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1.
Aqueous solutions of Fenton's reagent (Fe2+ + H2O2) have been used to effect the total decomposition of the chlorophenols: 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 3,4-dichlorophenol and 2,4,5-trichlorophenol. The mineralization of these chlorinated aromatic substrates to CO2 and free Cl has been studied as a function of [Fe2+] and [HClO4]. Increasing the concentration of Fe2+ enhances the decomposition process, while an increase in the concentration of HClO4, inhibits the reaction. The presence of Fe3+ alone (without any Fe2+) with H2O2 has no effect on the degradation of the chlorophenols. In all cases, the stoichiometric quantity of free Cl was obtained at the completion of the decomposition reaction; but the rates of disappaearance of the chlorophenol and of the formation of the Cl are not similar. This suggests that some chlorinated aliphatic species may be formed as possible intemediates.  相似文献   

2.
Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO4 ), which was generated by the activation of persulfate (S2O8 2?) with ferrous ion (Fe2+). S2O8 2? was activated by Fe2+ to produce SO4 , and iron powder (Fe0) was used as a slow-releasing source of dissolved Fe2+. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S2O8 2? or Fe2+ concentrations and then decreased with excess Fe2+ concentration. The adding mode of Fe2+ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe2+, while complete degradation was observed with continuous diffusion of Fe2+, and the latter achieved higher TOC removal rate. When Fe0 was employed as a slow-releasing source of dissolved Fe2+, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe0–S2O8 2? system, Fe0 as the activator of S2O8 2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe0–S2O8 2? system has perspective for future works.  相似文献   

3.
考察了pH值对"Fe0-厌氧微生物"体系降解2,4,6,-三氯酚(2,4,6-TCP)效果的影响,结果表明:pH值是影响"Fe0-厌氧微生物"体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH 7.0~9.0的中性偏碱范围较适于厌氧微生物生长。Fe0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面:Fe0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe0腐蚀产生的Fe2+和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe0腐蚀。  相似文献   

4.
Rates of CO2 production in the reaction CO + OH and CO + OH + halocarbon have been used to determine rate constants for some OH + halocarbon reactions at 29.5°C relative to that of k(CO + OH) = 2.69 × 10?13 cm3 molecule?1 sec?1. The following rate constants were obtained: k(OH + CH3Cl) = 3.1 ± 0.8, k(OH + CH2Cl2) = 2.7 ± 1.0, k(OH + C2H5Cl) = 44.0 ± 25, k(OH + CICH2CH2CI) = 6.5, (<29) and k(OH + CH3CCl3) = 2.1 (<5.7) cm3 molecule?1 sec?1 × 10?14. The k values, CH2Cl2 excepted, are in substantial agreement with determinations made in nonoxygen environments. The present results for CH2Cl2 are almost certainly in error due to difficulties with the competitive approach used.  相似文献   

5.
In this study, photocatalytic (photo-Fenton and H2O2/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H2O2). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H2O2]0 = 400 mg L?1. The photo-Fenton process mineralized 70% of the ETU with [H2O2]0 = 800 mg L?1 and [Fe2+] = 400 mg L?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H2O2 from 800 mg L?1 to 1200 mg L?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H2O2 and photo-Fenton processes were determined to be 6.2 × 10?4 mg L?1 min?1 and 7.7 × 10?4 mg L?1 min?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.  相似文献   

6.
In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R o = k o[S(IV)]], where k o is the first-order rate constant and R o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k obs = k o/(1 + B [Inh]), where k obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10?5 to 1.5?×?10?4 s?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?104) (ethanol) and (3.95?±?2.36)?×?104 (2-butanol) at 25 °C.  相似文献   

7.
In the last few years, several works dealing with Fenton oxidation of ionic liquids (ILs) have proved the capability of this technology for their degradation, achieving complete ILs removal and non-toxic effluents. Nevertheless, very little is known about the kinetics of this process, crucial for its potential application. In this work, the effect of several operating conditions, including reaction temperature (50–90 °C), catalyst load (10–50 mg L?1 Fe3+), initial IL concentration (100–2000 mg L?1), and hydrogen peroxide dose (10–200% of the stoichiometric amount for the complete IL mineralization) on 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) oxidation has been investigated. Under the optimum operating conditions (T = 90 °C; [Fe3+]0 = 50 mg L?1; [H2O2]0 = 100% of the stoichiometric amount), the complete removal of [C4mim]Cl (1000 mg L?1) was achieved at 1.5-min reaction time. From the experimental results, a potential kinetic model capable to describe the removal of imidazolium-based ILs by Fenton oxidation has been developed. By fitting the proposed model to the experimental data, the orders of the reaction with respect to IL initial concentration, Fe3+ amount and H2O2 dose were found to be close to 1, with an apparent activation energy of 43.3 kJ mol?1. The model resulted in a reasonable fit within the wide range of operating conditions tested in this work.  相似文献   

8.
原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制   总被引:1,自引:0,他引:1  
将不同摩尔比Fe3+与OH-([Fe3+]:[OH-]=1:0、1:1、1:2和1:3)反应获得原位水解生成的羟基氧化铁(in situ FeOxHy),研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示,In situ FeOxHy对磷的去除率随铁投量增大而升高,且均在中性pH范围内具有最佳除磷效果;在相同铁投量条件下,磷去除率随着[OH-]:[Fe3+]的升高而降低;当体系碱度较低时(pH<6),引入OH-可促进Fe3+水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷,且吸附过程符合准二级动力学模型;Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后,In situ FeOxHy表面Zeta电位明显降低,且[Fe3+]:[OH-]为1:0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示,对于碱度较低的体系,通过投加一定量OH-可促进Fe3+水解,进而使得其更易与水中H2PO4-与HPO42-结合,生成具有多核羟基的磷酸铁络合物,进而提高除磷效果。  相似文献   

9.
At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of kmax = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d− 1. The stable isotope-based biodegradation rate constant of 0.0027 d− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d− 1. With MM-kinetics a maximum degradation rate of kmax = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor εfield of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.  相似文献   

10.
The ability of free ferrous ion activated persulfate (S2O82−) to generate sulfate radicals (SO4) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO4 with excess Fe2+ and a quick conversion of Fe2+ to Fe3+. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe3+ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe3+ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe3+ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S2O82− and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe3+ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe3+ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.  相似文献   

11.
The aims of this study were (a) to evaluate the degradation of acetamiprid with the use of Fenton reaction, (b) to investigate the effect of different concentrations of H2O2 and Fe2+, initial pH and various iron salts, on the degradation of acetamiprid and (c) to apply response surface methodology for the evaluation of degradation kinetics.  相似文献   

12.
研究了超声波/零价铁(US/Fe^0)工艺对水中双酚A(BPA)的降解效果及影响因素。结果表明,US/Fe^0工艺可以有效降解水中的BPA,具有协同作用,且降解过程符合一级动力学规律;Fe^0具有促进和抑制的双重作用;超声功率越大,越有利于BPA的降解;初始浓度较低时,BPA的降解效果较好;弱酸性条件有利于BPA的降解;加入一定量的自由基捕获剂(正丁醇)可以抑制BPA的降解;联合作用2h后,TOC的去除率较低,说明其矿化程度不完全。  相似文献   

13.
重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石(HA)、纳米羟基磷灰石(nHA)、纳米零价铁(nFe0)和纳米TiO2nTiO2)对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量,有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性,增加了烟草叶中Cd的吸收量,有利于Pb、Cd的钝化和Cd的植物提取。nFe0nTiO2对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。  相似文献   

14.
Fan C  Tsui L  Liao MC 《Chemosphere》2011,82(2):229-236
The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H2O2] to [Fe2+] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe2+ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H2O2]/[Fe2+]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe2+ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L−1 of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.  相似文献   

15.
Electron microscopy-energy dispersive spectroscopy (EM/EDS) can be used to determine the elemental composition of individual particles. However, the accuracy with which atmospheric particle compositions can be quantitatively determined is not well understood. In this work we explore sources of sampling and analytical bias and methods of reducing bias. Sulfuric acid [H2SO4] and ammonium sulfate [(NH4)2SO4] particles were collected on beryllium, silicon, and carbon substrates with similar deposition densities. While [(NH4)2SO4] particles were observed on all substrates, [H2SO4] and ammonia-treated [H2SO4] particles could not be found on beryllium substrates. Interactions between the substrate and sulfuric acid particles are implicated. When measured with EM/EDS, [H2SO4] particles exposed to ammonia overnight were found having lower beam damage rates (0.000 ± 0.002 fraction s−1) than those without any treatment (0.023 ± 0.006 fraction s−1) For laboratory-generated [C10H6(SO3Na)2] particles, the composition determined using the experimental k-factors evaluated from independent particle standards of similar composition and size shows an error less than 20% for all constituents, while greater than 78% errors were found when k-factors were calculated from the theory. This study suggests (1) that sulfate beam damage can be reduced by exposure of atmospheric particle samples to ammonia before analysis, (2) that beryllium is not a suitable substrate for atmospheric particle analysis, and (3) calibration (k-factor determination) using particle standards of similar size and composition to particles present in the atmosphere shows promise as a way of improving the accuracy of quantitative EM analysis.  相似文献   

16.

Zero-valent iron (Fe0) has been widely used for Cr(VI) removal; however, the removal mechanisms of Cr(VI) from aqueous solution under complex hydrogeochemical conditions were poorly understood. In this research, the mixed materials containing cast iron and activated carbon were packed in columns for the treatment of aqueous Cr(VI)-Cr(III) in groundwater with high concentration of Ca2+, Mg2+, HCO3 , NO3 , and SO4 2−. We investigate the influences of those ions on Cr(VI) removal, especially emphasizing on the reaction mechanisms and associated precipitations which may lead to porosity loss by using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) techniques. The results show that the precipitations accumulated on the material surface were (Fe/Cr) (oxy)hydroxide, mixed Fe(III)-Cr(III) (oxy)hydroxides, Fe2O3, CaCO3, and MgCO3. During these reactions, the Cr(VI) was reduced to Cr(III) coupled with the oxidated Fe0 to Fe(II) through the galvanic corrosion formed by the Fe0-C and/or the direct electron transfer between Fe0 and Cr(VI). In addition, Cr(VI) could be reduced by aqueous Fe(II), which dominated the whole removal efficiency. The primary aqueous Cr(III) was completely removed together with Cr(III) reduced from Cr(VI) even when Cr(VI) was detected in the effluent, which meant that the aqueous Cr(III) could occupy the adsorption sites. In general, the combined system was useful for the Cr(VI)-Cr(III) treatment based on galvanic corrosion, and the hardness ions had a negative effect on Cr(VI) removal by forming the carbonates which might promote the passivation of materials and decrease the removal capacity of the system.

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17.
Brazil is the largest sugarcane producer in the world in which hexazinone (3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) are heavily used. Sugarcane harvesting is changing from the manual system with previous straw burning to the mechanized system without straw burning. The lack of burning results in soil organic carbon accumulation mainly in clayey soils, which should affect herbicides availability and fate. Therefore, we evaluated sorption of these herbicides in soil samples with and without straw burning. Both herbicides presented low apparent sorption coefficients (mean Kd,app= 0.6 and 2.4 L kg?1 for hexazinone and tebuthiuron, respectively), suggesting that they may leach to groundwater. Moreover, their sorption correlated primarily with soil organic carbon (SOC), but iron oxide contents extracted with ammonium oxalate (Fe2O3AOX) also affected it (Kd,app = ?0.228 + 0.0397 SOC + 0.117 Fe2O3AOX for hexazinone and Kd,app = ?1.407 + 0.201 SOC + 0.348 Fe2O3AOX for tebuthiuron). Soil organic carbon accumulation due to straw maintenance in the field positively affected sorption of both herbicides, but its effects were not enough to classify them as “non-leachers.”  相似文献   

18.

A two-component material (Fe3O4@CaSiO3) with an Fe3O4 magnetite core and layered porous CaSiO3 shell from calcium nitrate and sodium silicate was synthesized by precipitation. The structure, morphology, magnetic properties, and composition of the Fe3O4@CaSiO3 composite were characterized in detail, and its adsorption performance, adsorption kinetics, and recyclability for Cu2+, Ni2+, and Cr3+ adsorption were studied. The Fe3O4@CaSiO3 composite has a 2D core–layer architecture with a cotton-like morphology, specific surface area of 41.56 m2/g, pore size of 16 nm, and pore volume of 0.25 cm3/g. The measured magnetization saturation values of the magnetic composite were 57.1 emu/g. Data of the adsorption of Cu2+, Ni2+, and Cr3+ by Fe3O4@CaSiO3 fitted the Redlich–Peterson and pseudo-second-order models well, and all adsorption processes reached equilibrium within 150 min. The maximum adsorption capacities of Fe3O4@CaSiO3 toward Cu2+, Ni2+, and Cr3+ were 427.10, 391.59, and 371.39 mg/g at an initial concentration of 225 mg/L and a temperature of 293 K according to the fitted curve with the Redlich–Peterson model, respectively. All adsorption were spontaneous endothermic processes featuring an entropy increase, including physisorption, chemisorption, and ion exchange; among these process, chemisorption was the primary mechanism. Fe3O4@CaSiO3 exhibited excellent adsorption, regeneration, and magnetic separation performance, thereby demonstrating its potential applicability to removing heavy metal ions.

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19.
Y. Xu   《Chemosphere》2001,43(8):1281
The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe3+, H2O2 and TiO2 components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe2+–H2O2–UV  Fe2+–H2O2 > Fe3+–H2O2–UV > Fe3+–H2O2 > Fe3+–TiO2–UV > TiO2–UV > Fe3+–UV > TiO2–visible light (λ  450 nm) > H2O2–UV > Fe2+–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.  相似文献   

20.
The homogeneous gas phase hydrolysis kinetics of the above compounds has been investigated in the 470° to 620°K temperature range. The following biomolecular rate constants were obtained: k(CCl3COCl) = 2.54 × 106 exp (?18,350 ± 1750)/RT, k(CClH2COCl) = 1.14 × 108 exp (?22,630 ± 780)/RT, and fr(COCl2) = 9192 exp (?14,200 ± 2100)/RT liter mole?1 sec?1. Experimental difficulties prevented data being obtained for CHCl2COCl. The half lives of these species with respect to homogeneous gas phase hydrolysis in the atmosphere have been estimated and it is concluded that this is not an efficient conversion process. Heterogeneous hydrolysis by water droplets may be a more efficient atmospheric scavenging process for these compounds.  相似文献   

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