负载型TiO2在印染废水降解中的失活及原因分析

研究了负载型TiO2光催化剂在印染废水降解中的失活及其产生的原因.实验结果说明,催化剂活性下降的主要原因有废水中不溶于水的染料等悬浮物和催化反应中产生的无定形碳在催化剂表面的吸附;高含量的无机离子对催化剂活性位的占据或在表面的沉积;长时间的使用和反复冲洗使TiO2负载量减少.通过同时采用灼烧和酸洗的方法可以使TiO2的活性恢复到新催化剂的69.5%.     

SO2的气相光催化氧化及催化剂的失活和再生研究

在模拟大气环境中，紫外光照射以及纳米TiO2光催化剂的作用下，气相无机污染物SO2被完全氧化为SO2或H2SO4。本文提出了SO2的非均相光催化氧化机理，并得出光催化反应速率符合一级动力学过程；经过连续使用之后，TiO2的光催化活性降低，最后活性消失；经过水洗之后，失活的TiO2可以得到再生。失活的TiO2和新鲜的TiO2的IR和XPS光谱差异表明，失活的TiO2表面存在H2SO4，其被认为是使催化剂失活的成分。     

GeO_2改性TiO_2催化超声降解活性红（M-3BE）染料废水的应用研究

制备了经GeO2改性的纳米TiO2,并用之作为超声降解活性红M-3BE反应的催化剂,研究了各种因素对制备的GeO2改性的纳米TiO2催化超声降解活性红染料废水的影响,并用XRD,SEM等手段对催化剂进行了表征。结果表明：GeO2改性的纳米TiO2作为催化剂,其对超声降解活性红染料废水的催化剂作用明显优于单纯以锐钛矿型T...     

硫酸盐化对TiO2催化剂克劳斯活性的影响

采用硫酸铵浸渍的方法制得了一系列硫酸盐化的催化剂,运用TG、BET比表面测定、XRD、Raman、FTIR和SO2-TPD技术对催化剂进行了表征,并对催化剂进行了克劳斯活性评价。结果表明,硫酸盐化会导致催化剂比表面积和孔体积减小但不会使催化剂形成新的晶型,硫酸盐的形成使TiO2表面碱性变弱,硫酸根在TiO2表面形成的双齿螯合结构会阻碍SO2和H2S与催化剂表面的接触,碱性变弱和双齿螯合结构的形成导致了催化剂克劳斯活性降低,另外,负载的硫酸盐的量越多催化剂的克劳斯活性越低。     

锰铜铈氧化物催化剂氧化NO性能及动力学研究

实验以TiO2为载体采用浸渍法制备CuOx/TiO2、CeOx/TiO2、CuCeOx/TiO2和MnCuCeOx/TiO2催化剂,考察这些催化剂氧化NO活性,探究Cu、Ce摩尔比和添加Mn元素对CuCeOx/TiO2催化剂氧化NO活性的影响,使用扫描电镜观察催化剂表面结构。研究发现,Cu、Ce元素配合后的CuCeOx/TiO2催化剂氧化活性明显好于单独含Cu、Ce的催化剂,当Cu、Ce摩尔比为Cu:Ce=1∶2时,CuCeOx/TiO2催化剂氧化活性最好,在NO浓度500×10-6,O210%,空速为24 000 h-1,350℃时,NO氧化度为0.62;添加Mn元素可以提高CuCeOx/TiO2催化剂低温氧化活性,250℃时,MnCuCe/Ti-3和MnCuCe/Ti-5催化剂氧化度为0.53和0.69,300℃时,MnCuCe/Ti-3和MnCuCe/Ti-5催化剂氧化度均为0.76;此外,实验还研究了NO在MnCuCe/Ti-3催化剂上反应的动力学方程。     

具有SR-Fenton和光催化活性的Co-TiO_2的制备及其活性

以溶胶凝胶法制备了Co-TiO2催化剂,采用XRD、XPS、紫外漫反射对催化剂进行了表征,结果表明,一部分Co2+进入了TiO2晶格,另一部分在TiO2表面形成Co3O4。以亚甲基蓝为模拟废水,进行了Co-TiO2催化剂的基于硫酸根自由基的类Fenton(SR-Fenton)和光催化活性测试,且考察了催化剂钴掺杂量、灼烧温度对催化剂活性的影响。结果表明,CoTiO2催化剂为同时具有SR-Fenton和光催化活性的催化剂,Photo/Co-TiO2/过硫酸氢钾为光催化和SR-Fenton反应的协同体系。催化剂最佳钴掺杂量、灼烧温度分别为1%及773 K。     

膨胀珍珠岩负载TiO2光催化脱色性能的研究

以钛酸四丁酯为原料，膨胀珍珠岩为载体，用溶胶—凝胶法制备可漂浮于水面的负载型TiO2。利用该负载型TiO2对罗丹明B(RB)进行光催化脱色实验，结果表明，浸渍3次的负载型TiO2光催化活性最高，催化剂最佳用量为500mg／100mL RB，经5h光照，对100mL浓度为1mg／L和2．5mg／LRB脱色率分别为76．67％和47．27％；该催化剂使用寿命长，25h后催化剂脱色性能没有减弱，可重复使用；经8h光照，染料废水脱色效果好。     

SO2的气相光催化氧化及催化剂的失活和再生研究

在模拟大气环境中,紫外光照射以及纳米TiO2光催化剂的作用下,气相无机污染物SO2被完全氧化为SO3或H2SO4。本文提出了SO2的非均相光催化氧化机理,并得出光催化反应速率符合一级动力学过程;经过连续使用之后,TiO2的光催化活性降低,最后活性消失;经过水洗之后,失活的TiO2可以得到再生。失活的TiO2和新鲜的TiO2的IR和XPS光谱差异表明,失活的TiO2表面存在H2SO4,其被认为是使催化剂失活的成分。     

SO2的气相光催化氧化及催化剂的失活和再生研究

在模拟大气环境中,紫外光照射以及纳米TiO2光催化剂的作用下,气相无机污染物SO2被完全氧化为SO3或H2SO4.本文提出了SO2的非均相光催化氧化机理,并得出光催化反应速率符合一级动力学过程;经过连续使用之后,TiO2的光催化活性降低,最后活性消失;经过水洗之后,失活的TiO2可以得到再生.失活的TiO2和新鲜的TiO2的IR和XPS光谱差异表明,失活的TiO2表面存在H2SO4,其被认为是使催化剂失活的成分.     

SO_4~（2-）/TiO_2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明：随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温（〈550℃）焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时（〉550℃）SO42-在TiO2表面是桥式配位吸附。     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

骆马湖富营养化和生态状况调查与评价

为了了解骆马湖水质状况，在2005年对骆马湖富营养化状态和生态特性进行了调查，并结合“十五”期间的监测资料进行了分析。2005年骆马湖水体中总氮和总磷的平均值超《地表水环境质量标准》（GB3838-2002）中Ⅲ类，超标情况分别为0．78倍和0．54倍，达到湖库特定项目Ⅳ类水标准，骆马湖处于轻度富营养化状态。对骆马湖生态特征分析表明，由于该湖泊的形态以及“藻型浊水状态”和“泥沙型浊水状态”交替出现，遏制了湖水从高营养盐含量向全面富营养化状态演变，保障了底栖动物的良好生长环境，从而形成了骆马湖独特的环境生态平衡。     

Copper-catalyzed chlorination and condensation of acetylene and dichloroacetylene

The chlorination and condensation of acetylene at low temperatures is demonstrated using copper chlorides as chlorinated agents coated to model borosilicate surfaces. Experiments with and without both a chlorine source and borosilicate surfaces indicate the absence of gas-phase and gas-surface reactions. Chlorination and condensation occur only in the presence of the copper catalyst. C₂ through C₈ organic products were observed in the effluent; PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed that is consistent with the observed product distributions. Similar experiments with dichloroacetylene indicate greater reactivity in the absence of the copper catalyst. Reaction is observed in the gas-phase and in the presence of borosilicate surfaces at low temperatures. The formation of hexachlorobenzene is only observed in the presence of a copper catalyst. PCDD/F were only observed from extraction of the borosilicate surfaces. A global reaction model is proposed for the formation of hexachlorobenzene from dichloroacetylene.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

剩余污泥浓缩脱水投药量优化和模型建立

应用高分子阳离子絮凝剂（CPF-100）和聚丙烯酰胺（PAM）对污水厂剩余污泥进行浓缩脱水实验,研究表明：CPF-100的浓缩脱水效果优于PAM;当CPF-00投加量为1．16‰时,污泥沉降性能改善程度为37．51％;且在CPF-100投加量逐渐增大的初始阶段,污泥沉降性能改善程度随投加量的增加而增大,但CPF-100投加量也不宜过大,当CPF-100投加量超过1．16‰后,反而会使浓缩脱水效果变差。同时,建立了污泥沉降性能改善程度与絮凝剂CPF-100投加量、沉降时间之间的数学模型,其能较好地反映污水厂剩余污泥的浓缩脱水效果。     

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.