Cu-Mn-O制备条件对其催化燃烧甲苯性能的影响

以甲苯催化燃烧为模型反应,考察了Cu-Mn-O催化剂共沉淀制备方法中沉淀剂、滴加方式和焙烧温度对其催化活性的影响.结果表明,以Na2CO3为沉淀剂、反滴(金属离子溶液滴加到碱液)、500℃焙烧所制得的催化剂具有较高的活性,其甲苯完全燃烧(甲苯转化率98%以上)温度为220℃.多晶粉末衍射(XRD)和比表面积(BET)表征发现,在Cu1.5Mn1.5O4晶相中掺杂少量的CuO晶相可以有效地提高催化剂活性,催化剂的比表面积(BET)越大,活性越高.     

新型Cu-Co-O_x催化剂的制备及其催化燃烧甲苯的性能研究

采用浸渍法制备自制载体负载复合金属氧化物Cu-Co-Ox催化剂。研究了Cu-Co-Ox催化剂催化燃烧甲苯的活性。分别考察了Cu-Co-Ox负载量、Cu/Co(摩尔比)及焙烧温度对催化燃烧甲苯活性的影响,并采用X射线衍射(XRD)及扫描电镜(SEM)等表征技术,分别对复合金属氧化物Cu-Co-Ox的晶型与结晶形貌进行了分析。结果表明,焙烧温度为600℃,Cu-Co-Ox负载量为5%(质量分数),Cu/Co为1∶2时,Cu-Co-Ox催化燃烧甲苯的活性最高。当反应温度为250℃,甲苯的转化率达到95%以上。XRD分析表明,Cu-Co-Ox催化剂主要活性相为CuCo2O4尖晶石。     

CO3O4/介孔分子筛催化剂对苯催化完全氧化的研究

分别以介孔分子筛MCM-41、MCM-48、SBA-15为载体,采用等体积浸渍法制备了氧化钴/介孔分子筛催化剂,利用N2吸附、X射线衍射、程序升温还原等技术对催化剂进行了表征,考察了Co3O4的负载量及载体的孔结构对催化剂完全催化氧化苯的性能的影响.结果表明,Co3O4的负载量为20%时,催化剂的催化活性最好;载体的孔径和催化剂的可还原性能是影响催化活性的主要因素,催化剂活性顺序为Co3O4/SBA-15>Co3O4/MCM-41>Co3O4/MCM-48.     

沸石载体催化剂研制及其催化臭氧氧化染料废水的研究

以沸石为载体负载不同金属氧化物来制备催化剂,通过试验分析该催化剂催化臭氧氧化染料废水的效果及其影响因素。结果表明:(1)沸石对染料废水的吸附作用很小,总有机碳(TOC)去除率基本维持在3.2%左右,对于后期的试验可以忽略其影响。(2)以沸石作为载体制得的MnO2、Fe2O3、ZnO、CuO负载型催化剂(分别简写为MnO2/沸石、Fe2O3/沸石、ZnO/沸石、CuO/沸石),对臭氧氧化反应均有催化作用,其催化效果依次为MnO2/沸石Fe2O3/沸石ZnO/沸石CuO/沸石。同时,MnO2/沸石的重复使用率高。(3)MnO2/沸石催化臭氧氧化效率及重复使用率均优于以活性炭为载体的MnO2负载型催化剂。(4)臭氧氧化和MnO2/沸石催化臭氧氧化对染料的脱色率基本一致。MnO2/沸石催化臭氧氧化的TOC去除率比臭氧氧化提高较多,对染料废水有很好的处理效果。(5)以沸石为载体制得的负载型催化剂催化臭氧氧化实际染料废水的处理效果较好,具有较高的实用价值。     

烟气NO氧化催化剂Cu-V/Ti-PILCs的制备及其硫水稳定性

采用等体积浸渍法制备了以钛交联粘土为载体,Cu与V氧化物为活性组分的烟气NO氧化催化剂(Cu-v/Ti-PILCs),并考察了各种制备条件下催化剂的活性及稳定性.结果显示,当V水/V丙酮 =1∶2,负载4%CuO和2%V2O5,并在500℃煅烧时制得的Cu-V/Ti-PILCs催化剂,在NO浓度为350 mg/m3,O...     

无机盐离子对负载型催化剂Co_3O_4/GO降解PVA废水的影响

以氧化石墨烯(GO)作为Co3O4的载体,制备出应用于基于硫酸根自由基的高级氧化技术的负载型催化剂复合物——Co3O4/GO,采用XRD、FT-IR、Raman、EDS和SEM表征测试,并考察了无机盐离子(Cl-、HCO-3、H2PO-4和NO-3)对催化降解PVA的影响。结果表明,Co3O4已成功负载到GO上;负载型催化剂Co3O4/GO具有很高的催化活性;不同无机盐离子对催化降解反应的影响不同。本研究内容将对实际PVA废水处理过程起到借鉴和指导作用。     

气体循环条件下等离子体催化氧化吸附态苯

采用气体循环方式,对低温等离子体联合Mn Ox-Ag Ox、Co Ox-Ce Ox复合金属氧化物催化剂催化氧化吸附态的苯进行研究,主要考察了苯吸附存储量、氧化背景气体、催化剂对苯氧化性能的影响,并分析了催化剂对O3及N2O副产物产生的影响规律。研究结果表明,采用气体循环方式,有助于实现苯充分氧化为CO2。相同条件下,COx产率、CO2选择性及对O3的分解能力大小依次为:Mn Ox-Ag Ox/γ-Al2O3Co Ox-Ce Ox/γ-Al2O3γ-Al2O3。氧气背景下,气体循环75 min后,Mn Ox-Ag Ox/γ-Al2O3及Co Ox-Ce Ox/γ-Al2O3催化剂存在时,CO2选择性大于95%;气体循环90 min后,与γ-Al2O3所对应的COx产率相比,Mn Ox-Ag Ox/γ-Al2O3、Co Ox-Ce Ox/γ-Al2O3分别提高了38%、17%。FT-IR分析结果表明,等离子体催化氧化苯的主要产物为CO2、CO和H2O,副产物为少量的O3及N2O。     

La—K—Co—Mn-O钙钛矿型复合氧化物同时去除碳颗粒和NOx的性能

采用柠檬酸络合燃烧法合成制备了La1-xKxCo0.5Mn0.5O3(x为K+取代量,x=0、0.1、0.2、0.3、0.4、0.5)系列钙钛矿型复合金属氧化物催化剂,以X射线衍射、红外光谱和比表面积等手段对该催化剂进行表征,以常压固定床微型反应器程序升温氧化还原反应技术评价该催化剂同时去除模拟柴油机尾气中炭黑颗粒(表征柴油机尾气中的碳颗粒)和NOX的催化性能.结果表明,K+部分取代LaCo0.5Mn0.5O3中的La3+后,催化剂催化性能得到明显改善,炭黑颗粒的起燃温度(Tig)、峰值温度(Tm)和燃尽温度(Tf)均降低,NOX的转化率提高,最高为16.6%;La0.6K0.4Co0.5Mn0.5O3具有最佳的催化性能,炭黑颗粒的Tig、Tm和Tf分别为305、350、379 ℃,炭黑颗粒燃烧产物中CO2的体积分数为98.8%,NOX转化率为15.5%.     

膨胀石墨负载Co3O4催化过硫酸氢钾复合盐降解酸性橙Ⅱ的研究

以膨胀石墨(EG)作为Co3O4的载体,制备出应用于基于硫酸根自由基的高级氧化技术的非均相催化剂复合物——Co3O4/EG,并用其降解水中的偶氮染料酸性橙Ⅱ,同时考察了氧化剂投加量、催化剂投加量、温度等因素对降解性能的影响以及催化剂的稳定性.结果表明,Co3O4/EG具有很高的催化活性,在最佳条件下能在8 min内完全降解酸性橙Ⅱ,且具有很好的稳定性.     

类水滑石衍生复合氧化物催化水解羰基硫的研究

采用共沉淀法制备了一系列的类水滑石衍生复合氧化物催化剂,利用正交实验设计对催化剂的制备条件进行了优化,研究了金属组合、合成pH、M2+/M3+、二价金属比、焙烧温度和晶化温度等6个因素对羰基硫催化水解过程中催化剂硫容的影响。结果表明,金属组合、二价金属比和焙烧温度的影响极其显著(p=99%),晶化温度的影响显著(p=95%),合成pH与M2+/M3+对催化剂活性影响不显著(p=90%)。在设定实验条件下,金属组合取Co-Ni-Al、合成pH为9,M2+/M3+为3,二价金属比1,焙烧温度取350℃,晶化温度50℃时制得的催化剂具有最高的催化活性。对最佳制备条件下得到的催化剂进行了重复性实验以及XRD表征,结果表明制备的催化剂的硫容为7.10 g硫/g催化剂,Co3O4可能是其活性中心。     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.