Measurement of hydrogen peroxide and organic hydroperoxide concentrations during autumn in Beijing, China

Gaseous peroxides play important roles in atmospheric chemistry. To understand the pathways of the formation and removal of peroxides, atmospheric peroxide concentrations and their controlling factors were measured from 7:00 to 20:00 in September, October, and November 2013 at a heavily trafficked residential site in Beijing, China, with average concentrations of hydrogen peroxide (H₂O₂) and methyl hydroperoxide (MHP) at 0.55 ppb and 0.063 ppb, respectively. H₂O₂ concentrations were higher in the afternoon and lower in the morning and evening, while MHP concentrations did not exhibit a regular diurnal pattern. Both H₂O₂ and MHP concentrations increased at dusk in most cases. Both peroxides displayed monthly variations with higher concentrations in September. These results suggested that photochemical activity was the main controlling factor on variations of H₂O₂ concentrations during the measurement period. Increasing concentrations of volatile organic compounds emitted by motor vehicles were important contributors to H₂O₂ and MHP enrichment. High levels of H₂O₂ and MHP concentrations which occurred during the measurement period probably resulted from the transport of a polluted air mass with high water vapor content passing over the Bohai Bay, China.     

O3/H2O2法灭活水中剑水蚤类浮游动物

为解决水源水中孳生的水蚤类浮游动物难以被常规的水处理工艺有效地去除,困扰水厂正常生产运行的问题,进行了O₃氧化、H₂O₂氧化和O₃/H₂O₂高级氧化对水体中剑水蚤类浮游动物灭活效果的试验研究.发现3种方法中,O₃/H₂O₂联合时除蚤效果最佳,在蒸馏水中投量为O31.0mg/L、H₂O₂4mg/L时,接触30min达到100%的灭蚤率;单独O₃氧化效果也较好,投加1.0mg/L的灭蚤率为80%;H₂O₂氧化效果不理想,投加4mg/L几乎无灭蚤效果.进而考察确定了O₃/H₂O₂灭活剑水蚤的最佳工艺条件为:先加O₃后加H₂O₂,投加间隔时间30～60s为宜;并探讨了H₂O₂投量、水体pH值以及有机物含量对O₃/H₂O₂系统灭活剑水蚤效果的影响.试验中发现H₂O₂投量在4～10mg/L之间效果无较大变化,有机物含量对灭蚤影响较大,pH值的影响则较小.最后对O₃/H₂O₂预氧化与水处理混凝沉淀工艺的协同除蚤效能进行了考察.结果表明,O₃/H₂O₂预氧化与水处理混凝沉淀工艺的协同作用将会进一步提高除蚤的效果.     

Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

Aqueous solutions of phenol were oxidized by hydrogen peroxide assisted by microwave (MW) irradiation. A simple kinetic model for the overall degradation of phenol in the presence of excess H₂O₂ is proposed in which the degradation rate of phenol is expressed as a linear function of the concentrations of phenol and H₂O₂. A detailed parametric study showed that the degradation rate of phenol increased with increasing [H₂O₂] until saturation was observed. Phenol degradation followed apparent zero-order kinetics under MW radiation or H₂O₂ oxidation. However, after 90 min of irradiation, the observed kinetics shifted to pseudo first order. The overall reaction rates were significantly enhanced in the combined MW/H₂O₂ system, mainly because microwave could accelerate H₂O₂ to generate hydroxyl radical (·OH) and other reactive oxygen intermediates. The observed synergetic effects of the MW/H₂O₂ process resulted in an increased in the net reaction rate by a factor of 5.75. When hydrogen peroxide is present in a large stoichiometric excess, the time required to achieve complete mineralization is reduced significantly.     

Atmospheric H2O2 field measurements in a tropical environment: Bahia,Brazil

Concentrations of H₂O₂ in atmospheric gas and liquid phases were determined for the first time in the tropical Southern Hemisphere. Measurements were carried out in the Salvador area, Bahia, 13°S, 38°W) both at the seaside and 500 m away from it as well as at 270 km inland, in a rural area, during March–April 1988. Gaseous H₂O₂ was collected by cryogenic and rain by wet only sampling. Analyses were performed with the peroxyoxalate chemiluminescence method, employing a compact field apparatus. The measured gas phase concentrations ranged from 0.2 to 3.9 ppbv compared to 0.01-0.6 ppbv obtained from measurements with similar methodology in Dortmund (51°30'N, 7°30'E), F.R.G, during summer. The corresponding concentration ranges in rainwater are 0.9-6.8 ppmw (Bahia) and 0.1–2.2 ppmw (Dortmund, summertime). Gas/liquid H₂O₂ equilibrium during rain events is only attained at precipitation rates below 1 mm h⁻¹.     

A clean production process of sodium chlorite from sodium chlorate

This paper presents a novel cleaner production process for producing sodium chlorite by reducing sodium chlorate with hydrogen peroxide. In the new process, chlorine dioxide is generated by reducing chlorate ions with hydrogen peroxide in the presence of sulfuric acid: it then reacts with aqueous sodium hydroxide solution and hydrogen peroxide to produce sodium chlorite. The reaction conditions that were experimentally investigated included: reaction temperatures, concentrations of sodium chlorate solution, molar ratio of NaClO₃:H₂SO₄:H₂O₂, and acidity. Waste acid in the chlorine dioxide generator is dramatically reduced with recycling in the new process. The by-produced sodium sulfate in sulfuric acid is minimized and reclaimed.     

Magnetically recoverable Fe3O4@polydopamine nanocomposite as an excellent co-catalyst for Fe3+ reduction in advanced oxidation processes

Advanced oxidation processes are widely applied to removal of persistent toxic substances from wastewater by hydroxyl radicals(·OH),which is generated from hydrogen peroxide(H_2O_2) decomposition.However,their practical applications have been hampered by many strict conditions,such as iron sludge,rigid pH condition,large doses of hydrogen peroxide and Fe~(2+),etc.Herein,a magnetically recyclable Fe_3O_4@polydopamine(Fe_3O_4@PDA) coreshell nanocomposite was fabricated.As an excellent reducing agent,it can convert Fe~(3+)to Fe~(2+).Combined with the coordination of polydopamine and ferric ions,the production of iron sludge is inhibited.The minimum concentration of hydrogen peroxide(0.2 mmol/L and Fe~(2+)(0.18 mmol/L)) is 150-fold and 100-fold lower than that of previous reports,respectively.It also exhibits excellent degradation performance over a wide pH range from 3.0 to 9.0.Even after the tenth recycling,it still achieves over 99% degradation efficiency with the total organic carbon degradation rate of 80%,which is environmentally benign and has a large economic advantage.This discovery paves a way for extensive practical application of advanced oxidation processes,especially in environmental remediation.     

气相过氧化氢的生成及大气中浓度的测定

研究了ＨＣ－ＮＯ２－空气体系中Ｈ２Ｏ２和有机氢过氧化物的生成。模拟实验结果表明：Ｈ２Ｏ２生成浓度的最大值与碳氢化合物的初始浓度成正比;生成规律与Ｏ３生成规律类似,比值［Ｏ３］ｍａｘ／［Ｈ２Ｏ２］ｍａｘ随［ＨＣ］０增大而减小。在乙烯、戊烷体系中,Ｈ２Ｏ２在总过氧氢化物的比例为０．６左右;而丙烯体系中,随光照时间的延长,有较多的有机氢过氧化物产生。大气监测结果显示：Ｈ２Ｏ２的生成受污染物排放、日照及温度的影响,早晚浓度低,午后形成峰值,日变化规律与Ｏ３浓度变化相似,监测到的最大浓度值在春季为１．３×１０－９,在秋节为０．６４×１０－９。     

Sulfur dioxide in coastal new England fog

During six fog events in the year 1990, we investigated the concentration and oxidation capacity of SO₂ at a sampling site on the coast of New England. The SO₂ mixing ratio was usually in the range of a few parts per billion, and its variability during a single event was governed mostly by changes in air masses of different history and overall chemical composition, rather than chemical oxidation in cloud. Although the H₂O₂ mixing ratio was low during the foggy periods, it dominated the oxidation of SO₂. Ozone and manganese- and iron-catalysed reactions play minor roles. The overall oxidation capacity for SO₂ was low in most cases (<2% h⁻¹), probably because the oxidation of SO₂ by H₂O₂ was completed before the fog droplets were collectable. In one case with low SO₂ mixing ratios (<1 ppb), the oxidation intensity of SO₂ was intense (40% h⁻¹.     

纳米Fe3O4/CeO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/Ce O2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,在Fe3O4/Ce O2-H2O2非均相类Fenton体系中对目标污染物的降解进行研究,考察催化剂的催化效果和温度、p H、H2O2投加量等因素对催化剂催化效果的影响.结果表明,以纳米Fe3O4/Ce O2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/Ce O2的催化效果不断提高;在偏酸性环境中,p H越低催化效果越好,p H=2时反应去除效率可达96.67%;随着H2O2投加量的增加,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为15 mg·L-1时去除效果最好可达99.47%;随着催化剂投加量的增加,同样出现了处理效果先升高后降低的现象,投加量为0.5 g·L-1时催化效果最好可达99.64%.在以纳米Fe3O4/Ce O2为催化剂的非均相类Fenton体系中,3,4-二氯三氟甲苯的降解符合一级反应动力学,反应所需活化能较低只需30.26 k J·mol-1.     

Influence of drying and calcination temperatures for Ce-Cu-Al trimetallic composite catalyst on simultaneous removal H2S and PH3: Experimental and DFT studies

This work explored the influences of the drying and calcination temperatures on a Ce-Cu-Al trimetallic composite catalyst for the simultaneous removal of H₂S and PH₃. The effects of both temperatures on the structural features and activity were examined. The density functional theory method was used to calculate adsorption energies and further analyze their adsorption behavior on different slabs. Experiments revealed suitable drying and calcination temperatures to be 60 and 500°C, respectively. The capacity reached 323.8 and 288.1 mg/g. Adjusting drying temperature to 60°C is more inclined to form larger and structured grains of CuO. Rising calcinating temperature to 500°C could increase the grain size and redox capacity of CuO to promote performance. Higher temperatures would destroy the surface structure and lead to a crystal phase transformation, which was that the CuO and Al₂O₃ were gradually recombined into CuAl₂O₄ with a spinel structure. The exposed crystal planes of surficial CuO and CuAl₂O₄ were determined according to characterization results. Calculation results showed that, compared with CuO (111), H₂S and PH₃ have weaker adsorption strength on CuAl₂O₄ (100) which is not conducive to their adsorption and removal.     

UV和H2 O2联合消毒灭活饮用水中大肠杆菌研究

以大肠杆菌为研究对象,对单独紫外线(UV)、H2O2及两者不同组合方式的灭活效果进行了分析.结果表明,单独H2O2对大肠杆菌基本无灭活效果,加入浓度为20 mg·L-1的H2O2接触时间为30 min时,灭活率仅为0.02个对数级;单独UV工艺可在一定程度上灭活大肠杆菌,紫外线剂量为10 mJ·cm-2时,灭活率可达到4.51个对数级.紫外线和H2O2联合消毒在一定程度上提高了消毒效果,且不同的组合方式对灭活效果有很大的影响.先UV后H2O2消毒效果优于先H2O2后UV,当紫外线剂量为5 mJ·cm-2时,加入H2O2分别反应2.5、5、10、20 min后,两者的灭活率分别较单独UV消毒增加0.09、0.35、0.38、0.68和0.01、0.07、0.14、0.53个对数级.而UV与H2O2同时消毒效果优于UV与H2O2顺序消毒,当紫外线剂量为5 mJ·cm-2时,加入H2O2反应20 min后,灭活率较UV-H2O2和H2O2-UV工艺分别增加了0.43和0.58个对数级.随着紫外线强度的增加,大肠杆菌的灭活效果不断提高.     

Photochemical degradation of nonylphenol in aqueous solution：The impact of pH and hydroxyl radical promoters

The degradation of nonylphenol (NP) in aqueous solution with UV, H₂O₂/UV, and Fenton/photo-Fenton processes was studied. The efficacy of direct and hydrogen peroxide photolysis proved to be dependent on the pH value. The addition of H₂O₂ to UV treatment improved NP degradation. The application of UV photolysis and the H₂O₂/UV system at pH 7 resulted in low pseudo first-order rate constants at 10^-4 sec^-1. In the experiments at elevated pH values the pseudo-first order rate constants increased to 10^-3 sec^-1. The efficacy of the Fenton process was lower in comparison with UV and hydrogen peroxide photolysis. The addition of UV irradiation to the H₂O₂/Fe²⁺ system substantially improved NP degradation efficacy. In terms of performance, the photo-Fenton process was similar to the H₂O₂/UV process. The most favourable process for complete nonylphenol degradation considering both operational cost and treatment efficacy was H₂O₂/UV at pH 11 and 250 mol/L H₂O₂.     

UV/H2O2降解水中硝基酚及影响因素

UV/H₂O₂氧化对硝基酚实验表明,H₂O₂光解产生·OH自由基是对硝基酚降解的直接原因,12min内25mg/L的对硝基酚去除率达到98%以上.溶液中TOC变化与对硝基酚的去除并不同步,说明对硝基酚的降解中生成了一系列的中间产物,然后再达到完全矿化的.体系中H₂O₂浓度变化显示产生的中间产物对H₂O₂光解没有明显影响.研究中还对对硝基酚起始质量浓度、H₂O₂浓度及pH影响进行了考察.研究认为UV/H₂O₂是对硝基酚脱毒的一种有效方法.      

预处理方法对玉米芯作为反硝化固体碳源的影响

分别用1.5%NaOH、1%H2SO4、1.5%H2O2和碱性双氧水(含有1.5%H2O2的NaOH溶液)并联合紫外照射对玉米芯进行预处理,将预处理后玉米芯作为反硝化固体碳源和微生物载体进行静态释碳和静态反硝化实验,考察预处理后玉米芯释碳、反硝化性能及微生物附着情况.结果表明,经过碱和碱性双氧水预处理后的玉米芯碳源可利用性和反硝化效率均有显著的改善,尤其是碱预处理方法,静态反硝化反应至41 d时,仍能保持90%以上的硝酸盐去除率.因此,碱预处理方法可以改善玉米芯释碳性能,有利于微生物的附着和碳源的利用.     

Degradation of 4-aminophenol by hydrogen peroxide oxidation using enzyme from Serratia marcescens as catalyst

This paper reports on the degradation of 4-aminophenol using hydrogen peroxide as oxidizer and the enzyme from Serratia marcescens AB 90027 as catalyst. The effecting factors during degradation and the degrading mechanism were studied. Also, the location of the enzyme in the cell, which could catalyze the degradation of 4-aminophenol, was analyzed. The results showed that to degrade 50 mL of 4-aminophenol whose concentration was 500 mg/L, the optimal conditions were: volume of H₂O₂ = 3 mL, temperature = 40–60°C and pH = 9–10. In the degradation process, 4-aminophenol was first converted to benzoquinone and NH₃, then organic acids including maleic acid, fumaleic acid, and oxalic acid were formed, and then finally CO₂ and H₂O were generated as final products. The enzyme that could catalyze the degradation of 4-aminophenol was mainly extracellular enzyme. Translated from Environmental Chemistry, 2006, 25(2): 141–144 [译自: 环境化学]     

活性炭催化过氧化氢去除荧光增白剂

研究了活性炭(activated carbon,AC)吸附、改性活性炭(activated carbon modified,ACM)吸附、过氧化氢(H2O2)氧化、AC催化H2O2等方法对水体中荧光增白剂VBL的处理效果,并通过自由基俘获剂叔丁醇、催化过程气体分析等探讨了AC催化H2O2分解VBL的机制.结果表明,经硝酸铁[Fe(NO3)3]改性过的ACM对VBL的吸附去除率高于未改性的AC.活性炭催化H2O2对VBL的去除效果明显,但未改性AC催化去除率高于ACM.60 min时,AC催化氧化去除率即可达到95%以上,而ACM仅为58%.叔丁醇的加入降低了AC和ACM催化氧化对VBL的去除率,表明AC催化H2O2氧化能促进H2O2形成羟基自由基(·OH)和原子氧参与反应.AC催化H2O2分解及释放气体分析表明,AC能催化H2O2形成氧气并放热,且ACM明显快于AC.结合催化H2O2去除VBL效率的结果分析,ACM催化反应时活性中间物(自由基和原子氧等)产生速率快于AC,活性中间物自身消耗形成氧气,而不是用于分解VBL.催化反应中活性中间产物的形成速率与反应物供给速率的不匹配可能是导致ACM催化效果弱于AC的重要原因.     

响应面法分析卫生填埋渗滤液的Fenton处理过程

利用响应面法研究了Fenton试剂处理卫生填埋渗滤液过程中诸因素对COD去除率的影响,如渗滤液中高分子量有机物(HMWOM)与低分子量有机物(LMWOM)的TOC比例、LMWOM浓度以及双氧水和亚铁离子的摩尔比(H₂O₂/Fe²⁺).其中HMWOM/LMWOM值、LMWOM浓度和H₂O₂/Fe²⁺摩尔比值的高、低水平分别为14～38,975～3000 mg/L,1.75～4.00.由实验数据得到了1个2次响应曲面模型,该模型显示COD的去除率随着HMWOM/LMWOM值的增加而增加,但随着LMWOM浓度的增加而降低.Fenton试剂处理卫生填埋渗滤液存在着一个最佳的H₂O₂/Fe²⁺摩尔比值,COD去除率在该点能达到最高.     

满江红花青素在镉胁迫下的抗氧化作用

为了研究镉胁迫诱导满江红体内花青素合成的生理功能,采用镉诱导和体外实验的方法评价了满江红体内花青素的抗氧化作用.测试指标包括还原力、清除超氧阴离子(O-2)、过氧化氢(H2O2)、羟自由基(·OH)的能力.结果表明,花青素的还原力和对氧自由基的清除作用随花青素提取物浓度的增加而增加.因此,镉胁迫下合成的花青素是一种清除活性氧自由基的良好抗氧化剂.镉胁迫对满江红活性氧代谢影响的试验结果表明,在0.5mg·L-1Cd胁迫下,满江红体内O-2和H2O2大量积累,造成活性氧胁迫,说明花青素只能在一定程度上保护满江红免受过氧化伤害.本实验初步证实,花青素含量的增加是满江红抗性机理之一,可缓解镉的毒害.     

Degradation kinetics and mechanism of trace nitrobenzene by granular activated carbon enhanced microwave/hydrogen peroxide system

The kinetics of the degradation of trace nitrobenzene (NB) by a granular activated carbon (GAC) enhanced microwave (MW)/hydrogen peroxide (H₂O₂) system was studied. Effects of pH, NB initial concentration and tert-butyl alcohol on the removal efficiency were examined. It was found that the reaction rate fits well to first-order reaction kinetics in the MW/GAC/H₂O₂ process. Moreover, GAC greatly enhanced the degradation rate of NB in water. Under a given condition (MW power 300 W, H₂O₂ dosage 10 mg/L, pH 6.85 and temperature (60±5)℃), the degradation rate of NB was 0.05214 min^-1 when 4 g/L GAC was added. In general, alkaline pH was better for NB degradation; however, the optimum pH was 8.0 in the tested pH value range of 4.0-12.0. At H₂O₂ dosage of 10 mg/L and GAC dosage of 4 g/L, the removal of NB was decreased with increasing initial concentrations of NB, indicating that a low initial concentration was beneficial for the degradation of NB. These results indicated that the MW/GAC/H₂O₂ process was effective for trace NB degradation in water. Gas chromatography-mass spectrometry analysis indicated that a hydroxyl radical addition reaction and dehydrogenation reaction enhanced NB degradation.     

Amperometric hydrogen peroxide biosensor based on immobilization of DNA-Cu(II) in DNA/chitosan polyion complex membrane

DNA/chitosan polyion complex membrane was used as a support for immobilization of electrocatalytic species-copper ions, which specifically bound to dsDNA and catalyzed the hydrogen peroxide reduction. The polyion complex membrane consisted with DNA-Cu(II) complex and chitosan was prepared on a glassy carbon electrode (GCE). Electrochemical measurements of the DNA-Cu(II)/chitosan membrane-modified GCE revealed that the copper ion embedded in the DNA/chitosan layer exhibited good electrochemical behaviors. The DNA-Cu(II)/chitosan/GC electrode showed an excellent electrocatalytic activity for the H₂O₂ reduction. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid (response time, about 6 s) response to H₂O₂. The steady-state cathodic current responses of the sensor obtained at ?0.2 V versus Ag/AgCl in air-saturated 100 mmol/L phosphate buffer (pH 5.0) increased linearly up to 10 mmol/L with the detection limit of 3 μmol/L. Effects of applied potential and buffer pH upon the response currents of the sensor were investigated for an optimum analytical performance. Ascorbic acid and glucose almost have no interference to measurement of H₂O₂. In addition, the sensor exhibited good reproducibility.