直流电晕放电降解甲苯的特性研究

利用直流高压电晕产生的非平衡等离子体分解甲苯.考察了各种因素对甲苯降解效率的影响,并对降解机理进行分析.研究结果表明:放电时间的延长、放电电压的提高、适宜的相对湿度和较低甲苯的初始浓度都有利于提高甲苯的降解效率.     

介质阻挡放电和水吸收联合降解挥发性有机化合物

依据介质阻挡放电(DBD)和溶液吸收处理气态污染物的原理,设计出一种DBD和水吸收联合降解挥发性有机化合物(VOCs)的实验装置.研究其对甲苯的降解效果.考察了放电电压、甲苯初始浓度、模拟废气流量对甲苯降解效果的影响.分析了DBD和水吸收的相互作用.结果表明.DBD和水吸收联合可以提高甲苯的降解率.在放电电压为15.9 kV时甲苯的降解率为81.5%.比单独放电时提高了13.3百分点;甲苯的降解率随着放电电压增大而升高,随着气体流量和甲苯初始浓度增大而降低.该技术可以作为放电等离子体前处理工艺,为高效处理上业废气提供参考.     

电晕-介质阻挡协同放电低温等离子体降解大流量甲苯废气的研究

利用自制电晕-介质阻挡协同放电低温等离子体降解大流量甲苯废气,运用均匀设计法优化获得甲苯降解的适宜条件,探究了各因素及因素间交互作用对甲苯降解的影响,并开展甲苯降解动力学分析。结果表明:降解甲苯的最佳条件为工作电压13kV、放电频率6.5kHz、废气流量为1.0L/min,甲苯初始质量浓度924mg/m~3,在此条件下甲苯气体降解率为94.93%,能量效率为0.63g/(kW·h);甲苯降解符合一级反应动力学,甲苯降解反应速率常数与输入功率具有良好线性关系。     

介质阻挡放电联合催化臭氧化降解甲苯

采用介质阻挡放电区后结合MnOx/Al2O3/发泡镍去除甲苯,考察甲苯进气方式、臭氧产生方法及湿度对甲苯与O3同时去除的影响。结果表明,O3是等离子体区后催化降解甲苯的主要物种,介质阻挡放电联合催化臭氧化可实现甲苯及O3的同时高效去除。输入电压为9.0 kV时,甲苯的去除效率达92.8%,在80 min内O3的去除效率维持在99%以上。水蒸气对催化剂催化分解臭氧的活性没有直接的影响,O3浓度较高时湿度对甲苯降解效率的影响很小。GC-MS分析结果表明,甲苯降解的主要气相副产物有烷烃、酸、酮和含苯环有机物,提出了甲苯的降解途径。     

介质阻挡放电等离子体降解高浓度甲苯

为解决喷漆和涂装废气中VOCs的污染,采用同轴圆管式介质阻挡反应器进行低温等离子体降解高浓度甲苯探索,研究了反应器参数（放电间距、放电长度）、操作参数（初始甲苯浓度、气体流量、输入功率）等关键参数对甲苯转化率和产物CO2选择性的影响。结果表明：放电间距过大或者过小都不利于甲苯的降解,放电长度的增加对其影响相对较小;输入功率越大,甲苯的降解效果越好,并且反应产物中臭氧的浓度越低,但气体流量及初始甲苯浓度的增加不利于甲苯的降解。最后对产物进行GC-MS检测,分析了甲苯降解机理。     

DBD反应器电极结构对放电特征及甲苯降解效果的影响

为研究DBD反应器电极结构对放电特征和甲苯降解效果的影响,设计了具有3种不同结构高压电极(棒、螺纹棒、线圈)和接地电极(铜网、铜带、铜丝)的反应器。通过放电图像、发射光谱、电压-电流波形、李萨如图、放电功率和放电间隙气体温度分析了不同电极结构反应器的放电特性;以甲苯去除率、矿化率、能量效率为评价指标,考察了电极结构对甲苯降解效果的影响。结果表明：3种不同结构高压电极反应器的放电强度顺序为线圈>棒>螺纹棒;当甲苯质量浓度为678 mg·m⁻³、电压为12~20 kV、且以线圈为高压电极时,反应器的放电功率、放电间隙气体温度低,分别为0.4~10.3 W、28~64 ℃,而对甲苯的去除率、矿化率、能量效率均最高,分别为77.71%~100%、21.03%~35.96%、4.96~8.81 g·kWh⁻¹;3种不同结构接地电极反应器中以铜带为接地电极时放电强度最强,对甲苯的去除率、矿化率和能量效率最高,分别为25.3%~100%、3.41%~35.96%、4.96~23.17 g·kWh⁻¹。本研究可为DBD反应器在降解甲苯应用中的结构优化和材料选择提供参考。     

活性炭吸附和脱附-等离子体氧化净化有机废气的研究

根据滑动弧放电等离子体适于降解高浓度有机物废气的特性,结合活性炭吸附法,提出了吸附器的吸附浓缩和热脱附-等离子体氧化净化有机废气的方法。在活性炭吸附过程中,最初2 h内甲苯净化率达到100%,随着时间的增加净化率下降;在热脱附滑动弧放电等离子体净化过程中,甲苯降解效率最高为97.3%。将滑动弧放电等离子体反应器出口气相产物收集进行FT-IR检测,发现放电后有CO2、CO、H2O和NO2产生,并分析了甲苯的降解机理。     

介质阻挡放电-催化降解空气中甲苯的研究

着重考察了催化剂分解O3对介质阻挡放电-催化降解甲苯效果的影响,对比不同催化剂在3种催化剂结合方式下对O3分解能力及甲苯降解效果.同时研究了影响O3,产生及分解的条件--放电电压、水汽和氧含量对甲苯降解的影响.结果表明,催化剂的O3分解能力越强,对甲苯的降解效果越好,O3的催化分解在甲苯降解过程中起重要作用.当放电电压为10 kv时,在余辉区和等离子体区加入催化剂,甲苯的去除率分别由无催化剂时候的33.8%提高到55.6%～66.2%和65.2%～74.2%.气流中的水汽对O3的产生和分解都产生不利影响,可降低甲苯的去除率.氧气含量高时,一方面增加O3的产生,另一方面降低催化剂对O3的分解,在O3含量为5%时,甲苯去除效果较佳.     

脉冲放电降解实际空气流中甲苯的实验研究

研制了一种喷射式线-筒放电反应器,在室温条件下进行了降解实际空气流中甲苯的实验研究。结果表明,该反应器能够有效降解甲苯,但不同的通气方式对甲苯降解率有显著影响,验证了该反应器设计的合理性。同时证明,通过流场控制可以提高甲苯降解率。电场方向与气流方向一致则强化降解,两者方向相反则弱化降解。当电压为34kV时,正脉冲和负脉冲的甲苯降解率相差高达42.5%。当电压小于火花放电电压时,甲苯降解率随着电压的增大而升高;当电压过大时,电极间发生火花放电,甲苯降解率不升反降。小电压时,小电容放电的甲苯降解率较高;但随着电压的增大,大电容的优势得以体现。甲苯降解率随气流中甲苯初始浓度的升高而降低;随气体流量的增大而降低;环境湿度过大时,甲苯降解率下降,并且甲苯氧化不完全,有CO生成。     

单介质和双介质阻挡放电低温等离子体降解甲苯的比较

为研究介质阻挡放电(DBD)反应器结构对低温等离子体降解甲苯的影响,设计了具有单层介质和双层介质的DBD反应器。对2种反应器的放电特征、甲苯去除率、矿化率、CO₂选择性和能量效率进行了比较,并对施加电压和初始浓度对甲苯降解效果的影响进行了分析。结果表明：在相同电压下,双介质反应器(DDBD)具有更高的电场强度,而单介质反应器(SDBD)的输入功率更高;当甲苯浓度和电压分别为616、1 027、1 848 mg·m⁻³和14~24 kV时,双介质中的甲苯去除率为9.4%~100%、7.4%~99%、5.1%~64%,单介质为67%~98%、46%~90%、26%~59%。这说明低电压下单介质反应器的甲苯去除率更高,而高电压下则相反,并且,浓度降低、电压升高有利于甲苯的降解。单介质反应器的能量效率随电压升高而降低,双介质反应器则先升高后下降,且双介质反应器的能量效率高于单介质反应器(16~24 kV)。以上研究可为介质阻挡放电在VOCs去除方面的应用提供参考。     

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.     

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.     

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.     

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.     

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.     

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 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.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

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.