零价铁Fenton技术处理含聚乙烯醇的印染退浆废水

采用零价铁Fenton技术处理含聚乙烯醇(PVA)的印染退浆废水。通过单因素实验和正交实验,考察了初始pH、H2O2投加量、铁屑粒径及投加量和反应时间对实验结果的影响。结果表明,初始pH和H2O2投加量对处理效果影响很大。最佳反应条件是初始pH=4.0,H2O2投加量为100mmol/L,铁屑(粒径为1~3mm)投加量为15g/L,反应时间为30min。在该条件下,出水PVA质量浓度为0.9mg/L,PVA去除率为99.9%,COD去除率为23.6%,BOD5/COD由0.12升高至0.34,可生化性明显提高。无论从处理效果考虑还是从成本考虑,零价铁Fenton技术都优于传统Fenton技术。     

Fenton氧化-混凝联合工艺处理络合铜镍废水的研究

采用Fenton试剂氧化-混凝联合工艺对难处理络合铜镍电镀废水进行了研究,考察了废水初始pH值、H2O2初始浓度、[Fe2 ]/[H2O2]、反应时间和温度、混凝液pH、混凝剂质量浓度对处理过程的影响,探讨了废水的降解途径和机理.结果表明,在体系初始pH=4,温度30℃,H2O2投加量为800mg/L,[Fe2 ]/[H2O2]=0.1,反应时间60 min,混凝液pH=8及混凝剂质量浓度为500mg/L的条件下,废水的COD去除率为96.98%,Cu2 为99.91%,Ni2 为99.92%,处理水完全达到国家一级排放标准.同时依据GC/MS对X-GN降解最终产物的分析结果,推导出废水的基本降解机理和途径.     

TiO2光催化处理络合铜废水的实验研究

研究了以悬浮态TiO2为催化剂,在紫外光的作用下对络合铜废水进行光催化反应,分别考察了常温下TiO2投加量、反应时间、废水初始pH值、反应气氛等因素对处理效果的影响,并探讨了反应机理。结果表明:TiO2投加量为2 g/L,废水pH=4,300 W高压汞灯照射下,载入60 mL/min的空气反应40 min,120 mg/L EDTA络合铜废水的Cu(II)与COD的去除率达到最高,分别为96.56%和57.67%。     

TiO2光催化处理络合铜废水的实验研究

研究了以悬浮态TiO2为催化剂,在紫外光的作用下对络合铜废水进行光催化反应,分别考察了常温下TiO2投加量、反应时间、废水初始pH值、反应气氛等因素对处理效果的影响,并探讨了反应机理。结果表明：TiO2投加量为2 g/L,废水pH=4,300 W高压汞灯照射下,载入60 mL/min的空气反应40 min,120 mg/L EDTA络合铜废水的Cu（II）与COD的去除率达到最高,分别为96.56%和57.67%。     

混凝沉淀-Fenton-NaClO氧化深度处理垃圾渗滤液

用混凝沉淀-Fenton-NaClO氧化联合深度处理垃圾渗滤液,利用单因素变量法得出:混凝实验在PFS投加量为1.2g/L、pH=6、搅拌时间为30min的条件下进行,COD、氨氮和色度的去除率分别达到56.60%、15.62%和56.52%;混凝出水在初始pH为4、H2O2投加量为80mmol/L、n(H2O2)∶n(F2+)比为1∶1、反应时间为60min的条件下进行Fenton氧化,COD、氨氮和色度的去除率分别达到71.38%、21.43%和95.24%;Fenton氧化出水在pH为6、NaClO投加量为60mmol/L、反应时间为60min的条件下进行NaClO氧化,COD和氨氮去除率分别为83.42%和99.57%;联合工艺COD、氨氮和色度去除率分别为96.68%、99.69%和98.04%,出水浓度分别为63mg/L、0.47mg/L和18倍,均可满足《生活垃圾填埋污染控制标准(GB16889-2008)》中规定的排放标准。     

粉煤灰负载铁离子催化氧化活性黄染料废水

以粉煤灰为载体,制备铁/粉煤灰负载型催化剂,并利用该催化剂催化H2O2氧化降解活性黄染料废水,探讨了H2O2投加量、催化剂投加量、染料初始浓度和初始pH值等因素对染料废水COD去除率和脱色率的影响。结果表明,当染料废水COD初始浓度为200 mg/L,初始pH值为1.7,投加0.5 g/100 mL催化剂及加入1.0 mL浓度为1.13 mol/L的H2O2溶液时,处理效果最好,此时染料废水的COD去除率和脱色率分别达到63%和99%,并且废水的可生化性得到很大的提高。利用该负载催化剂能够有效地减少活性黄染料废水中Fe3+的残留量。     

Fe~0类芬顿法深度处理制药废水

以零价铁作为类芬顿反应中的催化剂,对某制药集团经生化处理后的制药废水进行深度处理。研究了H2O2和零价铁粉投加量、pH值以及Fe0的酸改性对处理效果的影响。结果表明:COD去除率20%时,可有效提高废水B/C比。在pH为3.0~3.5时,按H2O2∶COD质量比为1∶6进行投加,Fe0与H2O2按4∶1的摩尔比投加,反应在2 h时能达到处理目标,即去除20%的COD。Fe0的重复使用性良好,5次后仍能保持催化效能,进一步对其中的反应过程与机理做了探讨。研究结果可为制药废水的深度处理提供参考。     

UV/H_2O_2-NaOH沉淀法处理铜-酒石酸络合体系模拟电镀废水的研究

含铜电镀废水中酒石酸等络合剂的存在,使得采用普通氢氧化物或硫化物沉淀法难以满足达标排放的要求。采用UV/H2O2-NaOH沉淀法处理铜-酒石酸络合体系模拟电镀废水,考察了光照时间、初始pH、H2O2投加量等因素对处理过程的影响。结果表明,对于铜-酒石酸络合体系(酒石酸质量浓度为418mg/L,CuSO4·5H2O质量浓度为196mg/L),得出的最佳处理条件为:光照时间70min,H2O2投加量1.07g/L,初始pH 3.0,出水中铜质量浓度可以低于0.3mg/L的排放标准,为后续工业化应用奠定了基础。     

Fenton氧化-活性炭吸附协同深度处理垃圾渗滤液的研究

以上海某垃圾填埋场垃圾渗滤液为研究对象,采用Fenton氧化-活性炭吸附协同处理工艺对其处理效果进行研究。探讨了投加方式以及H2O2浓度、Fe2+浓度、活性炭投加量、温度、pH等因素对COD去除率的影响。结果表明:采用先投加活性炭吸附30 min后投加Fenton试剂反应150 min的方式能够获得最好的COD去除效果。正交实验表明各因素对COD去除的主次关系为:活性炭投加量Fe2+浓度反应温度H2O2浓度pH值;其最优化条件为:活性炭投加量为16g/L,Fe2+浓度为29 mmol/L,反应温度为60℃,H2O2浓度为78 mmol/L,pH值为3。     

Fenton氧化-混凝联合工艺处理络合铜镍废水的研究

采用Fenton试剂氧化-混凝联合工艺对难处理络合铜镍电镀废水进行了研究,考察了废水初始pH值、H2O2初始浓度、[Fe^2＋]/[H2O2]、反应时间和温度、混凝液pH、混凝剂质量浓度对处理过程的影响,探讨了废水的降解途径和机理.结果表明,在体系初始pH=4,温度30℃,H2O2投加量为800mg/L,[Fe^2＋]/[H2O2]=0.1,反应时间60 min,混凝液pH=8及混凝剂质量浓度为500mg/L的条件下,废水的COD去除率为96.98%,Cu^2＋为99.91%,Ni^2＋为99.92%,处理水完全达到国家一级排放标准.同时依据GC/MS对X-GN降解最终产物的分析结果,推导出废水的基本降解机理和途径.     

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.     

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.     

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.     

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.     

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.