低分子有机酸对土壤中Cu化学形态的影响

向石英砂岩坡积物发育的红壤中添加系列浓度CuSO4模拟土壤Cu污染,然后加入不同浓度的低分子量有机酸培养,采用改进的BCR连续提取法评价低分子有机酸对重金属Cu形态的影响.结果表明,对不同程度的Cu污染(Cu 0～400mg·kg-1)土壤,随着有机酸添加浓度的升高,最具活性的弱酸溶解态Cu含量均有不同程度的提高,土壤重金属Cu得到活化;Cu活化效果随柠檬酸浓度升高而升高,随酒石酸和草酸浓度升高呈先上升后基本不变趋势;整体活化效果是柠檬酸>酒石酸≈草酸.可还原态Cu随着有机酸浓度的增加而减少,其中添加柠檬酸的处理减少最明显.当有机酸浓度为10 mmol·kg-1、20 mmol·kg-1时,酒石酸和草酸、柠檬酸活化Cu效果分别达到最优.     

基于均匀设计的类Fenton's体系去除污染土壤中蒽和芘的研究

分别以乳酸、L-酒石酸、柠檬酸为助剂,将其添加至类Fenton's体系中去除污染土壤中的蒽和芘等多环芳烃.结果发现,以柠檬酸为助剂时,多环芳烃的去除率为83.75%.同时,以均匀实验设计法考察了H2O2用量、Fe SO4用量、反应温度、反应时间、水土比、柠檬酸用量和多环芳烃染毒浓度对多环芳烃去除率的影响.实验数据和结果经DPS(Data Processing Station)软件处理后得到多环芳烃去除率与各反应因素之间的回归方程,经随机验证实验和计算结果对比表明,该回归方程的拟合误差低于5%,具有精确的预报性.     

Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl⁻ formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH• radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH• radicals together. With the inhibition of OH• radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH• were proposed in this study. Translated from Acta Scientiae Circumstantiae, 2005, 25(12): 1619–1623 [译自: 环境科学学报]     

Organic ligand-induced dissolution kinetics of antimony trioxide

The influence of low-molecular-weight dissolved organic matter(LMWDOM) on the dissolution rate of Sb_2O_3 was investigated. Some representative LMWDOMs with carboxyl, hydroxyl,hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen, namely oxalic acid, citric acid, tartaric acid, EDTA, salicylic acid, phthalandione, glycine, thiolactic acid,xylitol, glucose and catechol. These LMWDOMs were dissolved in inert buffers at pH = 3.7, 6.6and 8.6 and added to powdered Sb_2O_3 in a stirred, thermostatted reactor(25°C). The addition of EDTA, tartaric acid, thiolactic acid, citric acid and oxalic acid solutions at pH 3.7 and catechol at pH 8.6 increased the rate of release of antimony. In the 10 mmol/L thiolactic acid solution, up to 97% by mass of the antimony was released after 120 min reaction. There was no effect on the dissolution of Sb_2O_3 for the other ligands. A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found. All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb_2O_3 was not determined by the stability of the dissolved complex, but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface. This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands, but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals.     

微生物修复辽东湾油污染湿地研究

通过向受污湿地土样中添加菌株,探讨微生物对石油烃的降解.实验发现,混合菌能够充分发挥各菌种之间的协同作用,比单菌降解更为有效.最适降解条件控制在pH8.0,温度25℃.适宜的表面活性剂对微生物繁殖进而对油降解具有促进作用,加入300mg·kg^-1TW-80降解8d后,菌落数增加了6.22倍,油的降解率提高了20.1%.适量的H₂O₂有助于细菌分解油,过量会造成菌株死亡,每次添加计量控制在400mg·L^-1为宜.经过11d,H₂O₂累计量达到7000mg·L^-1,土样中油的降解率由39.81%提高到66.79%.     

Effect of phosphate on heterogeneous Fenton oxidation of catechol by nano-Fe3O4: Inhibitor or stabilizer?

The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene, in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy (ATR-FTIR) was used to monitor the surface speciation at the nano-Fe₃O₄ catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H₂O₂. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H₂O₂. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H₂O₂ and formation of hydroxyl radicals, and inhibit the catalytic ability of Fe₃O₄ catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H₂O₂ stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.     

Pd/C气体扩散电极用于电生成H2O2降解苯酚的研究

采用自制的Pd/C气体扩散阴极和Ti/IrO2/RuO2阳极,在无隔膜电解槽中对苯酚模拟废水降解效果及机制进行了研究,采用电子自旋共振法(ESR)对电解体系中产生的羟自由基(·OH)进行了检测.结果表明,在Pd/C气体扩散体系中掺杂Pd催化剂可以促进H2 O2的生成(H2 O2的稳定浓度是7.5 mg/L),有利于·OH的产生.经电化学氧化处理120 min后,苯酚和COD的去除率分别达到97.2%和50%,表明在电催化氧化过程中苯酚被氧化生成了大量低分子量中间产物.废水的BOD5/COD值达到0.73是处理前的9.1倍,苯酚废水的可生化降解性通过电化学氧化处理后显著提高.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2 O2、·OH的氧化共同作用下完成的.通过对紫外扫描光谱图的分析推断出苯酚在电解过程中有醌类物质生成;由GC-MS检测到了邻苯二酚、对苯二酚、苯醌等芳香族化合物和己二酸、顺丁烯二酸、反丁烯二酸、丁二酸、丙二酸、乙二酸等短链羧酸,据此提出了苯酚降解的可能历程.     

铁刨花-Fenton-絮凝工艺对染料生产废水中AOX、色度和TOC的去除效果研究

采用铁刨花-Fenton-絮凝工艺处理染料生产废水,考察了不同Fe~(2+)与H_2O_2摩尔比(1∶3~1∶15)、铁刨花反应时间(2~5h)、Fenton氧化反应时间(20~80 min)下可吸附性有机卤代物(AOX)、色度和总有机碳(TOC)的去除效果.结果表明,AOX、色度和TOC去除率随Fe~(2+)与H_2O_2摩尔比的降低先升高后减少,随铁刨花和Fenton反应时间的增加而持续升高.最优化条件为Fe~(2+)与H_2O_2摩尔比1∶8、铁刨花反应时间4 h和Fenton反应时间60 min,该条件下AOX、色度和TOC的去除率分别为94.2%、93.7%和27.2%.比较实验结果表明,铁刨花-Fenton-絮凝组合工艺对废水AOX、色度和TOC的去除效果远优于铁刨花处理、Fenton氧化、絮凝沉淀的单个技术或两两技术组合效果.GC-MS分析表明,废水中的有机卤代物和苯胺类污染物得到高效去除,此外硝基苯类、苯酚类、苯甲醛类、醚类、腈类和杂环化合物等有毒有害物质也均得到高效去除.叔丁醇捕获·OH实验表明·OH在Fenton反应中的主导作用.     

Heterogeneous Fenton-like degradation of 4-chlorophenol using iron/ordered mesoporous carbon catalyst

Ordered mesoporous carbon supported iron catalysts(Fe/OMC) were prepared by the incipient wetness impregnation method and investigated in Fenton-like degradation of 4-chlorophenol(4CP) in this work. XRD and TEM characterization showed that the iron oxides were well dispersed on the OMC support and grew bigger with the increasing calcination temperature. The catalyst prepared with a lower calcination temperature showed higher decomposition efficiency towards 4CP and H2O2, but more metals were leached. The effect of different operational parameters such as initial pH, H2O2 dosage, and reaction temperature on the catalytic activity was evaluated. The results showed that 96.1% of 4CP and 47.4% of TOC was removed after 270 min at 30°C, initial pH of 3 and 6.6 mmol/L H2O2. 88% of 4CP removal efficiency was retained after three successive runs, indicating Fe/OMC a stable catalyst for Fenton reaction. 4CP was degraded predominately by the attack of hydroxyl radical formed on the catalyst surface and in the bulk solution due to iron leaching. Based on the degradation intermediates detected by high performance liquid chromatography, possible oxidation pathways were proposed during the 4CP degradation.     

低分子量有机酸对三峡水库消落区土壤中汞赋存形态及其活性的影响

为研究植物根系分泌物的主要成分——低分子量有机酸对土壤汞的活化作用,利用室内模拟实验,通过分析不同浓度的柠檬酸、酒石酸和草酸溶液对三峡库区消落带土壤中汞赋存形态的影响及其随培养时间的变化特征,探究了低分子量有机酸对汞迁移能力和生物有效性的作用.结果表明,柠檬酸可增强土壤汞的迁移能力,而草酸和酒石酸则表现出软弱的抑制作用.3种低分子量有机酸均能明显地增强土壤中汞的生物有效性,整体活化效果为:柠檬酸酒石酸≈草酸.有机酸对土壤中汞形态的作用随其浓度的增加而增强,且当浓度为15 mmol·L~(-1)(柠檬酸)、10 mmol·L~(-1)(酒石酸和草酸)时开始趋于稳定.在15 mmol·L~(-1)柠檬酸培养的土壤中,汞形态分布的变化随培养时间的延长而愈加显著,直到14d时才基本停止,此时胃酸溶解态汞增加最为明显,其主要来自于部分被活化的强络合态汞.     

O3/H2O2氧化苯乙烯气体性能及机制

O3/H2O2体系能产生大量自由基,臭氧与自由基的耦合氧化作用能提高苯乙烯的氧化去除效率.采用O3/H2O2氧化高浓度苯乙烯有机废气,研究了臭氧投加量、停留时间、H2O2体积分数、循环液喷淋密度和O3/C8H8摩尔比对苯乙烯去除率的影响.结果表明,O3/H2O2气液两相氧化能高效净化苯乙烯有机废气,苯乙烯去除率可达85.7%.适宜运行条件:停留时间为20.6 s,H2O2体积分数为10%,喷淋密度为1.72 m3·(m2·h)-1,O3/C8H8摩尔比为0.46.采用GC-MS分析O3/H2O2气液两相高级氧化苯乙烯出口气样,研究结果表明苯甲醛(C6H5CHO)和苯甲酸(C6H5COOH)为O3/H2O2氧化苯乙烯的中间产物,并推测出苯乙烯的降解机制.     

土壤锌、铜、铁、锰形态区分方法的选择

用化学连续提取的方法将土壤中的锌、铜、铁、锰依结合状态区分为交换态、碳酸盐结合态(石灰性土壤)、氧化锰结合态、有机结合态、无定形氧化铁结合态、晶形氧化铁结合态和硅铝酸盐矿物态.初步认为选定的形态及提取方法适于土壤中锌、铜、铁、锰等元素的研究.     

缺氧酸化联合零价铁-过氧化氢改善污泥脱水性能的研究

为探讨缺氧酸化联合零价铁(ZVI)-过氧化氢(H_2O_2)调理对污泥脱水性能的影响,本文通过单因素试验,以污泥比阻(SRF)作为参考指标,系统考察了调理条件对污泥脱水性能的影响.同时,在试验的最佳调理条件下,分析了污泥各层胞外聚合物(EPS)有机物质量浓度及荧光光谱强度以阐明该联合作用机理.结果表明,当初始pH为2,ZVI投加量为280 mg·g~(-1)(以干污泥量(DS)计,下同),缺氧时间为4 h,H_2O_2投加量为30 mg·g~(-1)(以DS计,下同),类芬顿反应时间为10 min时,SRF降低了90.39%,处理效果较单独类芬顿处理提升了1倍.机理探究试验表明,在缺氧条件下,酸化处理可加速污泥的水解,溶解得到更多的二价铁离子,促使EPS结构发生改变;ZVI-H_2O_2调理可有效地氧化部分EPS,使得紧密结合胞外聚合物(TB-EPS)破解转化至松散结合胞外聚合物(LB-EPS)和上清液胞外聚合物(SB-EPS).EPS分析结果表明,蛋白质的减少能有效提高污泥脱水性能,腐殖酸和富里酸类有机物的产生能提高污泥疏水性能.此外,ZVI的再次利用效率高,重复利用仍能使SRF降低率达到82.04%.因此,缺氧酸化联合ZVI-H_2O_2处理能实现污泥的水解、氧化和絮凝过程,达到改善污泥脱水性能的目的.     

纳米Fe3 O4-H2 O2 非均相Fenton反应催化氧化邻苯二酚

由四氧化三铁(Fe3O4)-过氧化氢(H2O2)构成的非均相Fenton体系主要利用H2O2分解产生的羟基自由基氧化去除难降解有机污染物.研究了邻苯二酚在纳米Fe3O4-H2O2构成的非均相Fenton体系中的催化氧化特征,同时对实验室制备的纳米级Fe3O4和商品微米级Fe3O4两种催化剂的催化活性进行比较,并考察了H2O2初始浓度对邻苯二酚的催化氧化的影响.结果表明,自制纳米Fe3O4-H2O2体系较商品Fe3O4-H2O2体系,能更快速地去除溶液中的邻苯二酚和总有机碳(TOC),邻苯二酚的去除率接近100%,同时能迅速催化H2O2分解.邻苯二酚的催化氧化反应遵循准一级反应动力学方程,H2O2的分解反应能用三级反应动力学方程较好拟合.此外,反应过程中铁释放低于0.3 mg.L-1,不足以启动均相Fenton反应,反应机制为由界面反应控制的非均相反应机制.     

Advanced oxidation of bromide-containing drinking water：A balance between bromate and trihalomethane formation control

Addition of H2O2 has been employed to repress bromate formation during ozonation of bromide-containing source water. However, the addition of H2O2 will change the oxidation pathways of organic compounds due to the generation of abundant hydroxyl radicals, which could affect the removal efficacy of trihalomethane precursors via the combination of ozone and biological activated carbon （O3-BAC）. In this study, we evaluated the effects of H2O2 addition on bromate formation and trihalomethane formation potential （THMFP） reduction during treatment of bromide-containing （97.6-129.1 μg/L） source water by the O3-BAC process. At an ozone dose of 4.2 mg/L, an H2O2/O3 （g/g） ratio of over 1.0 was required to maintain the bromate concentration below 10.0 μg/L, while a much lower H2O2/O3 ratio was sufficient for a lower ozone dose. An H2O2/O3 （g/g） ratio below 0.3 should be avoided since the bromate concentration will increase with increasing H2O2 dose below this ratio. However, the addition of H2O2 at an ozone dose of 3.2 mg/L and an H2O2/O3 ratio of 1.0 resulted in a 43% decrease in THMFP removal when compared with the O3-BAC process. The optimum H2O2/O3 （g/g） ratio for balancing bromate and trihalomethane control was about 0.7-1.0. Fractionation of organic materials showed that the addition of H2O2 decreased the removal efficacy of the hydrophilic matter fraction of DOC by ozonation and increased the reactivity of the hydrophobic fractions during formation of trihalomethane, which may be the two main reasons responsible for the decrease in THMFP reduction efficacy. Overall, this study clearly demonstrated that it is necessary to balance bromate reduction and THMFP control when adopting an H2O2 addition strategy.     

五氯酚在土壤胶体界面的还原转化

提取玄武岩发育的红壤胶体,用恒温厌氧平衡动力学方法,研究土壤胶体界面五氯酚的降解效果,以及外加Fe2+和草酸对五氯酚还原转化的影响. 结果表明,厌氧条件下玄武岩发育赤红壤和砖红壤胶体对五氯酚均具有一定的降解能力,其表观降解速率常数分别为(0.032±0.002)和(0.057±0.003) d-1. 草酸或Fe2+对土壤表面五氯酚的降解均有显著的促进作用. 在探讨土壤胶体对五氯酚的降解能力与其理化性质关系的基础上,说明利用铁氧化物可进行复杂土壤体系中有机氯类污染物的修复.      

Comparisons of the film peeling from the composite oxides of quartz sand filters using ozone, hydrogen peroxide and chlorine dioxide

To solve the problem of shortened backwashing intervals in groundwater plants, several disinfectants including ozone (O₃), hydrogen peroxide (H₂O₂) and chlorine dioxide (ClO₂) were examined to peel off the film from the quartz sand surface in four pilot-scale columns. An optimized oxidant dosage and oxidation time were determined by batch tests. Subsequently, the optimized conditions were tested in the four pilot-scale columns. The results demonstrated that the backwashing intervals increased from 35.17 to 54.33 (H₂O₂) and to 53.67 hr (ClO₂) after the oxidation treatments, and the increase of backwashing interval after treatment by O₃ was much less than for the other two treatments. Interestingly, the treatment efficiency of filters was not affected by O₃ or H₂O₂ oxidation; but after oxidation by ClO₂, the treatment efficiency was deteriorated, especially the ammonia removal (from 96.96% to 24.95%). The filter sands before and after the oxidation were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. Compared with the oxidation by O₃ and H₂O₂, the structures on the surface of filter sands were seriously damaged after oxidation by ClO₂. The chemical states of manganese on the surfaces of those treated sands were only changed by ClO₂. The damage of the structures and the change of the chemical states of manganese might have a negative effect on the ammonia removal. In summary, H₂O₂ is a suitable agent for film peeling.     

Photocatalytic degradation of phenanthrene on soil surfaces in the presence of nanometer anatase TiO2 under UV-light

The effect of nanometer anatase TiO₂ was investigated on the photocatalytic degradation of phenanthrene on soil surfaces under a variety of conditions. After being spiked with phenanthrene, soil samples loaded with different amounts of TiO₂ (0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, and 4 wt.%) were exposed to UV-light irradiation for 25 hr. The results indicated that the photocatalytic degradation of phenanthrene followed the pseudo first-order kinetics. TiO₂ significantly accelerated the degradation of phenanthrene with the half-life reduced from 45.90 to 31.36 hr for TiO₂ loading of 0 wt.% and 4 wt.%, respectively. In addition, the effects of H₂O₂, light intensity and humic acid on the degradation of phenanthrene were investigated. The degradation of phenanthrene increased with the concentration of H₂O₂, light intensity and the concentration of humic acids. It has been demonstrated that the photocatalytic method in the presence of nanometer anatase TiO₂ was a very promising technology for the treatments of soil polluted with organic substances in the future.     

模拟淹水条件下紫色土镉的释放特征及影响因素

研究了在模拟淹水条件下紫色土镉的释放迁移特征及影响因素 .结果表明 ,土壤初始镉污染水平、水体初始酸度和有机酸组成显著影响土壤镉向水体的迁移释放 .土壤初始镉浓度每增加 1mg·kg-1,淹水平衡后水体中镉的浓度增加 0 0 0 6—0 0 0 7mg·L-1.当水体初始pH <6时 ,镉的释放量随pH的降低呈线性增加 ,每降低一个pH单位 ,水中镉浓度平均将增加 0 0 6mg·L-1.水体中多种有机物共存时对土壤重金属的释放存在复杂的交互作用 .草酸、柠檬酸、EDTA以及草酸、柠檬酸、富里酸、EDTA共存时显著促进土壤镉的释放 ;而草酸、柠檬酸、富里酸共存时 ,反而抑制了土壤镉的释放 .讨论了淹水过程中镉的释放与体系pH、Eh 变化之间的关系 .     

Fe2+-H2O2法处理DSD酸生产氧化母液的研究

为改善DSD酸氧化母液的可生化降解性,将废液先用有机絮凝剂TS-1(一种季胺盐)处理,TS-1的投加量为3g/L,其后用Fe²⁺-H₂O₂法氧化,Fe²⁺和H₂O₂的量分别为150mg/L,7g/L,废液COD和色度的去除率分别可达64%和62%。经处理后的废水,其BOD₅/COD≈0.3,可以认为已达到生化处理的要求。当H₂O₂的投量为2g/L,经Fe²⁺-H₂O₂氧化处理后的废液,再用FeCl₃进行两级混凝处理(FeCl₃的投加量分别为5g/L和2g/L),则COD和色度的去除率可达90%和95%。