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.     

Photodegradation of 2,4-dichlorophenoxyacetic acid in various iron-mediated oxidation systems

The oxidation of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by different iron-mediated processes, with or without the presence of ultraviolet (at 253.7 nm) and oxalate, was investigated and compared. The initial decay rate and the overall removal percentage were used as the performance indexes. To extensively explore the associated processes, the following combinations or blank systems were investigated: UV radiation only, Fe(2+)/H(2)O(2), Fe(2+)/H(2)O(2)/UV, ferrous oxalate/H(2)O(2), ferrous oxalate/H(2)O(2)/UV, Fe(3+)/H(2)O(2), Fe(3+)/H(2)O(2)/UV, ferrioxalate/H(2)O(2), and ferrioxalate/H(2)O(2)/UV. This study showed that the degradation of 2,4-D by sole UV or dark processes (without UV) is generally slow, except by the conventional Fenton's process (Fe(2+)/H(2)O(2)). However, these slow reactions can be accelerated by exposure to UV irradiation, which can increase the initial 2,4-D decay rate from ten to more than one hundred times. Furthermore, if the reaction is initiated by ferrous oxalate or ferrioxalate instead of Fe(2+) or Fe(3+) ions, the rates can be further improved, because of the higher light sensitivity of the organometallic complexes. These reactions were also found sensitive to the initial hydrogen peroxide concentration. The competition of hydroxyl free radicals by the primary intermediate, 2,4-dichlorophenol, was also observed.     

Application of ferrous hydrogen peroxide for treatment of DSD-acid manufacturing process wastewater

A pretreatment method for the biological treatment of wastewater from 4,4'-diaminostilbene-2,2'-disulfonic acid (DSD-acid) manufacturing processes, a refractory dye intermediate wastewater, based on combined ferrous hydrogen peroxide oxidation and coagulation-flocculation, was developed. When the wastewater was treated with ferrous hydrogen peroxide oxidation ([Fe2+] = 2.7 mmol/L, [H2O2] = 0.21 mol/L) after a flocculation using an organic flocculant TS-1 at a dosage of 3 g/L, the overall COD and color removals were 64 and 62%, respectively. BOD5/COD value of the effluent was 0.3. Ferrous hydrogen peroxide oxidation treatment can reduce the solubility of organic molecules with sulfonic group and increase the efficiency of coagulation treatment. The COD and color removals were both more than 90% when FeCl3 was used as the coagulation (dosages of two-step coagulation were 0.031 and 0.012 mol/L respectively) after a ferrous hydrogen peroxide oxidation pretreatment at a H2O2 dosage of 0.06 mol/L.     

Degradation of TCE,Cr(VI), sulfate,and nitrate mixtures by granular iron in flow-through columns under different microbial conditions

Flow-through aquifer columns packed with a middle layer of granular iron (Fe0) were used to study the applicability and limitations of bio-enhanced Fe0 barriers for the treatment of contaminant mixtures in groundwater. Concentration profiles along the columns showed extensive degradation of hexavalent chromium Cr(VI), nitrate, sulfate, and trichloroethene (TCE), mainly in the Fe0 layer. One column was bioaugmented with Shevanella algae BRY, an iron-reducing bacterium that could enhance Fe0 reactivity by reductive dissolution of passivating iron oxides. This strain did not enhance Cr(VI), which was rapidly reduced by iron, leaving little room for improvement by microbial participation. Nevertheless, BRY-enhanced nitrate removal (from 15% to 80%), partly because this strain has a wide range of electron acceptors, including nitrate. Sulfate was removed (55%) only in a column that was bioaugmented with a mixed culture containing sulfate-reducing bacteria. Apparently, these bacteria used H2 (produced by Fe0 corrosion) as electron donor to respire sulfate. Most of the TCE was degraded in the zone containing Fe0 (50-70%), and bioaugmentation with BRY slightly increased the removal efficiency to about 80%. Microbial colonization of the Fe0 surface was confirmed by scanning electron microscopy.     

UV-based processes for reactive azo dye mineralization

In the present study, advanced oxidation processes, UV/H2O2, UV/O3, and UV/H2O2/O3 have been applied to bleach and degrade organic dye C.I. Reactive Red 45 in water solution. Influence of pH and hydrogen peroxide dosage on process efficiency was investigated. The rate of color removal was studied by measuring the absorbance at the characteristic wavelength while mineralization rates were obtained on the basis of total organic carbon (TOC) and adsorbable organic halides (AOX) measurements. Complete bleaching was achieved by all applied processes after 60 min while the maximal mineralization extent depended on the reaction conditions for each of the processes. It has been found that UV/H2O2/O3 process was the most efficient with 61.1% TOC removal and 72.0% AOX removal, respectively, achieved after a 1-h treatment. Time required for complete mineralization of RR45 by UV/H2O2 and UV/H2O2/O3 processes was determined as well.     

Discoloration and mineralization of Reactive Red HE-3B by heterogeneous photo-Fenton reaction

Discoloration and mineralization of Reactive Red HE-3B were studied by using a laponite clay-based Fe nanocomposite (Fe-Lap-RD) as a heterogeneous catalyst in the presence of H2O2 and UV light. Our experimental results clearly indicate that Fe-Lap-RD mainly consists of Fe2O3 (meghemite) and Fe2Si4O10(OH)2 (iron silicate hydroxide) which have tetragonal and monoclinic structures, respectively, and has a high specific surface area (472 m2/g) as well as a high total pore volume (0.547 cm3/g). It was observed that discoloration of HE-3B undergoes a much faster kinetics than mineralization of HE-3B. It was also found that initial HE-3B concentration, H2O2 concentration, UV light wavelength and power, and Fe-Lap-RD catalyst loading are the four main factors that can significantly influence the mineralization of HE-3B. At optimal conditions, complete discoloration of 100 mg/L HE-3B can be achieved in 30 min and the total organic carbon removal ratio can attain 76% in 120 min, illustrating that Fe-Lap-RD has a high photo-catalytic activity in the photo-assisted discoloration and mineralization of HE-3B in the presence of UV light (254 nm) and H2O2.     

Treatment of trichlorophenol by catalytic oxidation process

The oxidation of 2,4,6-trichlorophenol (TCP) by ferrous-catalyzed hydrogen peroxide was quantified and modeled in the study. TCP was effectively degraded by hydroxyl radicals that were generated by Fe(II)/H(2)O(2) in the oxidation process. The oxidation capacity (OC) of the process depends on the concentrations of oxidant (hydrogen peroxide) and oxidative catalyst (ferrous ion). Up to 99.6% of TCP removal can be achieved in the process, provided the doses of Fe(II) and H(2)O(2) are selected correctly. The OC of the process was successfully predicted through a kinetic approach in a two-stage model with some simple and measurable parameters, which makes the model useful for predicting, controlling and optimizing the catalyzed oxidation process in the degradation of TCP.     

UV/H2O2/微曝气处理微污染水中苯胺的试验研究

采用UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺处理受苯胺污染的水源水.试验结果表明,采用UV/H2O2/微曝气工艺,H2O2投加量分别为1,2,5,10和20 mL,对苯胺均有理想的去除效果.随着投加量的增加,苯胺的去除率并没有明显的提高,反应30 min后去除率分别达到94.3%,96.4%,96.5%,97.3%和96.8%.原水苯胺为0.90 mg/L时,投加1 mL H2O2反应30 min后,出水苯胺为0.06 mg/L,满足标准要求.UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺对苯胺的去除率均随着时间的增长而提高,40 min后趋于平稳,最高去除率分别为97.9%,94.5%,64.27%和13.84%,UV/H2O2/微曝气、UV/H2O2出水苯胺均低于规定限值.     

新生态铁锰氧化物的混凝及强化混凝效能分析

采用FeSO4与KMnO4反应制备成新生态铁锰氧化物,并对松花江水进行处理。试验结果表明：新生态铁锰氧化物较新生态二氧化锰的除污效果好,但新生态铁锰氧化物的除污能力会随着放置时间的延长而逐渐下降;在不同温度和浊度的松花江水的混凝试验中,浊度低时新生态铁锰氧化物对水中有机物的去除效果较好,温度对其混凝效果影响较小;利用新生态铁锰氧化物强化硫酸铝的混凝过程,能够明显提高对低温、低浊水中有机物的去除效果,对UV254的去除率较单独投加硫酸铝时几乎提高了1倍,对TOC的强化去除作用在混凝剂投量低时更为明显。     

微电解/Fenton法深度处理土霉素废水的研究

采用微电解/Fenton法对土霉素废水二级出水进行深度处理。正交和单因素试验结果表明,微电解法的最佳工艺条件:Fe投量为125 g/L、铁炭质量比为1.5∶1、初始pH值为4.0、反应时间为2 h,在进水COD为361～395 mg/L的条件下,处理后出水COD可降至198～207 mg/L,对COD的去除率可达44%以上;采用Fenton法进一步处理微电解出水,其最佳工艺条件:H2O2(浓度为30%)投加量为2 mL/L、初始pH值为3.0、反应时间为60 min,处理后出水COD<120 mg/L,组合工艺对COD的总去除率达到70%以上,满足《发酵类制药工业水污染物排放标准》(GB21903—2008)的要求。     

FeSO_4应用于SBBF强化除磷

序批式生物膜滤池(SBBF)是基于序批式生物膜法的改进污水处理新型工艺,针对SBBF处理城市污水的除磷的效果较差的弊端,通过直接投加FeSO_47H_2O到反应体系实现协同除磷,使得该工艺能够较好地应用于污水脱氮除磷。Fe(Ⅱ)的投加量从0.03~0.3mM进行协同除磷试验,结果表明0.2mM的Fe(Ⅱ)投加可为有效投加量。进一步将0.2mM的Fe(Ⅱ)在进水阶段后投加到反应体系,稳定运行1个月,发现出水的TP稳定保持在0.5mg/L以下,而COD和氮的去除基本不受影响。COD、NH_4~+-N、TN和TP的平均去除率分别为84.9%、83.2%、46.3%和88.2%。反应器出水的各项指标均稳定达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)的一级A排放标准。     

Degradation of Pb--EDTA complex by a H(2)O(2)/UV process

The degradation of PbEDTA in aqueous solution by a H(2)O(2)/UV process was studied. The effect of H(2)O(2) content, pH of the solution and the presence of nitrate were investigated. PbEDTA degradation by a H(2)O(2)/UV process was shown to be accompanied by simultaneous lead precipitation. PbEDTA was decomposed rapidly in acidic solutions while lead precipitation was achieved only when the pH of the solution was higher than 6. The presence of nitrate in significant amounts (0.04 M) inhibited remarkably the degradation of the complex and metal precipitation. The degradation of CdEDTA and ZnEDTA was also studied. It was found that the decomposition of metal-EDTA complex and metal removal by the H(2)O(2)/UV process depend greatly on the nature of the metal. CdEDTA and ZnEDTA were decomposed rapidly but metal precipitation was not achieved. The major by-products of the degradation of metal-EDTA complexes observed were nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), oxalic acid and nitrate.     

Effect of medium-pressure UV irradiation on bromate concentrations in drinking water, a pilot-scale study

This study investigated the potential for bromate removal from drinking water on irradiation with medium-pressure UV lamps-a technique gaining considerable interest for drinking water disinfection. Waters from two different sources were spiked with 20microg/L of bromate and irradiated with UV fluences up to 718mJ/cm(2) utilizing a pilot-scale reactor (Calgon Carbon Corp.) at a flow of 76L/min (20 gallon/min). Essentially no removal was observed in one of the source waters. Limited bromate removal, up to 19%, was observed in the second source water at high UV fluences (696mJ/cm(2)) and a fluence-response relationship was clearly evident. All removals would be negligible at UV fluences anticipated for drinking water disinfection (< or =40mJ/cm(2)). Different water characteristics, in particular competitive absorption by nitrate and possibly DOC, were most likely responsible for the differences in bromate removal in the waters tested. The source water that did not show any removal had a higher nitrate concentration (4 vs. 0.1mg N/L) and also a higher DOC concentration (4.1 vs. 3.1mg C/L) than the other source water which showed 19% bromate removal.     

Effect of precursor concentration on the characteristics of nanoscale zerovalent iron and its reactivity of nitrate

Differing precursor concentrations, 1.0, 0.1, and 0.01 M FeCl(3) x 6H(2)O, were performed to produce nanoscale Fe(0) and the results were discussed in terms of the specific surface area, particle size and electrochemical properties. The results indicated that the nanoscale Fe(0) prepared by 0.01 M FeCl(3) had absolutely reduced in size (9-10nm) and possessed the greatest specific surface area (56.67 m(2) g(-1)). These synthesized nanoscale Fe(0) particles were attempted to enhance the removal of 40 mg-NL(-1) unbuffered nitrate solution. The first-order degradation rate constants (k(obs)) increased significantly (5.5-8.6 times) with nanoscale Fe(0) prepared by 0.01 M precursor solution (Fe(0.01 M)(0)). When normalized to iron surface area concentration, the specific rate constant (k(SA)) was increased by a factor of approximately 1.7-2.4 using Fe(0.01 M)(0) (6.84 x 10(-4) L min(-1) m(-2) for Fe(0.01 M)(0), 4.04 x 10(-4) L min(-1) m(-2) for Fe(0.1 M)(0) and 2.80 x 10(-4) L min(-1) m(-2) for Fe(1 M)(0)). The rise of reactivity of the reactive site on the Fe(0.01 M)(0) surface was indicated by the specific rate constant (k(SA)) calculation and the i(0) value of the electrochemical test.     

Nitrate removal in zero-valent iron packed columns

Nitrate removal by laboratory and field continuous-flow zero-valent iron (Fe(0)) packed bed columns was evaluated for different influent water qualities (pH, dissolved oxygen (DO), nitrate concentration) and several months of operation (600-1500 bed volumes (BVs)). In contrast to previous batch experiments with Fe(0) where nitrate was stoichiometrically converted to ammonium, only 70% of the applied nitrogen was recovered as nitrate, ammonium, or nitrite (<0.1mg/L) during shorter-term column tests (2-20 BVs) and less than 25% of the applied nitrogen was recovered during longer-term field testing (500-1000 BVs) at elevated nitrate levels (approximately 25mg N/L). Nitrate removal was accompanied by a pH increase, DO decrease, and soluble iron increase. During longer-term operation (500-1500 BVs) iron and calcium precipitates were observed, by SEM and EDX analyses, to form in the packed columns. Precipitation led to cementation and reduction in permeability for the Fe(0)/sand media in the packed column. Different abiotic and microbial-mediated mechanisms may be involved during shorter- and longer-term operation of Fe(0) systems and the role of iron precipitates should be further evaluated.     

The role of hydroxyl radicals for the decomposition of p-hydroxy phenylacetic acid in aqueous solutions

The chemical decomposition of p-hydroxyphenylacetic acid, a priority phenolic pollutant present in wastewaters from some agro-industrial plants, is studied by means of a single photochemical process produced by a polychromatic UV radiation and by hydroxyl radicals generated by the combination of UV radiation plus hydrogen peroxide and by the Fenton's reagent (hydrogen peroxide plus ferrous salts). Batch experiments were conducted to establish the degradation levels obtained and the quantum yields in the single photodecomposition process. An improvement in the decomposition of the phenolic acid in the combined UV/H2O2 oxidation is observed, due to the generation of OH radicals, and the contribution of the radical reaction to the global process is determined. In the Fenton's reagent oxidation, the effects of the operating variables (H2O2 and Fe2+ initial concentrations, pH, type of buffer used) are established and the rate constant for the reaction of p-hydroxyphenylacetic acid with OH radicals is evaluated from a kinetic model, its value being 7.02 x 10(8) M-1 s-1 at 20 degrees C.     

Comparison of different advanced oxidation processes for phenol degradation

Advanced Oxidation Processes (O3, O3/H2O2, UV, UV/O3, UV/H2O2, O3/UV/H2O2, Fe2+ /H2O2 and photocatalysis) for degradation of phenol in aqueous solution have been studied in earlier works. In this paper, a comparison of these techniques is undertaken: pH influence, kinetic constants, stoichiometric coefficient and optimum oxidant/pollutant ratio. Of the tested processes, Fenton reagent was found to the fastest one for phenol degradation. However, lower costs were obtained with ozonation. In the ozone combinations, the best results were achieved with single ozonation. As for the UV processes, UV/H2O2 showed the highest degradation rate.     

Effects of iron surface pretreatment on sorption and reduction kinetics of trichloroethylene in a closed batch system

The decline of trichloroethylene (TCE) in a metallic iron-water system results from the combination of reduction reaction and sorption onto iron surfaces. Sorption, particularly by highly impure iron, accelerates the removal of TCE from the aqueous phase, but delays the prevalence of steady-state conditions. In this case, an overly high value of reaction rate constant in the design of a treatment system would be used. In this work, the effects of an iron surface with 8.0% C, 6.1% O and 0.8% Si separately following HCl-washing and H2-reducing pretreatment on sorption and reduction rates were examined. The amounts of both aqueous and sorbed TCE were measured using a modified solvent-extraction method. TCE sorption onto an iron surface, as quantified by the Langmuir sorption maximum, followed the trend H2-reduced Fe0 > HCl-washed Fe0 > untreated Fe0 (0.887, 0.365 and 0.311 mg/g, respectively). Measurements of the concentration of sorbed TCE revealed that about 34-37% of the initial mass of TCE in the aqueous phase was removed by sorption by H2-reduced Fe0, 16-19% was removed by HCl-washed Fe0 and 13-16% was removed by untreated Fe0. A combination of new and previously reported data on cast iron's capacity to sorb TCE revealed a linear relationship between this capacity and the C fraction in the surface of the iron, with the coefficient of determination (r2) exceeding 0.99. The first-order observed rate constants (k(obs)) of the reduction of TCE in contact with Fe0 were obtained from the slope of a plot of total TCE loss rate (-dC(T)/dt) versus the amount of TCE in the aqueous phase (C(w)) using linear least-squares analysis. The k(obs) values were 0.080, 0.148 and 0.191 h(-1) for untreated, HCl-washed and H2-reduced Fe0, respectively. Normalized to iron surface area concentration, the specific rate constants (k(SA)) were 2.3 7x 10(-3) , 2.31 x 10(-3) and 5.62 x 10(-3) h(-1) m(-2) L, respectively. The results indicated that HCl-washing approximately doubled k(obs), primarily because of the increase in the surface area of the iron, and it slightly decreased k(SA) due to rapid corrosion during the rinsing process. Both the number of reactive sites and the sorption capacity per unit iron surface area through the H2-reducing pretreatment were increased due to the reduction of iron oxide layer and the carbonization of carbon-containing subjects on the iron's surface. Hence, the H2 reduction of cast iron promotes the removal of TCE from contaminated water by the concurrent sorption and reduction.     

硫酸铝强化纳米铁还原硝酸盐氮的研究

在水体溶解氧较高的条件下,采用投加硫酸铝的方式强化纳米铁对硝酸盐氮的去除效果。结果表明,投加硫酸铝可明显提高纳米铁对硝酸盐氮的去除效果,当硝酸盐氮初始浓度为10mg/L、纳米铁投量为5g/L、硫酸铝投量为100mg/L时,反应6h后对硝酸盐氮的去除率可达到83%,而不投加硫酸铝的情况下仅为51%。纳米铁对硝酸盐氮的还原过程符合拟一级反应动力学规律,其反应速率常数k随纳米铁投量和硫酸铝投量的增加而增大;纳米铁对硝酸盐氮的去除率随pH的降低而升高,随初始硝酸盐氮浓度的增加而下降;纳米铁还原硝酸盐氮的表观活化能较低,还原反应在常温下即很容易进行;硝酸盐氮的最终还原产物为氨氮。     

Destruction of estrogenic activity in water using UV advanced oxidation

The transformation of the steroidal Endocrine Disrupting Compounds (EDCs), 17-beta-estradiol (E2) and 17-alpha-ethinyl estradiol (EE2) by direct UV photolysis and UV/H(2)O(2) advanced oxidation was studied from the perspective of the removal of estrogenic activity associated with the compounds. First, experiments were performed to link the oxidation of E2 and EE2 with subsequent reduction in estrogenic activity. No statistically significant difference between removal rates was observed, implying that the oxidation products of E2 and EE2 are not as estrogenic (measured by the Yeast Estrogen Screen (YES)) as the parent compounds. Utilizing the YES, 90% removal of estrogenic activity of E2 and EE2 at environmentally relevant concentrations ( approximately 3 microg L(-1)) was achieved using a combination of 5 mg L(-1) H(2)O(2) and a UV fluence of less than 350 mJ cm(-2). Thus, these compounds, when considered at environmentally relevant levels, are significantly degraded at much lower UV fluences than previously thought. A steady state OH radical model was used to predict oxidation of EE2 in laboratory and natural waters.