用H2O2/Fe3+处理高浓度含甲醛废水的研究

研究采用H₂O₂/Fe³⁺催化氧化处理高浓度含甲醛废水，探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响，并通过酸溶解回用失活催化剂。结果表明，较优的操作条件为：H₂O₂/COD（质量比）=2.2～2.6，Fe³⁺/H₂O₂（摩尔比）=0.048～0.058，反应pH 1.80～2.68，反应温度50℃，反应时间40 min；在上述操作条件下，甲醛去除率达到99%以上，COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用，其效果与三价铁盐作催化剂的基本相同。采用H₂O₂/Fe³⁺处理含甲醛废水具有比采用H₂O₂/Fe³⁺较优的效果。     

Fenton氧化/高浓度泥浆法处理矿山废水

为了解决某大型铜矿废水COD不达标问题，采用Fenton氧化对原有高浓度泥浆（HDS）工艺进行改进。探讨了Fenton氧化矿山废水各指标的去除效果以及H₂O₂浓度对出水COD去除效果的影响，结果表明，Fenton氧化-电石乳中和絮凝沉淀工艺处理矿山废水是可行的，最优实验条件为：pH稳定在3.0～4.5，H₂O₂投加量0.5 mL/L，电石乳投加量8.5 g/L，PAM投加量1.5 mg/L；系统对废水COD的去除机理是加入的H₂O₂和矿山酸性废水中的Fe²⁺离子在低pH下形成Fenton试剂；系统对TFe、Zn²⁺、Cu2+ 的去除效果比Mn²⁺的去除效果更稳定。     

UV/Fenton法预处理N-甲基苯胺生产废水

采用UV/Fenton法对N-甲基苯胺生产废水进行预处理。当原水COD约为3 400 mg/L时，在适宜操作条件（H₂O₂投加量为50 mL/L，Fe²⁺投加量为1.209 g/L，pH＝5.0，反应时间为30 min）下的COD去除率可达90％以上。同时得到Fenton试剂处理该废水的适宜条件为：H₂O₂投加量为60 mL/L，Fe²⁺投加量为1.692 g/L，pH为5.0，反应时间30 min；单独UV辐照处理该废水的较适宜条件为：反应时间为20 min， pH＝5.0。最后就3种处理方法进行了比较，发现UV对Fenton试剂处理N-甲基苯胺生产废水具有一定促进作用。反应前后的紫外光谱说明，经UV/Fenton反应后，原水中的含苯环物质已得到了彻底的氧化分解。     

氨吹脱-Fenton氧化预处理阿奇霉素废水的研究

采用氨吹脱-Fenton试剂氧化法对阿奇霉素废水进行预处理，考察了各种因素对处理效果的影响。实验结果表明：在pH值为11，吹脱时间160 min，温度30℃的条件下，氨氮浓度从2 458.7 mg/L降低到421.7 mg/L，去除率可达82.85%；Fenton氧化吹脱出水的适宜工艺条件：初始pH值为3、反应时间90 min、FeSO₄·7H₂O投加量为0.01 mol/L、H₂O₂/Fe²⁺的投加比16∶1，此时，COD去除率为72.6%；废水经预处理后，有效地改善了废水水质，提高了废水的可生化性，由初始的0.1增至0.37，为后续废水的生化处理提供了有利条件。     

微曝气Fenton氧化法处理模拟双酚A废水的效果及其生物验证

研究了微曝气Fenton氧化法关键工艺参数对模拟双酚A（BPA）废水处理效果的影响，并从活性污泥性质和污染物去除率两方面，采用膜生物反应器(membrane bioreactor, MBR)对微曝气Fenton氧化法的处理效果进行了实验验证，为实现BPA废水的生物处理奠定基础。结果表明，初始pH值、反应时间、H₂O₂/COD(质量浓度比)、H₂O₂/Fe²⁺ (摩尔浓度比)、反应温度及曝气量均对预处理效果有较大影响，在最佳条件下，COD去除率可达70%，BOD/COD值则由原废水的0.02提高到0.50以上。MBR处理上述出水的结果表明，经微曝气Fenton氧化处理BPA的废水，可较好地适应后续的生化处理。     

不同高级氧化法对水中低浓度药物甲硝唑降解过程的比较

采用UV、H₂O₂、UV/H₂O₂、Fenton、UV/Fenton和UV/TiO₂方法，对水中低浓度的药物甲硝唑进行降解。通过HPLC和UV-Vis光谱得到的甲硝唑去除率。详细讨论了Fe²⁺、TiO₂和H₂O₂的初始浓度以及溶液的初始pH值对降解效率的影响。结果表明，UV/Fenton和UV/TiO₂ 2种系统对水中低浓度甲硝唑均有很好的去除效果，但前者的光催化效率更高。在甲硝唑浓度=6 μmol/L，H₂O₂和Fe²⁺的初始浓度分别为0.5 mg/L和2.94 μmol/L，pH=4的条件下，UV/Fenton方法对甲硝唑水溶液光催化的最佳效率为95.8%。     

Fenton氧化破解污水处理厂污泥

研究了Fenton氧化反应的影响因素pH值、H₂O₂/Fe²⁺投加比、反应温度和反应时间对污泥破解效果的影响，并以污泥上清液中蛋白质、糖类、SCOD及污泥TSS、VSS的变化来表征污泥破解的程度。结果表明，最佳破解条件为：pH=5，最佳H₂O₂/Fe²⁺投加比为24：1，反应温度为70℃，反应时间为90 min，在该条件下，SCOD、溶解性蛋白质和多糖分别由88.76、19.70和14.95 mg/L增加到3 714.64、2 039.90和289.70 mg/L；TSS及VSS分别由34.60 g/L、19.76 g/L降为26.60 g/L、14.22 g/L，去除率分别为23.12%和 28.14%。Fenton氧化破解污泥，能够有效促进污泥絮体分解，有利于进行后续的厌氧消化处理。     

Fe(Ⅱ)EDTA/H2O2电催化降解甲基橙模拟废水的研究

在无隔膜电解槽中,采用SPR(Ru-Ir-Ti0₂)为阳极,石墨为阴极,考察了Fe(Ⅱ)EDTA/H₂O₂电催化降解甲基橙(methyl orange)模拟废水的影响,发现EDTA很大程度上促进了类电Fenton试剂对甲基橙模拟废水的降解。实验研究表明,在外加电压为5.0 V,EDTA∶Fe²⁺=2∶1(摩尔比,Fe²⁺=40 mmol/L),H₂O₂=48 mmol/L,电解质Na₂SO₄=40 mmol/L,废水pH值为(6.5±0.1)的条件下,降解260 mg/L的甲基橙模拟废水90 min, EDTA的加入可以使甲基橙模拟废水的脱色率由29.5%上升到78.4%,COD由571.429 mg/L降至80 mg/L,COD的降解率为86%，EDTA在此过程中既是催化剂又是反应物,可有效避免EDTA带来二次环境污染的可能性。     

天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La₂O₃(0.5%)-ZnO(20%)-TiO₂/沸石复合光催化剂，以20 W紫外灯为光源，在自制的光催化反应器中降解活性艳红K-2BP，考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H₂O₂与Fe³⁺投加量等对活性艳红K-2BP光催化降解率的影响。结果表明，当溶液初始浓度为60 mg/L，催化剂投加量为12 g/L，通气量为1 200 mL/min，光照2.5 h，活性艳红K-2BP的降解率可达99.2%；H₂O₂和Fe³⁺投加量为4 mL/L和3 g/L时，光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外可见吸收光谱显示，LZTZ光催化剂可有效降解印染废水。     

微波-Fenton 氧化-PAFSi 絮凝法处理含油废水简

采用微波-Fenton氧化-PAFSi絮凝法处理含油废水，结果表明，200 mL水样先经微波辐射6 min，在pH=2，H₂O₂（30%）3.5 g/L，Fe²⁺ 1.3 g/L的条件下氧化4 h后，采用聚硅酸铝铁（Al：Fe：Si=10：2：1）和聚丙烯酰胺在pH=8时进行絮凝实验，处理后废水浊度、SS、COD、含油量和色度分别降低了99.46%、96.66%、91.94%、97.97%和95.00%，且经处理后废水的BOD₅/COD由原水的0.04提高到0.53。实验还分析了含油废水的降解机理。     

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.     

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.     

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.