbicides in the presence of Fe(II). Because the selected dinitroaniline herbicides have a mixture of electron withdrawing and electron donating groups, linear free energy relationships were developed for the H(2)S/(mercapto)juglone and Fe(II)/goethite systems. Anilines resulting from reduction of the nitro group as well as cyclization products (benzimidazoles) were observed in the degradation of trifluralin. Only one aniline product was observed for pendimethalin.     

Reductive immobilization of chromate in water and soil using stabilized iron nanoparticles

Laboratory batch and column experiments were conducted to investigate the feasibility of using a new class of stabilized zero-valent iron (ZVI) nanoparticles for in situ reductive immobilization of Cr(VI) in water and in a sandy loam soil. Batch kinetic tests indicated that 0.08g/L of the ZVI nanoparticles were able to rapidly reduce 34mg/L of Cr(VI) in water at an initial pseudo first-order rate constant of 0.08h(-1). The extent of Cr(VI) reduction was increased from 24% to 90% as the ZVI dosage was increased from 0.04 to 0.12g/L. The leachability of Cr preloaded in a Cr-loaded sandy soil was reduced by nearly 50% when the soil was amended with 0.08g/L of the ZVI nanoparticles in batch tests at a soil-to-solution ratio of 1g: 10mL. Column experiments indicated that the stabilized ZVI nanoparticles are highly deliverable in the soil column. When the soil column was treated with 5.7 bed volumes of 0.06g/L of the nanoparticles at pH 5.60, only 4.9% of the total Cr was eluted compared to 12% for untreated soil under otherwise identical conditions. The ZVI treatment reduced the TCLP leachability of Cr in the soil by 90%, and the California WET (Waste Extraction Test) leachability by 76%. The stabilized ZVI nanoparticles may serve as a highly soil-dispersible and effective agent for in situ reductive immobilization of chromium in soils, groundwater, or industrial wastes.     

Systematic evaluation of nitrate and perchlorate bioreduction kinetics in groundwater using a hydrogen-based membrane biofilm reactor

To evaluate the simultaneous reduction kinetics of the oxidized compounds, we treated nitrate-contaminated groundwater (∼9.4 mg-N/L) containing low concentrations of perchlorate (∼12.5 μg/L) and saturated with dissolved oxygen (∼8 mg/L) in a hydrogen-based membrane biofilm reactor (MBfR). We systematically increased the hydrogen availability and simultaneously varied the surface loading of the oxidized compounds on the biofilm in order to provide a comprehensive, quantitative data set with which to evaluate the relationship between electron donor (H₂) availability, surface loading of the electron acceptors (oxidized compounds), and simultaneous bioreduction of the electron acceptors. Increasing the H₂ pressure delivered more H₂ gas, and the total H₂ flux increased linearly from ∼0.04 mg/cm²-d for 0.5 psig (0.034 atm) to 0.13 mg/cm²-d for 9.5 psig (0.65 atm). This increased rate of H₂ delivery allowed for continued reduction of the acceptors as their surface loading increased. The electron acceptors had a clear hydrogen-utilization order when the availability of hydrogen was limited: oxygen, nitrate, nitrite, and then perchlorate. Spiking the influent with perchlorate or nitrate allowed us to identify the maximum surface loadings that still achieved more than 99.5% reduction of both oxidized contaminants: 0.21 mg NO₃-N/cm²-d and 3.4 μg ClO₄/cm²-d. Both maximum values appear to be controlled by factors other than hydrogen availability.     

Microbial reduction of perchlorate with zero-valent iron

Microbial reduction of perchlorate in the presence of zero-valent iron was examined in both batch and column reactors to assess the potential of iron as the electron donor for biological perchlorate reduction process. Iron-supported mixed cultures completely removed 65 mg/L of perchlorate in batch reactors in 8 days. The removal rate was similar to that observed with hydrogen gas (5%) and acetate (173 mg/L) as electron donors. Repeated spiking of perchlorate to batch reactors containing iron granules and microorganisms showed that complete perchlorate reduction by the iron-supported culture was sustained over a long period. Complete removal of perchlorate by iron-supported anaerobic culture was also achieved in a bench-scale iron column with a hydraulic residence time of 2 days. This study demonstrated the potential applicability of zero-valent iron as a source of electrons for biological perchlorate reduction. Use of zero-valent iron may eliminate the need to continually supply electron donors such as organic substrates or explosive hydrogen gas. In addition, iron is inexpensive, safe to handle, and does not leave organic residuals in the treated water.