Effective degradation of para-chloronitrobenzene through a sequential treatment using zero-valent iron reduction and Fenton oxidation

In this study, zero-valent iron (ZVI) was used to pretreat para-chloronitrobenzene (p-CNB), and the major product was para-chloroaniline (p-CAN). By adding H(2)O(2) directly, further p-CAN degradation can be attributed to Fenton oxidation because ferrous ions (Fe(2+)) released during the ZVI corrosion could be used as an activator for H(2)O(2) decomposition. In the reduction process, the reduction efficiency of p-CNB as well as Fe(2+) concentration increased with increasing iron dosage and decreasing solution pH. Under the optimal conditions, 25 mg L(-1) of p-CNB could be transformed in 3 h when initial solution pH was 3.0 and ZVI dosage was 2.0 g L(-1). A sufficient amount of Fe(2+) (50.4 mg L(-1)) was obtained after the above reaction to activate H(2)O(2). In the Fenton process, the oxidization of p-CAN was also more effective in acidic conditions and it increased with increasing H(2)O(2) concentration. The control experiments showed that the sequential treatment was more effective than Fenton oxidation alone in treating p-CNB wastewater since the removal rate of total organic carbon (TOC) was improved by about 34%. It suggested that the amino function group is more susceptible to oxidative radical attack than the nitro function group. Therefore, sequential treatment using zero-valent iron reduction followed by Fenton oxidation is a promising method for p-CNB degradation.     

Decolorization of anthraquinone dye Reactive Blue 19 by the combination of persulfate and zero-valent iron

Decolorization of anthraquinone dye Reactive Blue 19 (RB19) with sulfate radicals generated in situ from persulfate and zero-valent iron (ZVI) was investigated. The effects of initial solution pH, initial concentration of RB19, ZVI and persulfate, reaction temperature and common dissolved anions were studied. 100% color removal efficiency and 54% TOC removal efficiency were achieved in 45 min with an initial RB19 concentration of 0.1 mM under typical conditions (pH 7.0, 0.8 g L(-1) ZVI, 10 mM persulfate and 30 C). The decolorization efficiency of RB19 increased with higher iron dosage, higher initial persulfate concentration, and higher reaction temperature. It is also an acid driven process. The decolorization process followed pseudo-first order kinetics and the activation energy was 98.1 kJ mol-1. RB19 decolorization was inhibited by common dissolved anions such as CL-, NO3-, H2PO4- and HCO3- since they reacted with sulfate radicals that retarded the oxidation process. The experiment demonstrated that the combination of persulfate and ZVI was a promising technology for the decolorization of dye wastewater.     

Mechanistic evidence and efficiency of the Cr(VI) reduction in water by different sources of zerovalent irons.

The objective of this research was to assess the mechanism and effectiveness of the zerovalent iron (ZVI) to remediate the Cr(VI) contaminated water. The mechanism of Cr(VI) reduction by ZVI was evaluated by characterising surface properties and chemical compositions of Fe and Cr products using SEM-EDS, XRD and XPS analyses. The effectiveness of ZVI in Cr(VI) reduction was assessed by the luminescent bacteria (Photobacterium Phosphoreum). The Cr(VI) was reduced to Cr(III), when the reactive Fe(o) was oxidised to Fe(II, III), showing the presence of Fe2O3, (Fe-Cr)2O3 and FeOOH. The SEM-EDS analysis showed that ZVI with a higher reducing capacity was more subject to changes of surface and morphological properties due to ionisation of ZVI. The Cr and Fe in precipitates subsisted exclusively in the Cr(III) or Fe(III) states with the respective forms of Cr(OH)3 or Cr2O3 and FeOOH or Fe2O3. Electrons produced from ZVI oxidation reduced Cr(VI) to Cr(III), thus resultantly Cr(III) precipitated or co-precipitated with Fe(III) to form Fe(III)-Cr(III) hydroxide or Fe(III)-Cr(III) oxyhydroxide. Toxicity of water reacted with ZVI was significantly lower than that of the untreated water.     

New insights into the mechanisms of the thermal Fenton reactions occurring using different iron(II)-complexes.

Although the Fenton reagent (a mixture of hydrogen peroxide and an iron(II) salt) has been known for more than a century, the manifold mechanisms occurring during the thermal Fenton reaction are still under discussion. Indeed, this discussion served as a powerful driving force for the steadily increasing insight into the field of inorganic radical and electron transfer chemistry. In this work, an experimental approach towards the elucidation of the first steps taking place in the reaction between several iron(II)-complexes and hydrogen peroxide (H2O2) in water at pH = 3.0 is presented. 2,4-xylidine (2,4-dimethylaniline) reacts differently with reactive intermediates via the addition or hydrogen abstraction by the hydroxyl radical (HO*) or electron transfer reactions to higher valent iron-species, such as a hydrated ferryl-complex (Fe(IV)). The chemical reactivity of the employed iron(II)-complexes with H2O2 differed strongly depending on their ground-state one-electron oxidation potentials. The results are interpreted in accordance with the paradigm originally developed by Goldstein et al. which is based on the evidence obtained from the Marcus theory that outer-sphere electron transfer reactions between metal complexes are not likely to occur because they are too slow. Therefore, most of the "Fenton-reagents" form transient metal complexes, which can be described as [LnFe-H2O2]m+. They form, depending on the reaction conditions, either the hydroxyl radical or higher-valent iron complex species.     

纳米铁还原TNT红水中二硝基甲苯磺酸(钠)的影响因素研究

考察了纳米铁的投加量、二硝基甲苯磺酸钠(DNTS)初始浓度、初始pH、纳米铁超声、干燥处理等因素对纳米铁还原TNT红水中DNTS效果的影响。结果表明:考察范围内,纳米铁/DNTS质量比越大,DNTS的去除率越高,单位质量纳米铁去除DNTS总质量越小;当初始pH<10时,去除率受pH影响不大,但准一级反应速率常数随pH上升而接近直线下降,酸性条件下还原更彻底,碱性条件下吸附沉淀作用更明显;干燥处理使纳米铁被部分氧化,还原能力下降;超声有助于促进纳米铁的充分分散和表面氧化层的剥离,提高反应活性。去除率随时间变化曲线表明,2,4-DNT-5-SO3Na(H)比2,4-DNT-3-SO3Na(H)容易被还原。     

Fenton试剂对铁锰矿井废水处理的实验研究

使用Fenton试剂对铁锰矿井水进行处理试验,论述了反应温度、H2O2的投加量、pH、反应时间对Fenton试剂处理矿井水的影响,讨论了Fenton试剂处理酸性矿井废水的机理。结果表明:芬顿试剂对铁锰矿井水中锰的去除效率很高,矿井水中的Fe2+能与H2O2形成Fenton试剂后产生的具有强氧化性的.OH能有效处理矿井水中的Mn2+。对于原水Mn2+的初始浓度为2 mg/L,Fe2+的初始浓度为250 mg/L,pH为5,当控制反应温度为25℃,H2O2的投加量为8 mmol/L,调节pH值为4.5,反应时间为10 m in,Mn2+去除效率可以达到78.1%以上。     

Photo-Fenton reaction using a nanocomposite.

A laponite RD clay-based Fe nanocomposite (Fe-Lap-RD) has been synthesized by the so-called pillaring technique. The X-ray diffraction (XRD) results reveal that the Fe-Lap-RD mainly consists of Fe2O3 (maghemite) crystallites and Fe2SiO10(OH)2 (iron silicate hydroxide) crystallites. The photo-catalytic activity of the Fe-Lap-RD for the degradation of an organic azo dye Orange II is examined. It is found that the rate of mineralization of Orange II is slower than that of discoloration. Under optimal conditions, 100% color and 70% total organic carbon (TOC) of 0.2 mM Orange II can be removed in 45 and 90 minutes, respectively. In addition, the performance of a strongly acidic type of ion exchange resin based catalyst as a heterogeneous photo-Fenton catalyst for the degradation of salicylic acid is also discussed.     

Significance of acetogenic H2 consumption in dark fermentation and effectiveness of pH.

Two identical thermophilic H(2) fermenters (R1 and R2) were operated at different pH levels between 4.7 and 5.7. In R1, several unexpected and severe drops in H(2) yield inversely proportional to increase in acetate production were experienced at pH 5.5 and 5.7. In contrast, R2 operated at pH 5 and 4.7 performed more stable H(2) production mainly through butyrate fermentation. Although the H(2) partial pressure (>50 kPa) was far above the favorable values, acetate was produced as well as butyrate in all pH levels tested. To determine whether some portion of the acetate is produced through another pathway such as autotrophic synthesis via H(2) dependent reduction of CO(2) or not, batch dissolved H(2) consumption rate tests were performed at pH 5.0, 5.5 and 6. The specific H(2) consumption rate was 488(+/-49) micromol/gVSS.hr at pH 6 and slightly higher than at pH 5 and 5.5. The results of continuous and batch experiments revealed that acetogenic H(2) consumption is more favorable at pH levels above 5.5 and is one of the reasons of instabilities in dark fermentative H(2) production.     

Heterogeneous catalytic oxidation of hypophosphite by H2O2: pH effect.

Phosphorus chemicals control key aspects of eutrophication and other environmental process. Hypophosphite (HP) originating from manmade and natural sources was evidenced as present in the environment and was investigated rarely. Recently, iron oxide has been used as a catalyst for oxidising organic contaminants with hydrogen peroxide (i.e. heterogeneous Fenton-like reaction). This study focused mainly on the oxidation of 1.0 mM HP by hydrogen peroxide in the presence of a novel iron oxide catalyst (B1 catalyst) which was prepared through a fluidised-bed Fenton reactor (FBR-Fenton). The background experiments including the oxidation experiment of HP by air only, by H2O2 only and adsorption of HP by B1 catalyst were first elucidated. It was found that HP could not be oxidised at all by air and H2O2 at pH 2.5-12 in 24 hours. On the other hand, it could be adsorbed by B1 catalyst with 89.8% removal at pH 2.5 in 5 hours and complete desorption at pH 11.0. Then, we investigated the effects of pH and Fe leaching from the catalyst on the oxidative efficiency of HP. We found that although the removal rate of HP at pH 2.5 is faster than that at pH 4.0, B1 catalyst has a higher HP oxidation efficiency at pH 4.0 than that at pH 2.5. We conclude that it is a major heterogeneous catalytic oxidation by our novel iron oxide catalyst to oxidise HP at pH 4.0. Also, B1 could be a useful and potential catalyst for the treatment of HP wastewater.     

The denitration pathway of p-nitrophenol in the hydrogen peroxide catalytic oxidation with an Fe(III)-resin catalyst

The liquid-phase hydrogen peroxide catalytic oxidation of p-nitrophenol was performed with an Fe(III)-resin catalyst. The conversion and mineralization of p-nitrophenol was effectively achieved at mild reaction conditions with the Fe(III)-resin catalyst. It was found that the oxidant concentration, pH, and temperature dominated the degradation rate of p-nitrophenol. The denitration pathway of p-nitrophenol was proposed, in which the concentration of H(2)O(2) and temperature showed strong influence on the conversion of nitrite to nitrate. To study the factors influencing the denitration of p-nitrophenol, a comparable kinetic study was attempted to know the possible denitration pathway of p-nitrophenol. The results of this investigation indicated that denitration was the possible step occurring with the decomposition of p-nitrophenol.     

Potential of UV/H2O2 oxidation for enhancing the biodegradability of municipal reverse osmosis concentrates

UVC/H2O2 and VUV/H2O2 oxidation processes were evaluated for the degradation of organic pollutants in reverse osmosis concentrate (ROC) produced from a municipal secondary effluent. It was found that the oxidation by UVC/H2O2 and VUV/H2O2 processes could be described as a pseudo first-order reaction. For UVC increased oxidation occurred with increasing H2O2 dosage up to 2 mM above which improvement in oxidation performance decreased. At the same H2O2 dosage, VUV irradiation gave better overall oxidation performance. Compared with UVC/6 mM H2O2, VUV/2 mM H2O2 gave a greater rate of reduction of chemical oxygen demand, but a lower rate for reduction of dissolved organic carbon, suggesting that oxidation of organics by the two methods followed different pathways. The change of absorbance at 254 nm and fluorescence excitation emission matrix spectra of irradiated samples indicated that the large and complex compounds were fragmented rapidly by the *OH, resulting in rapid decolourisation. The biodegradability of the organics in the ROC was increased from 11% to 35% after 1 h treatment by UVC/3 mM H2O2, whereas a greater increase (41%) was obtained with VUV/2 mM H2O2. This increase in biodegradability indicates the potential for employing a subsequent biological treatment process.     

Kinetics of anaerobic biodecolourisation of azo dyes.

Kinetics of anaerobic biodecolourisation (methanogenic environment) of four azo dyes (Acid Orange 6, Acid Orange 7, Methyl Orange and Methyl Red) was investigated with regard to their electrochemical properties as well as under variation of dye and sludge concentrations, pH and temperature. Cyclic voltammetry revealed a correlation between the potential of irreversible reduction peak of the dye and its first-order decolorisation constant. For each dye tested, this decolourisation constant was adversely proportional to dye concentration (0.086-1.7 mM) and had a saturation (hyperbolic) dependency on sludge concentration (0.04-1.1 g VSS/l), a bell-shape dependency on pH (4.0-9.0) and Arrhenius dependency on temperature (24-40 degrees C). Transfer from methanogenic to sulphate reducing environment led to an increase of decolorisation constant for all the dyes investigated due to the abundant presence of sulphide as a reducing agent in the reaction medium. Similar transfer to a denitrifying environment resulted in an almost complete decease of decolourisation because nitrate easily outcompetes azo dyes as an electron acceptor.     

Effect of Fenton's treatment on the biodegradability of chromium-complex azo dyes.

Pretreatment of an acid dyebath effluent bearing a new generation chromium complex azo dyestuff (C0 = 350 mg/L) with Fenton's reagent was investigated. Preliminary optimisation (baseline) experiments were conducted to determine the Fe2+, H2O2 concentrations and pH required to the highest possible COD and colour removals. Kinetic studies were carried out at varying temperatures (20 degrees C < T < 70 degrees C) to establish a relationship between COD abatement and H2O2 consumption. The activation energy found for catalytic H2O2 decomposition (Ea = 9.8 kJ/mol) appeared to be significantly less than that of fermentative (Ea = 23 kJ/mol) and of thermal (Ea = 76 kJ/mol) H2O2 decomposition, implying that H2O2 decomposition during the Fenton's reaction occurs more spontaneously. The experimental studies indicated that approximately 30% COD and complete colour removal could be achieved under optimised Fenton pretreatment conditions (Fe2+ = 2 mM; H2O2 = 30 mM; pH = 3; at T = 60 degrees C). Long-term activated sludge experiments revealed that although the raw and pretreated acid dyebath effluent contained practically the same amount of "readily biodegradable" COD (inert COD fraction < or = 10%), biodegradation of the chemically pretreated acid dye effluent proceeded appreciably faster than that of the untreated acid dyebath effluent.     

Phosphorus removal from synthetic and municipal wastewater using spent alum sludge.

In the present study, phosphorus removal was studied using as coagulant spent alum sludge from a water treatment plant of EYDAP (Athens Water Supply and Sewerage Company) and compared to alum (Al2(SO4)3.18H2O), iron chloride (FeCl3.7H2O), iron sulfate (Fe2(S04).10H2O) and calcium hydroxide (Ca(OH)2) at a constant pH (equal to 6).The comparison was based on their efficiency to remove phosphorus in synthetic wastewater consisting of 10 mg/L P as potassium dihydrogen phosphate and 50 mg/L N as ammonium chloride, The experiments were carried out using a jar-test apparatus and the measurements were performed according to the Standard Methods for the Examination of Water and Wastewater. Pure alum, iron chloride and iron sulfate were much more efficient in phosphorus removal than the spent alum sludge but in the case of calcium hydroxide, phosphorus removal was very low in pH = 6. Specifically, orthophosphate were totally removed by alum using 15 mg/L as Al, by alum sludge using 75 mg/L as Al and by FeCl3.7H2O or Fe2(SO4).10H2O using 30 mg/L of Fe while in the case of calcium hydroxide P removal was actually zero. pH measurements showed that the uptake of phosphates is associated to the release of OH ions in the solution and that the end of P uptake is accompanied by the stabilization of pH. Finally this spent alum sludge was tested on municipal wastewater and proved to be effective as apart from phosphorus it was shown to remove turbidity and COD.     

Zero-valent iron treatment of RDX-containing and perchlorate-containing wastewaters from an ammunition-manufacturing plant at elevated temperatures.

The use of zero-valent iron for treating wastewaters containing RDX and perchlorate from an army ammunition plant (AAP) in the USA at elevated temperatures and moderately elevated temperature with chemical addition was evaluated through batch and column experiments. RDX in the wastewater was completely removed in an iron column after 6.4 minutes. Increasing the temperature to 75 degrees C decreased the required retention time to 2.1 minutes for complete RDX removal. Perchlorate in the wastewater was completely removed by iron at an elevated temperature of 150 degrees C in batch reactors in 6 hours without pH control. Significant reduction of perchlorate by zero-valent iron was also achieved at a more moderate temperature (75 degrees C) through use of a 0.2 M acetate buffer. Based on the evaluation results, we propose two innovative processes for treating RDX-containing and perchlorate-containing wastewaters: a temperature and pressure-controlled batch iron reactor and subsequent oxidation by existing industrial wastewater treatment plant; and reduction by consecutive iron columns with heating and acid addition capabilities and subsequent oxidation.     

H2O2、Fenton试剂与活性炭联用对CODCr去除效果的对比试验研究

为了开发高效低成本、达到回用水质标准的污水处理工艺,本试验采用H2O2、Fenton试剂与活性炭联用对CODCr进行去除的对比试验研究。结果表明：在室温下200 mL水样,当pH为3,震荡强度为150 rpm时,Fenton试剂-活性炭联用与H2O2-活性炭相比,活性炭用量少200 mg,时间缩短10 h,CODCr去除率高17.6%。试验揭示了Fenton试剂-活性炭联用的反应机理：Fe2＋与活性炭共同催化分解H2O2生成大量.OH,能快速氧化降解有机物,使CODCr浓度迅速降低。从工程应用角度和技术经济方面考虑,Fenton试剂-活性炭联用的pH值在5～7适宜;且处理成本更低。Fenton试剂-活性炭联用是处理二级出水CODCr高效、低耗的方法,值得进一步研究和推广应用。     

The effects of dissolved organic matter on the decomposition of di-n-butyl phthalate by ozone/hydrogen peroxide process.

The effects of the dissolved organic matter (DOM) on the ozone decay and the di-n-butyl phthalate (DBP) decomposition during ozone/hydrogen peroxide (O3/H2O2) process were investigated (DBP-d4 was used instead of DBP). Four surface waters, two secondary municipal sewage effluents (SMSEfs) and Suwannee river natural organic matter were used as DOM. The ozone decompositions in the DOM solutions were separated by instantaneous ozone consumption and slower ozone decay. The effect of H2O2 addition on the ozone decay was clearly observed at slower ozone decay. Ozone decomposition rate at slower ozone decay increased linearly with H2O2 dose. DBP-d4 was exponentially decreased with ozone consumption. Ozone consumption required to decompose 90% of DBP-d4 ((deltaO3)90%) in SMSEFs was higher than those in surface waters. The (deltaO3)90% per DOC of DOM values were from 22 to 23 micromole/mgC for SMSEFs and from 10 to 17 micromole/mgC for surface waters. The (deltaO3)90% values were correlated to specific ultraviolet absorbance at 254 nm (SUVA254) for surface waters.     

Multiple responses analysis and modeling of Fenton process for treatment of high strength landfill leachate

Landfill leachate is one of the most recalcitrant wastes for biotreatment and can be considered a potential source of contamination to surface and groundwater ecosystems. In the present study, Fenton oxidation was employed for degradation of stabilized landfill leachate. Response surface methodology was applied to analyze, model and optimize the process parameters, i.e. pH and reaction time as well as the initial concentrations of hydrogen peroxide and ferrous ion. Analysis of variance showed that good coefficients of determination were obtained (R2 > 0.99), thus ensuring satisfactory agreement of the second-order regression model with the experimental data. The results indicated that, pH and its quadratic effects were the main factors influencing Fenton oxidation. Furthermore, antagonistic effects between pH and other variables were observed. The optimum H2O2 concentration, Fe(II) concentration, pH and reaction time were 0.033 mol/L, 0.011 mol/L, 3 and 145 min, respectively, with 58.3% COD, 79.0% color and 82.1% iron removals.     

Reductive dehalogenation of iopromide by zero-valent iron.

Iodinated X-ray contrast media (ICM), as derivatives of 2, 4, 6-triiodo benzoic acid, are applied in high doses to humans and are excreted unchanged via urine within 24 h. Common as well as advanced wastewater treatment is not able to remove the iodinated compounds leading to an environmental pollution. A specific treatment of contaminated urine or hospital wastewater could minimise the emission. For that reason the deiodination of iopromide, the most commonly used ICM, was investigated using zero-valent iron. Initial experiments carried out in stirred batch reactors with an initial pH of 2 using iron powder and iopromide dissolved in ultra pure water showed that iopromide can be deiodinated by zero-valent iron. Even in contaminated urine collected in a hospital a deiodination of ICM was possible. Further experiments at different constant pH values, temperatures and stirring speeds were performed. The kinetic studies at constant pH showed that the deiodination can be described by pseudo-first order for equal iopromide and iron concentrations. In general, the reaction depends strongly on the pH, the temperature and the stirring speed. The observed rate constant K(obs) has an optimum at pH 3 and rises with increasing temperature and stirring speed.     

UV/H2O2和UV/TiO2/H2O2去除水中微量硝基苯的比较研究

研究比较了UV/H2O2和UV/TiO2/H2O2对水中微量硝基苯的降解效果,并考察了水中常见HCO-3和腐殖酸对硝基苯降解的影响.结果表明,薄膜状TiO2的存在对UV/H2O2降解硝基苯有显著的促进作用,在最佳H2O2投加量2.1 mg/L时,UV/TiO2/H2O2的反应速率常数比UV/H2O2高32.8%;2 min内UV/TiO2/H2O2对硝基苯的去除率达到80%以上.HCO-3和腐殖酸对硝基苯降解有很强的抑制作用,HCO-3和腐殖酸浓度分别为2 mmol/L和3.2 mg/L时,UV/TiO2/H2O2对硝基苯的反应速率常数分别下降84.6%和92.2%.