印刷线路板废弃物的热解与动力学实验研究

分别应用管式炉反应器和热重分析手段对印刷线路板废弃物的热解行为和热解动力学进行了实验研究。在管式炉中，研究不同的热解温度：700～950℃，对产物分布和气体成分分布的影响。实验结果表明：PCB热解气体的主要成分是H2和CO2，气体的热值较低，仅为2．09～5．41MJ/m^3，PCB不适合以气体产物为目标的能源利用方式。应用Friedman方法对PCB的热解动力学进行了研究，求得PCB的热解动力学参数分别是：表观活化能190．92kJ/mol，反应级数5．97，指前因子lnA47．14min^-1。     

废聚氨酯的热解及产物分析

利用热重分析仪和管式炉对废聚氨酯进行热解实验,研究了废聚氨酯的热解特性及热解产物.结果表明,废聚氨酯热解有3个失重阶段,热失重主要发生在200～440℃,600℃热失重趋于稳定.红外光谱图分析发现,热解过程中有大量CO和CO2产生.气质联用检测结果分析显示,热解产物复杂,液体产物中检出苯胺、p-苯胺、苯甲腈等多种芳香类化合物,气体产物以低碳的烷烃和烯烃为主,还检测出有机氯化合物,这是废聚氨酯中氟利昂类发泡剂所致.     

灰色预测模型及分布活化能模型在废电路板热解中的应用

分别在管式炉反应器和热天平上对废电路板的热解行为进行实验研究。在管式炉反应器上考察了在同一升温速率（20 K/min）下不同热解终温 (400、500、600、700和800℃) 对废电路板热解产物产率的影响。在相关实验数据的基础上尝试用灰色理论及方法建立基于热解终温的废电路板热解灰色产率预测模型GM(1,1)，预测结果与实验数据对比表明，该预测模型精度较高，能够较好地对不同热解终温下废电路板热解产物产率进行预测。此外，在热天平上获得的不同升温速率（10、15和20 K/min）下的热失重曲线表明，废电路板的失重速率峰随升温速率的提高逐渐向高温侧移动。采用分布活化能模型对废电路板热失重曲线进行动力学分析，获得废电路板热解活化能的变化曲线。计算结果表明，废电路板热解过程中活化能并不是单一数值，而是随失重率变化的一个函数。所得废电路板热解活化能值在140～250 kJ/mol范围内变化，当失重率在10%～60%之间，活化能值总体呈缓慢上升的趋势，但当失重率＞60%时，活化能值由155.4 kJ/mol迅速增加到244.4 kJ/mol。     

热解技术在废旧印刷电路板处理及资源化中的应用

综述了热解技术在废旧印刷电路板(printed circuit board,PCB)处理及资源化中应用的研究状况.热解技术可以改善和提高PCB中金属物质的回收效果,减少污染.同时,以热解为基础的PCB中非金属物质回收技术也有着很好的发展前景.PCB热解动力学的研究表明其在1000℃以下的热解过程可划分为分别服从不同反应机理的2个阶段.PCB热解产物中的油、气产物可以回收作为化工原料或燃料.PCB热解过程中含溴阻燃剂的转化和迁移规律以及热解产物中含溴污染物的控制和脱除、热解技术与其他PCB资源化技术的合理有效整合是今后研究的重点.     

利用旋转炉热解城市污泥的产物特性

采用旋转管式加热炉实验台在惰性条件下对城市污泥进行了热解实验,系统研究了不同热解温度对气态产物和固态产物成分的影响。结果表明:污泥经热解后的产物在600℃时,比表面积最大值为158.02 m2/g,孔容最高为109.58 mm3/g。随着热解温度的升高,气态产物和液态产物的产率增加,而固态产物则减少。在热解温度450~750℃,热解产物中的固态产物产率由53.65%降至31.69%;气体产率从11.23%升至24.74%,其中H_2、CO、CO_2、CH_4、C_2H_4、C_2H_6和C_2H_2占总气体的75%以上,H_2含量随着热解温度的升高而升高。热解气中小分子碳氢化合物含量较高,600℃时热解气体中含氢气体主要包括:H_2、CH_4、C_2H_4、C_3H_8、正丁烷(C_4H_(10))及C_2H_6等,其中H_2和CH_4含量分别为27.98%和23.63%。CH4、C3H8、C_4H_(10)等气体的含量随着热解温度的升高呈现先增后减趋势,且在600℃达到最大值,C_2H_2、C_2H_6在450℃时其浓度最高。随着热解温度的升高,N、C和H3种元素在热解固态产物中的质量分数呈明显下降的趋势。     

热解技术在废旧印刷电路板处理及资源化中的应用

综述了热解技术在废旧印刷电路板（printed circuit board，PCB）处理及资源化中应用的研究状况。热解技术可以改善和提高PCB中金属物质的回收效果，减少污染。同时，以热解为基础的PCB中非金属物质回收技术也有着很好的发展前景。PCB热解动力学的研究表明其在1000℃以下的热解过程可划分为分别服从不同反应机理的2个阶段。PCB热解产物中的油、气产物可以回收作为化工原料或燃料。PCB热解过程中含溴阻燃剂的转化和迁移规律以及热解产物中含溴污染物的控制和脱除、热解技术与其他PCB资源化技术的合理有效整合是今后研究的重点。     

初始温度对废轮胎热解的影响

以管式炉热解实验和热重分析为基础,研究了初始温度对废轮胎热解产率及气相产物特性影响。结果表明,初始温度对废轮胎的热解存在重要影响。热重分析结果表明,废轮胎的热解过程存在2个主要失重过程,第一失重温度区间为200～500℃,第二失重温度区间为650～800℃;升温速率仅改变了热解的最大失重速率,并未改变废轮胎最终热解失重率;可通过提高升温速率能够缩短热解反应时间。在初始温度低于100℃时,废轮胎在800℃时热解已基本结束;当终温为800℃、初始温度在100～550℃范围内时,随着初始温度的提高,固、气两相产物产率均提高,而液相产物产率降低;其中气相中H2、CO和CH4的含量高于初始温度小于100℃时的含量;分析认为,可以通过调节热解的初始温度调节废轮胎热解在不同热解阶段的时间分配,适当提高热解初始温度有利于提高整个热解过程中的时间利用效率、改变废轮胎热解产物的分布;废轮胎热解气化的最佳温度区间为500～800℃。     

有机固体废弃物热解生产脱水内醚糖的研究

以有机固体废弃物 (废棉絮、废纸 )为原料 ,在管式炉热解反应器热解生产脱水内醚糖。研究了热解温度对热解产物相态分布的影响。同时 ,利用HPLC对脱水内醚糖的产量进行了测定。HPLC分析结果表明 :热解液水相中主要化学物质是乙酸 ,而非水相中主要化学物质是脱水内醚糖     

干化污泥热解制备可燃气过程中石英砂的影响

污水污泥样品经过105℃干燥处理后,在管式电阻炉和热天平上分别以15℃/min升温速率,在0～950℃温度范围进行污泥混合石英砂的热解实验研究。石英砂污泥混合热解实验发现:混合热解的产气总量得到提高,石英砂的加入不改变污泥热解生成可燃气的规律。在热解的高温段(800～950℃),由于加入了石英砂,CO浓度得到了提高。     

废弃中药渣催化热解制取生物油的研究

利用热重分析仪(TGA)对植物类中药渣的热解特性进行了研究,用Coats-Redfern积分法计算了其热解动力学参数,得出中药渣热解反应符合一级反应动力学方程,其活化能较低,为36.0kJ/mol。考察了热解温度对气体、液体、固体产物的影响,在723K时,液体产物生物油产率最高,为39%。以介孔分子筛SBA-15以及分别负载Al、Sn、Ni、Cu和Mg的SBA-15作为催化剂,研究催化热解对气体、液体、固体产率及生物油组分的影响。研究表明,Al-SBA-15的催化效果较好,液体产率最高,为36%;采用元素分析仪和热值测定仪,得到用Al-SBA-15作为催化剂时生物油的氧质量分数最低,低位热值最高。用GC/MS对生物油组分的分析结果表明,添加Al-SBA-15后,热解产物中脂肪族和芳香族化合物增加,而含氧化合物减少。     

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.     

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.