包覆型纳米零价铁的制备及其去除水中的活性艳蓝

采用流变相法,以FeSO4.7H2O∶KBH4=1∶2(摩尔比)为固相介质,0.06 g/mL CMC(羧甲基纤维素)水溶液为液相介质,固液比1∶2,反应2 h制备出包覆型纳米零价铁;采用XRD、TEM等手段对合成的纳米零价铁进行表征。探讨不同反应条件对包覆型纳米铁去除活性艳蓝的影响。实验结果表明,初始活性艳蓝(浓度100 mg/L)pH为5,包覆型纳米铁的投加量为6 g/L,反应时间为30 min时,活性艳蓝的去除率可达96%。通过研究机理,其吸附过程符合二级吸附动力学,降解过程符合一级反应动力学。     

磁性LDH负铜催化剂的制备及其对直接青莲D-BL的脱色

实验以滴定共沉淀法制备Mg-Al LDH晶体包覆的Fe3O4颗粒,利用LDH的层间阴离子交换性使其吸附[Cu(C2O4)2]-络合离子,通过焙烧获得磁性焙烧态LDH载体的负铜催化剂。并通过SEM、X-Ray、FT-IR等方法以及静态实验,表征及考察了材料的物化特性及其直接性偶氮染料直接青莲的脱色性能。结果表明,材料对该染料废水有较强去处能力,且磁性良好易于分离回收;其最佳制备条件为用浓度为20 g/L的K2[Cu(C2O4)2]溶液改性一次,反应结束后于450℃下焙烧5 h;上述条件下制备的材料投加量为1 g/L、H2O2浓度为6.53 g/L、处理时间2 h,对200、300和500 mg/L浓度的模拟直接青莲D-BL染料废水去除率分别为99.62%、90.43%和81.92%。     

Fenton氧化法降解丙烯酸废水的研究

利用废铁屑与H₂O₂形成的Fenton氧化反应来降解工业丙烯酸废水中的丙烯酸。在间歇反应器中,系统地考察了反应时间、H2O2浓度、液固比(废水质量∶固体质量)和反应温度对丙烯酸的降解率的影响,优选了工艺条件。在连续固定床反应器中进行了对比实验,以考察固液接触状态的影响及系统的稳定性。结果表明,废铁屑与H₂O₂构成的Fenton体系能有效地降解废水中的丙烯酸。在间歇工况下,适宜的条件为,液固比40∶1,温度20～25℃,H₂O₂浓度800 mg/L ,反应时间35 min,在此条件下,丙烯酸的降解率可达到95%以上。对比实验表明,固液接触状态对降解效果的影响不大,铁屑的性能稳定,在连续93 h的稳定性实验中,丙烯酸的降解率保持在90%左右。     

负载型纳米复合半导体WO_3-TiO_2/AC光催化降解刚果红废水

采用溶胶-凝胶-浸渍-焙烧法制备了负载型纳米复合半导体WO3-TiO2/AC光催化剂,以偶氮染料刚果红为目标降解物,通过正交实验优化了刚果红废水的降解条件,并对其光催化动力学进行了探讨.结果表明,刚果红废水的最佳降解条件为:催化剂投加量10 g/L,pH=7,H2O2用量为3.5 mL/L.在最佳条件下,当刚果红废水起始浓度为40 mg/L时,反应120 min后,刚果红溶液的去除率可达95.21%,较相同条件下TiO2/AC对刚果红染料的降解率提高了19.57%.光催化剂对刚果红的光催化降解符合Langmuir-Hinshelwood(L-H)模型.     

MIL-101前体制备多孔铁碳材料构建高效异相电芬顿体系

通过水热法合成MIL-101(Fe)材料,并在N2氛围中进行高温碳化制备多孔铁碳(N-MIL-FeC)电极材料,探究其电催化氧还原性能及阴极电芬顿降解模拟染料废水性能。将制备的N-MIL-FeC材料进行电催化氧还原反应(ORR)性能测试,结果表明,Fe/H_2BDC摩尔比为2∶1,碳化温度为900℃,N-MIL-FeC材料CV扫描所得图形峰电位最小且峰电流最高,具有最优的ORR催化活性。在此基础上,将最佳条件下制得的N-MIL-FeC负载在碳纸上制成催化阴极应用于电芬顿反应催化降解模拟染料废水RhB。在催化剂负载量为1.5 mg·cm~(-2),pH为7条件下,浓度10 mg·L~(-1)的RhB溶液经过70 min降解率达到99%以上。通过淬灭实验和电子顺磁共振(EPR)测试证明羟基自由基(·OH)是参与催化降解反应的主要活性中间体。以MIL-101(Fe)为前驱体制备的多孔铁碳材料性能较好,有一定的应用前景。     

剩余污泥催化剂的制备及其脱色性能

以焦化废水脱水污泥为载体、ZnCl2为活化剂和催化剂的活性组分,采用一步法制备污泥催化剂。实验结果表明,当ZnCl2浓度为4 mol/L、固液比1∶3、焙烧温度550℃、焙烧时间40 min时,制备的污泥催化剂对亚甲基蓝的脱色性能最佳。利用制备的催化剂对活性红X-3B、弱酸性艳红B、活性蓝X-BR溶液进行脱色处理,研究反应时间、染料浓度、溶液pH、催化剂投加量和H2O2用量对染料脱色性能的影响。最佳条件下,3种废水的脱色率分别达到90.7%、97.5%和94.4%。对脱色数据进行动力学模拟,结果表明,3种染料废水脱色反应分别符合二级动力学模型、一级动力学模型、二级动力学模型。     

铁碳微电解/H_2O_2耦合类Fenton法深度处理制药废水

采用铁碳微电解/H2O2耦合类Fenton法深度处理制药废水,考察不同铁碳比、H2O2投加量、溶液p H及反应时间对COD去除效果的影响,通过单因素实验和正交实验确定最优条件并与铁碳微电解法的去除效果进行对比。结果表明,各因素对COD的去除效果均呈现先增加后降低或趋于稳定的趋势,且对去除效果的影响顺序为:Fe/CH2O2投加量溶液p H反应时间;在固液比为1∶10的条件下,Fe/C(质量比)为1∶1,溶液p H为2.5,反应时间为60 min,H2O2(30%)投加量为12.24 mmol/L时对COD的去除效率最高,可达71.56%;H2O2对铁碳微电解法有显著的加强作用。     

包埋固定化微生物法处理含油废水研究

本研究通过包埋固定化微生物法固定除油(Y1#菌),用于处理含油废水,并以水体中乳化油去除率为指标考察了影响乳化油降解的各种因素.选用聚乙烯醇(PVA)-海藻酸钠(SA)复配作为包埋固定化载体材料,制备成固定化微生物小球(IMB),通过实验优化了IMB制备的工艺条件.连续批次除油实验结果表明,在25～40℃,固液比1∶10,HRT为6 h的条件下,进水油含量在20～50 mg/L,乳化油去除率可达85%～90%,出水油含量低于5 mg/L.     

废汞触媒中汞的浸出及其再生活性炭的吸附性能

对电石法生产聚氯乙烯产生的废汞触媒进行浸出及再生活性炭的研究,以6 mol·L~(-1)HCl溶液作为浸出剂,在浸出反应温度为65℃、浸出反应时间为90 min和液固比为15∶1的实验条件下得到Hg~(2+)的优化浸出率为61.25%。采用扫描电镜(SEM)、Brunauer-Emmet-Tller(BET)比表面积等方法分析再生活性炭特征。结果表明焙烧废汞触媒浸出渣热再生活性炭是可行的,焙烧最佳工艺条件为:焙烧温度850℃,焙烧时间90 min。得到的焙烧产物亚甲基蓝吸附值为120.5 mg·g~(-1),BET表面积为704.25 m~2·g~(-1),平均孔径为3.28 nm。再生前后的汞含量与从1.067%降至0.351%,再生后能再次作为汞触媒生产的催化剂载体材料,同时减缓固废堆积过程中汞流失造成的一系列环境问题。     

锰掺杂WO3-TiO2复合光催化剂的制备及其性能研究

溶胶-凝胶和浸渍相结合的方法制备锰掺杂WO3-TiO2复合光催化剂,RXD表征,考察WO3和Mn2 掺入量、焙烧温度、焙烧时间及催化剂用量对光催化降解甲基橙的影响.结果表明,500℃焙烧2 h,掺杂量n(Mn2 )∶n(wo3)∶n(TiO2)=0.8∶1∶100时,光催化活性最高,光催化降解甲基橙溶液,120 min后,降解率达90%,比单纯TiO2的光催化活性提高81%.     

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.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

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.     

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.