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 pretreatment for enhancing the biodegradability of RDX

Hexahydro-1,3,5-trinitro-1,3,5-triazine (C₃H₆N₃(NO₂)₃, royal demolition explosive or RDX) is a common nitramine explosive and one of the major constituents in wastewaters from ammunitions plants. The objective of this study is to investigate zero-valent iron (Fe(0)) pretreatment for enhancing the biodegradability of recalcitrant RDX. It was hypothesized that iron pretreatment can reductively transform RDX to products that are more amenable to biological treatment processes such as activated sludge. Results of batch and column experiments showed rapid and complete removal of RDX by Fe(0) regardless of the buffering capacity. Formaldehyde (HCHO), a major reduction product of RDX, was readily biodegraded by a mixed culture. Respirometric data indicate that iron-treated RDX solution exerted substantially higher biochemical oxygen demand (BOD) than untreated RDX solution. We propose that an integrated iron reduction—activated sludge process may be a feasible option for treating RDX-laden wastewater.     

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.     

Chemical reduction of nitrate by nanosized iron: kinetics and pathways

This study was conducted to investigate chemical reduction of nitrate by nanoscale zero-valent iron (ZVI) in aqueous solution and related kinetics and pathways. In the last decade, employment of micro-scale ZVI has gained its popularity in nitrate reduction. To further study chemical reduction of nitrate, nanosized iron was synthesized and tested in this work. It has a size in the range of 50-80 nm and a BET surface area of 37.83 m(2)g(-1). Chemical reduction of nitrate by nanosized iron under various pHs was carried out in batch experiments. Experimental results suggest that nitrate reduction by nanosized ZVI primarily is an acid-driven surface-mediated process. A stronger acidic condition is more favorable for nitrate reduction. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. Additional test results also showed that the reduction rate of nitrate increased as the dose of nanosized ZVI increased. In all tests, reaction rate equations developed do not obey the first- or pseudo-first-order reaction kinetics with respect to the nitrate concentration. Based on the research findings obtained, two possible reaction pathways for nitrate reduction by nanoscale iron particles have been proposed in this work.     

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.     

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.     

Removal of organics in water using hydrogen peroxide in presence of ultraviolet light

The optimum conditions for the removal of dissolved organic impurities from water using hydrogen peroxide (50%) followed by ultraviolet irradiation were investigated. The photochemically initiated hydroxyl radical (OH) oxidation reduced the total organic carbon (TOC) content of distilled water samples by about 88% and of tap water by 98%. Extraction with hexane of equal volumes of water samples before and after H₂O₂/u.v. treatment followed by gas chromatographic analysis of the concentrated extracts indicated that about 12% of the electron-capturing, residual organics remained after this treatment. These results support the conclusion drawn from total organic carbon analysis that this simple method yields water nearly free of organic impurities.     

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.     

Measurement of hydrogen peroxide in an advanced oxidation process using an automated biosensor

A hydrogen peroxide biosensor was used to monitor hydrogen peroxide concentrations in a UV/hydrogen peroxide immobilised Fenton advanced oxidation process (AOP). The biosensor is based on gas phase monitoring and thus is more resistant to fouling from the liquid phase constituents of industrial processes. The biosensor is supplied with catalase continually, therefore overcoming any problems with enzyme degradation, which would occur in an immobilised enzyme biosensor. The biosensors response was linear within the experimental range 30-400mg H(2)O(2)l(-1) with a R(2) correlation of 0.99. The hydrogen peroxide monitor was used to monitor residual peroxide in an AOP, operated with a step overload of hydrogen peroxide, with correlation factors of 0.96-0.99 compared to offline hydrogen peroxide determinations by UV spectroscopy. Sparging the sample with nitrogen was found to be effective in reducing the interference from dissolved gases produced with the AOP itself. It is proposed that this biosensor could be used to improve the effectiveness of AOPs via hydrogen peroxide control.     

双氧水的发泡及其在制造轻混凝土中的应用

主要研究了双氧水发泡剂在制备超轻混凝土过程中的效果,同时通过对制得混凝土的容重、气孔和强度等方面对其检测来对发泡剂进行评价。     

A shift in pathway of iron-mediated perchloroethylene reduction in the presence of sorbed surfactant--a column study

Surface modification of zero-valent iron (ZVI) to enhance its reduction rates for chlorinated ethanes and ethenes has recently attracted great attention. In this research, the enhancement of perchloroethylene (PCE) reduction by ZVI in the presence of sorbed micelles of the cationic surfactant hexadecyltrimethylammonium (HDTMA) was examined in a series of laboratory column tests with varying flow rates and input PCE concentrations. Model simulations using HYDRUS-1D showed that the overall pseudo first-order rate constants for PCE reduction by ZVI increased by a factor of four in the presence of sorbed HDTMA admicelles. The increase in reduction rate was attributed to a higher distribution coefficient (K_d) for contaminant sorption on surfactant-modified ZVI (SM-ZVI) compared to untreated ZVI. Modeling results also showed that in the presence of HDTMA admicelles 58–100% of PCE reduction occurred via hydrogenolysis. In contrast, only 12–25% PCE underwent hydrogenolysis when HDTMA was absent. The significant increase in TCE production during PCE reduction by SM-ZVI verified a shift in reaction pathway previously observed in batch studies, most likely from β-elimination to hydrogenolysis. Although this shift in reaction pathway resulted in a higher accumulation of TCE, the combined concentrations of chlorinated hydrocarbons in the effluent were 1.5–5 times lower when SM-ZVI rather than unmodified ZVI was used.     

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.     

Field assessment of carboxymethyl cellulose stabilized iron nanoparticles for in situ destruction of chlorinated solvents in source zones

This study pilot-tested carboxymethyl cellulose (CMC) stabilized zero-valent iron (ZVI) nanoparticles (with a trace amount of Pd catalyst) for in situ destruction of chlorinated ethenes such as perchloroethylene (PCE) and trichloroethylene (TCE) and polychlorinated biphenyls (PCBs) that had been in groundwater for decades. The test site was located in a well-characterized secondary source zone of PCBs and chlorinated ethenes. Four test wells were installed along the groundwater flow direction (spaced 5 ft apart), including one injection well (IW), one up-gradient monitoring well (MW-3) and two down-gradient monitoring wells (MW-1 and MW-2). Stabilized nanoparticle suspension was prepared on-site and injected into the 50-ft deep, unconfined aquifer. Approximately 150 gallons of 0.2 g/L Fe-Pd (CMC = 0.1 wt%, Pd/Fe = 0.1 wt%) was gravity-fed through IW-1 over a 4-h period (Injection #1). One month later, another 150 gallons of 1.0 g/L Fe-Pd (CMC = 0.6 wt%, Pd/Fe = 0.1 wt%) was injected into IW-1 at an injection pressure <5 psi (Injection #2). When benchmarked against the tracer, approximately 37.4% and 70.0% of the injected Fe was detected in MW-1 during injection #1 and #2, respectively, confirming the soil mobility of the nanoparticles through the aquifer, and higher mobility of the particles was observed when the injection was performed under higher pressure. Rapid degradation of PCE and TCE was observed in both MW-1 and MW-2 following each injection, with the maximum degradation being observed during the first week of the injections. The chlorinated ethenes concentrations gradually returned to their pre-injection levels after ∼2 weeks, indicating exhaustion of the ZVI's reducing power. However, the injection of CMC-stabilized nanoparticle and the abiotic reductive dechlorination process appeared to have boosted a long-term in situ biological dechlorination thereafter, which was evidenced by the fact that PCE and TCE concentrations showed further reduction after two weeks. After 596 days from the first injection, the total chlorinated ethenes concentration decreased by about 40% and 61% in MW-1 and MW-2, respectively. No significant long-term reduction of PCB 1242 was observed in MW-1, but a reduction of 87% was evident in MW-2. During the 596 days of testing, the total concentrations of cis-DCE (dichloroethylene) and VC (vinyl chloride) decreased by 20% and 38% in MW-1 and MW-2, respectively. However, the combined fraction of cis-DCE and VC in the total chlorinated ethenes (PCE, TCE, cis-DCE and VC) increased from 73% to 98% and from 62% to 98%, respectively, which supports the notion that biological dechlorination of PCE and TCE was active. It is proposed that CMC-stabilized ZVI-Pd nanoparticles facilitated the early stage rapid abiotic degradation. Over the long run, the existing biological degradation process was boosted with CMC as the carbon source and hydrogen from the abiotic/biotic processes as the electron donor, resulting in the sustained enhanced destruction of the chlorinated organic chlorinated ethenes in the subsurface.     

Heterogeneous catalytic degradation of cyanide using copper-impregnated pumice and hydrogen peroxide

The main objective of this research was to investigate the oxidative destruction of free cyanide with hydrogen peroxide and copper-impregnated pumice as a heterogeneous catalyst. Original or copper-impregnated pumices added alone were not effective adsorbents of negatively charged cyanide ions due to incompatible surface interactions. Peroxide and original pumices added together were also ineffective in removing cyanide. However, for all of the three natural pumices tested with various particle size fractions, the use of copper-impregnated pumices and peroxide together significantly enhanced both the initial rate and extent of cyanide removal. Although copper-impregnated specific surface area was the major factor affecting the rate and extent of cyanide destruction for a particular pumice source with similar surface chemistries, the type of surface chemistry (i.e., specific functional groups) within different pumice sources also appears to be a very important factor. Lower rates and extents of cyanide removals were observed at pH 11 compared to pH 8 probably because of the negative impacts of alkaline conditions in terms of scavenging peroxide and forming more negatively charged pumice surfaces. Both the initial rate and ultimate extent of cyanide removals were generally higher at a temperature of 20 degrees C compared with those found at 10 degrees C. The use of copper-impregnated pumice as a light, cheap, readily available, natural, and porous heterogeneous catalyst either in completely mixed/suspended or fixed-bed reactor configurations may be an effective treatment technology for cyanide removal from solution. This new approach may minimize downstream metal removal problems experienced in conventional cyanide oxidation technologies.     

The role of effluent nitrate in trace organic chemical oxidation during UV disinfection

Most conventional biological treatment wastewater treatment plants (WWTPs) contain nitrate in the effluent. Nitrate undergoes photolysis when irradiated with ultraviolet (UV) light in the 200-240 and 300-325 nm wavelength range. In the process of nitrate photolysis, nitrite and hydroxyl radicals are produced. Medium pressure mercury lamps emitting a polychromatic UV spectrum including irradiation below 240 nm are becoming more common for wastewater disinfection. Therefore, nitrified effluent irradiated with polychromatic UV could effectively become a de facto advanced oxidation (hydroxyl radical) treatment process. UV-based advanced oxidation processes commonly rely on addition of hydrogen peroxide in the presence of UV irradiation for production of hydroxyl radicals. This study compares the steady-state concentration of hydroxyl radicals produced by nitrate contained in a conventional WWTP effluent to that produced by typical concentrations of hydrogen peroxide used for advanced oxidation treatment of water. The quantum yield of hydroxyl radical production from nitrate by all pathways was calculated to be 0.24 ± 0.03, and the quantum yield of hydroxyl radicals from nitrite was calculated to be 0.65 ± 0.06. A model was developed that would estimate production of hydroxyl radicals directly from nitrate and water quality parameters. In effluents with >5 mg-N/L of nitrate, the concentration of hydroxyl radicals is comparable to that produced by addition of 10 mg/L of H₂O₂. Nitrifying wastewater treatment plants utilizing polychromatic UV systems at disinfection dose levels can be expected to achieve up to 30% degradation of some micropollutants by hydroxyl radical oxidation. Increasing UV fluence to levels used during advanced oxidation could achieve over 95% degradation of some compounds.     

Biodegradation of monoaromatic hydrocarbons in aquifer columns amended with hydrogen peroxide and nitrate

The ability of indigenous microorganisms to degrade benzene, toluene, ethylbenzene and xylenes (BTEX) in laboratory scale flow-through aquifer columns was tested separately with hydrogen peroxide (110 mg/l) and nitrate (330 mg/l as NO₃⁻) amendments to air-saturated influent nutrient solution. The continuous removal of individual components from all columns relative to the sterile controls provided evidence for biodegradation. In the presence of hydrogen peroxide, the indigeneous microorganisms degraded benzene and toluene (> 95%), meta- plus para-xylene (80%) and ortho-xylene (70%). Nitrate addition resulted in 90% removal of toluene and 25% removal of ortho-xylene. However, benzene, ethylbenzene, meta- and para-xylene concentrations were not significantly reduced after 42 days of operation. Following this experiment, low dissolved oxygen (< 1 mg/l) conditions were initiated with the nitrate-amended column influent in order to mimic contaminated groundwater conditions distal from a nutrient injection well. Toluene continued to be effectively degraded (> 90%), and more than 25% of the benzene, 40% of the ethylbenzene, 50% of the meta- plus para-xylenes and 60% of the ortho-xylene were removed after several months of operation.     

Evaluation of the catalytic reduction of nitrate for the determination of dissolved organic nitrogen in natural waters

The catalytic reduction of nitrate ions into nitrogen gas was tested to partly remove dissolved inorganic nitrogen (DIN) before the determination of dissolved organic nitrogen (DON). Experiments were conducted on nitrate solutions enriched with natural organic matter (NOM) isolates previously extracted from surface waters. Three catalysts Pd-In/Al2O3, Pd-Sn/Al2O3 and Pd/SnO2 were tested. Their noble metal (palladium) and promoter metal (indium or tin) contents are 5 and 1.75 wt%, respectively. Preliminary experiments performed on a solution containing 17 amino acids showed that most compounds were removed by less than 15%, probably due to sorption onto the catalysts. Reduction of nitrate in absence of NOM was complete after 20 min of reaction time and the removal of DIN was about 80% (about 19% formation of ammonium). In the presence of NOM (DOC 20 mgC/L, DON 0.67 mg N/L), the kinetic of nitrate reduction was slower and the reduction in DIN content was limited to 15% i.e. selectivity toward ammonium reached 85%. Adsorption tests showed a similar removal of both DOC and DON of about 70% and 30% onto Pd-Sn/Al2O3 and Pd/SnO2 catalysts, respectively, which confirmed that NOM probably compete with nitrate for active catalytic sites. In conclusion, catalytic reduction of nitrate before DON determination cannot be used because of DON sorption and low DIN removal.     

Oxidation kinetics of two pesticides in natural waters by ozonation and ozone combined with hydrogen peroxide

The oxidation of bromoxynil and trifluralin was investigated using ozone (O₃) and O₃ combined with hydrogen peroxide (H₂O₂) in natural waters using batch reactors. The results indicated that these pesticides could not be completely degraded during ozonation, achieving degradation levels lower than 50%. An enhancement of the level of degradation was observed using O₃/H₂O₂ process. A biphasic behaviour of O₃ was also observed. Depending on the experimental conditions, the rate constant for O₃ decomposition was estimated to be between 7.4 × 10⁻⁴ s⁻¹ to 5.8 × 10⁻² s⁻¹, and 3.2 × 10⁻³ s⁻¹ to 4.2 × 10⁻² s⁻¹ for bromoxynil and trifluralin samples, respectively. Acute toxicity analysis performed using Microtox^® showed a decrease in the toxic effects of the samples on the luminescent bacteria during the first few minutes of treatment, followed by an increase of the toxic effects at the end of the reaction for both pesticides. The quantification of oxidation by-products generated during treatment was also addressed. The total molar balances of the degradation by-products versus the initial pesticide concentrations ranged from 60 to 103% under different experimental conditions.     

The photocatalytic degradation of dicamba in TiO2 suspensions with the help of hydrogen peroxide by different near UV irradiations

The direct photolysis and the photocatalytic degradations of dicamba in TiO2 suspensions with and without the use of hydrogen peroxide were studied using two different monochromatic UV irradiations (300 and 350 nm). Both the direct photolysis and photocatalytic degradations of dicamba follow pseudo-first-order decay kinetics. Photolysis reactions were slow but the corresponding photocatalysis rates were increased by about 3 and 5 times in the presence of TiO2 at 300 and 350 nm of UV, respectively. Photocatalytic rates were increased with the pH at acidic to neutral ranges because of the increase of hydroxide ions, but the reaction was gradually retarded at the alkaline medium due to the effect of charges repulsion. The different proton sources causing various degrees of rate retardation were due to the presence of the corresponding counter anions. The results of H2O2-assisted photocatalysis experiments showed that a low H2O2 dosage in photocatalysis using UV 300 nm would enhance the decay rate of dicamba by 2.4 times, but an overdose of H2O2 will retard the rate because of the expenditure of hydroxyl radicals. However, this process was found impracticable at UV 350 nm due to the absorption characteristic of H2O2. A neutral initial pH level was found to favour the H2O2-assisted photocatalysis at UV 300 nm. The reactions were highly retarded at the alkaline medium due to the unstable properties of H2O2.