H2O2对COD测定的干扰及消除研究

COD是表征水体有机物污染状况的重要参数,而实际水样成分复杂往往对COD测定产生干扰,其中H2O2尤为明显。通过实验分析H2O2对COD干扰状况并提出消除干扰的措施。研究表明,H2O2作为还原剂使COD测定值高于实际值;H2O2浓度与COD之间呈现线性关系,R2为0.999 7,线性方程为y=0.466 4x+0.249 5,1mg的H2O2能引起0.466 4mg的COD变化。在低、高2种浓度的COD标准溶液体系中,线性方程计算的ΔCOD1(即H2O2引起的COD变化值)与ΔCOD2(COD测定值与原水COD的差值)差值为原水COD的1.28%～11.80%、0.16%～5.95%;在低、高2种浓度的工业废水体系中,线性方程计算的ΔCOD1与ΔCOD2差值分别为0.1～5.9、32.7～75.6mg/L,为原水COD的1.28%～14.00%、2.35%～5.44%;在生活污水体系中,线性方程计算的ΔCOD1与ΔCOD2差值为6.8～30.3mg/L,为原水COD的2.98%～13.40%。通过线性方程,较好地反映出实际的COD差异,可以消除H2O2对COD测定的干扰。该方法简单准确,能够较好地反映实际水样的COD情况。     

Effect of ZnFe2O4 doping on the photocatalytic activity of TiO2

The photocatalytic oxidation of the organic pollutants with the TiO2 as photocatalyst has been widely studied in the world, and many achievements have been got. The degradation of pollutants is highly related with the photocatalytic activity of TiO2. It is demonstrated that doping ions or oxides to TiO2 is one way to enhance the photocatalytic activity of TiO2. In this paper, the ZnFe2O4-doped TiO2 nanoparticles were prepared from butyl titanate by a sol-gel method and characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that when TiO2 was doped with ZnFe2O4, its particle size will decrease and its crystal structure will partly transform from anatase to rutile. The photocatalytic activity of the elaborated powders was studied following the degradation of Rhodamine B. The results showed that doping ZnFe2O4 to TiO2 will enhance the photocatalytic activity of TiO2 and that ZnFe2O4-doped TiO2 in the coexistence of anatase and rutile has higher efficiency for the degradation of Rhodamine B than that in the anatase phase alone. Also the different role of O2 in the direct photolysis and photocatalysis of Rhodamine B was discussed.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Rate Constants for the Reaction of OH with Halocarbons in the Presence of O2 + N2

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.     

浮游球衣菌对Pb2+、Cu2+、Zn2+、Cd2+的吸附性能研究

研究了浮游球衣菌（Sphaerotilus natans）在不同吸附条件下对溶液中Pb^2＋、Cu^2＋、Zn^2＋、Cd^2＋的吸附规律。结果表明,Sphaerotilus natans对这4种重金属离子均有一定的吸附作用,并在20min内达到吸附平衡,pH对吸附过程影响较大,pH为5.5时Sphaerotilus natans对这4种金属离子的吸附效果最好,Sphaerotilus natans对它们的吸附选择性为Pb^2＋〉Cu^2＋〉Zn^2＋〉Cd^2＋,Pb^2＋、Cu^2＋能部分置换出已被菌体吸附的Zn^2＋、Cd^2＋。HCI和EDTA溶液可有效地将金属离子从菌体上解吸下来,解吸后的菌体可重复使用。     

载银TiO2催化剂的制备与性能研究

本文是采用负载金属银对TiO2改性后得到了载银TiO2,利用不同反应时间的胭脂红降解率反映光催化氧化反应的速率,结果表明,载银TiO2比TiO2的催化反应速率提高了3倍.通过实验确定最佳含银量和催化剂最佳投加量,并讨论了载银TiO2的催化机理,提出了制取载银TiO2催化剂的方法.     

低浓度Pb2+、Cd2+对鲫鱼肝脏组织中 HSP70诱导的影响

以鲫鱼(Carassius auratus)作为实验对象,经过40 d Pb2+、Cd2+不同浓度的暴露后,运用SDS-PAGE和Western Blotting方法检测鱼肝脏组织内应激蛋白HSP70的诱导表达情况.结果表明,在实验浓度下,与对照组相比,Pb2+、Cd2+对鱼肝脏内HSP70有显著的诱导(P＜0.05),但在Cd2+浓度为0.2 mg/L有停止表达HSP70的现象,可能是由于浓度过高造成了组织病理损伤而破坏了诱导表达机制.实验还发现,在实验浓度低于国家渔业用水标准时,HSP70仍然表现为明显诱导(P＜0.05),充分说明运用分子生物学指标要比传统的环境检测指标敏感,具有对污染物早期预警的作用.     

The effect of the limited availability of H2O2 in the competitive deposition of sulfur and oxidized nitrogen

To understand the influence of the reduction of SO2 emissions from a single source in the S and N deposition around its local environment, the application of the Sulphur Transport Eulerian Model 2 (STEM-II) was introduced in this paper. Observed local deposition patterns were analysed and explained in terms of the main processes involved in the pollutants deposition. It was necessary to take into account the limited availability of H2O2 because of its influence on both S(IV) and oxidized nitrogen deposition. In order to estimate the quantitative relationship between the SO2 emissions reduction and the observed S and N deposition patterns, these processes were simulated for different meteorological conditions. Simulation results were in agreement with both observed deposition patterns and limited availability of H2O2, specially if significant changes in the S deposition patterns were considered. Both observed and estimated S deposition patterns changed their top value location from the Southwest (1990) to the Northwest (1997) of the domain, because of the reduction of dry deposition. The global reduction of total S depositions, estimated and observed, were in good agreement too. Model simulations could explain the higher S dry deposition reduction, considering the emissions reduction strategy applied.     

N2O profiles in the enhanced CANON process via long-term N2H4 addition: minimized N2O production and the influence of exogenous N2H4 on N2O sources

Environmental Science and Pollution Research - Production of the greenhouse gas nitrous oxide (N2O) from the completely autotrophic nitrogen removal over nitrite (CANON) process is of growing...     

在Ru/Al2O3催化剂上用H2对SO2选择性催化还原的研究

本文对用H2来使SO2选择性催化还原为单质硫在Ru/Al2O3催化剂上的行为进行研究.当物料比经过优化确定为SO2/H2=12.8时,在500℃下,SO2的转化率为90%以上,单质硫的产率为70%左右.比较于其他的催化还原SO2的催化剂,本催化剂采用金属而不是金属硫化物,这样既省去了催化剂预硫化的过程,同时也使在有氧条件下的选择性催化还原成为可能.实验考察了O2及水蒸气存在对过程的影响.在实验过程中发现,H2S作为中间产物生成,可推论该过程在催化剂上分两步进行SO2首先在催化剂金属上被H2深度还原为H2S,然后在Al2O3载体的酸性中心上SO2与H2S发生Claus反应产生单质硫.     

Kinetics of the Homogeneous Gas Phase Hydrolysis of CCl3COCl,CCl2HCOCl,CH2CICOCl and COCl2

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.     

Role of cupric ions in the H2O2/UV oxidation of humic acids

The purpose of this study is to reveal the role of cupric ions as a natural water contaminant in the H2O2/UV oxidation of humic acids. Humic acids are naturally occurring organic matter and exhibit a strong tendency of complexation with some transition metal ions. Chlorination of humic acids causes potential health hazards due to formation of trihalomethane (THM). The removal of THM precursors has become an issue of public concern. The H2O2/UV process is capable of mineralizing humic acids due to formation of a strong oxidant, hydroxyl radicals, in reaction solution. Experiments were conducted in a re-circulated photoreactor. Different cupric concentrations (0-3.8 mg/l) and different pH values (4-9) were controlled to determine their effects on the degradation of humic acids, UV light absorbance at 254 nm, and H2O2. The presence of cupric ions inhibits humic mineralization and decreases the rate of destruction of humic acids which absorb UV light at 254 nm. On the other hand, the higher the cupric concentration, the lower the H2O2 decomposition rate. In the studied pH range, the minimum of total organic carbon (TOC) removal occurs at pH = 6 in the presence of 2.6 mg/l of cupric ions; both acidification (pH = 4) and alkaline condition (pH = 9) lead to a better removal of TOC. It is inferred from this study that the cupric-complexed form of humic acids is more refractory than the non-complexed one.     

The effect of O2 and NO2 on the ring retaining products of the reaction of toluene with hydroxyl radicals

The reaction of toluene with hydroxyl radicals produces ring retaining products either from H-atom abstraction from the methyl group: benzaldehyde and benzylalcohol or from the addition of the hydroxyl radical to the aromatic ring: o-, m+p-cresol. The yields obtained in experiments carried out in nitrogen and in air matrix were statistically not significantly different. The addition of NO₂ to the reactants had no effect on the formed o-cresol, indicating that reaction of the hydroxy-methylcyclohexadienyl radical with NO₂ is not contributing significantly to the formation of o-cresol. This is in agreement with recent studies postulating the more stable toluene oxide as the intermediate resulting from the reaction of hydroxy-methylcyclohexadienyl with oxygen rather than the peroxy radical. m-nitrotoluene was the major nitrotoluene formed in the presence of NO₂, increasing linearly with increasing the initial concentration of NO₂ with zero intercept. The observed 2-methyl 1,4 benzoquinone and traces of phenol and benzene were determined to be secondary products.     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

超声-过氧化氢-氧化铜组合技术催化氧化水中苯酚

研究了超声-H2O2-CuO组合技术对苯酚的降解效果。考察了苯酚初始浓度、溶液温度及鼓入空气对苯酚去除率的影响。实验结果表明，与未鼓入空气时相比，连续鼓气时苯酚的降解效果较好；初始浓度低，苯酚去除率高；溶液温度从20％上升到55％时，苯酚去除率随温度升高而增大，温度对该过程的影响主要表现为对催化剂的影响而不是对超声作用的影响。高效液相色谱分析表明，苯酚降解的中间产物主要为对苯二酚、邻苯二酚及其他有机小分子物质，最终产物为草酸、二氧化碳和水。     

超声-过氧化氢-氧化铜组合技术催化氧化水中苯酚

研究了超声-H2O2-CuO组合技术对苯酚的降解效果。考察了苯酚初始浓度、溶液温度及鼓入空气对苯酚去除率的影响。实验结果表明,与未鼓入空气时相比,连续鼓气时苯酚的降解效果较好;初始浓度低,苯酚去除率高;溶液温度从20℃上升到55℃时,苯酚去除率随温度升高而增大,温度对该过程的影响主要表现为对催化剂的影响而不是对超声作用的影响。高效液相色谱分析表明,苯酚降解的中间产物主要为对苯二酚、邻苯二酚及其他有机小分子物质,最终产物为草酸、二氧化碳和水。     

Decolorization of synthetic dyes by the Fenton reagent and the Cu/pyridine/H2O2 system

Representative azo, triphenylmethane, heterocyclic and polymeric synthetic dyes have been decolorized by two biological non-ezymatic systems, copper/pyridine/H2O2 and the Fenton reagent. With the former system, intensive decolorization measured after 1 h was obtained with phenol red (89%), tropaeolin 00 (58%), Evans blue (95%), eosin yellowish (84%), and Poly B-411 (92%). The rate of decolorization was not affected by pH in the range of 3-9 and increased with increasing temperature. The use of the radical scavengers thiourea and superoxide dismutase showed that hydroxyl radicals rather than superoxide anions are involved in the reaction. Omission of pyridine led to a substantial decrease in the extent of decolorization (20-50% decolorization). The use of organic peroxide instead of H2O2 resulted in slightly slower decolorization, similar values of decolorization being obtained only after a 2-h incubation. Decolorization of the dyes by the Fenton reagent was also very effective but slower than that obtained with the first system. Except for phenol red and eosin yellowish, (decolorization 8% and 52%, respectively) the dyes were decolorized up to 99% after 1-day incubation.     

微量NO2对氨氧化过程中产物的影响

在无O2条件下,氨氧化速率越高,氨氧化过程中产生的NO-2-N、NO-3-N浓度和氮损失越大;NO2为25×10-6 mg/L时氮损失率最大,约为20.93%.在相同浓度的O2条件下,氮损失与氨氧化速率相关,氨氧化速率增加时,氮损失增大.在O2的体积分数为2%时,50×10-6 mg/L NO2时的氮损失率最大,为27.57%;在O2的体积分数为21%时,100×10-6 mg/L NO2时的氮损失率最大,为34.19%.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.