印刷电路板基材的热解实验研究

采用热重法对废旧印刷电路板(PCB)在氮气气氛下进行了不同升温速率的热解实验，发现电路板的热解可以分为以下几个阶段：在300℃以下时质量没有什么变化，在300～360℃时质量急剧减少，在360～1000℃时质量减少得比较缓慢。随后本文对电路板的热解进行了动力学回归。研究表明，样品热解反应分为2个阶段，这2个阶段反应过程中的活化能有很大差别，说明这2个阶段受不同的化学反应机理控制。     

含油污泥与玉米秸秆共热解协同特性

利用热重-傅里叶变换红外分析仪(TG-FTIR)对含油污泥与玉米秸秆共热解特性进行了研究,分析了各温度段的协同效应。TG分析表明,共热解主要呈现3个阶段:挥发分的析出(210～520℃)、碳酸盐的分解(600～780℃)、长链难分解重质油的热裂解和半焦的气化(900～1100℃),且在不同热解阶段呈现出不同的协同效应。热解动力学分析表明,含油污泥与玉米秸秆共热解后,第1阶段的活化能有所增高,而第2、3阶段的活化能大幅降低。FTIR分析表明,第1、2阶段,共热解与单一物料热解的产物种类基本一致,而在第3阶段,共热解使含油污泥热解产物甲基化合物发生分解和转化。含油污泥与玉米秸秆共热解可促进CO_2、CO、CH_4和C=O化合物的析出,其中添加玉米秸秆质量分数为10%时,对CO_2、CO和CH_4析出的促进作用最强,添加30%时则对C=O化合物的析出更为有利。     

废弃电路板中环氧树脂真空热解规律的研究

真空条件下,应用程序升温管式电炉对废弃电路板中环氧树脂热解规律进行了研究.考察了不同的热解终温(200～700 ℃)、升温速率(5～30 ℃/min)、真空度(以压力表征,3～30 kPa)及保温时间(10～150 min)对热解产物产率的影响.实验结果表明,热解终温是影响热解油产率最重要的因素;选择适当的热解终温(400～550 ℃)、升温速率(15～20 ℃/min)、真空度(15 kPa)及保温时间(30 min)有利于提高热解油产率.     

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.     

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。     

市政污泥热解特性及含碳官能团演化过程分析

我国市政污泥年产量大,研究其热解机理和碳形态转化可为实现污泥无害化和资源化提供理论基础。采用热重、动力学拟合、红外光谱(FTIR)、X射线光电子能谱(XPS)等检测和分析方法,对市政污泥热解特性、活化能变化和含碳官能团进行分析。结果表明：市政污泥热解过程中含碳官能团的生成在不同的阶段存在差异,进一步采用Kissinger-Akahira-Sunose (KAS)法、 Flynn-Wall-Ozawa (FWO)法和Friedman法进行动力学分析,其活化能结果显示在转化率为0.40～0.70时,市政污泥热解速率加快,污泥中含碳官能团加速发生热解转化。FTIR和XPS结果表明,在400℃以下时,醇羟基的分解是导致污泥结构中羟基减少的主要原因。在400℃时,酚羟基和C=O键相对质量分数最多,而在500℃时,羧基和C-O键相对质量分数最高。C=C键和C-N键随温度升高持续减少,C-C结构则先减少后增加,在500℃时相对质量分数最低,而芳香结构随温度的上升持续增加。在400～600℃内,污泥残炭的含碳氧官能团较多,吸附性和稳定性较高。本研究结果可为市政污泥热解机理及碳形态转化提供参考。     

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。     

不干胶废弃物热重分析

为了探索不干胶类包装废弃物的热解特性,采用热重分析手段分析了不同升温速率条件下不干胶类废弃物的失重特点,并且采用Ozawa法和KAS法比较分析不同转化率条件下的表观活化能分布.热重分析结果表明,不干胶类废弃物的热解主要分为3个阶段:第1阶段(室温～ 200℃)为不干胶类废弃物的干燥阶段,第2阶段(200 ～ 590℃)为热解的主要阶段,第3阶段(590 ～800℃)为热解半焦的深度热解阶段.升温速率对热解失重率有重要影响,Ozawa法和KAS法计算结果表明,2种方法计算的热解活化能比较接近,Ozawa法得到的活化能为349.9 kJ/mol,KAS法得到的活化能为336.9kJ/mol;并且不干胶类废弃物的热解表观活化能呈现出阶段性分布.     

城市生活垃圾与园林废弃物的共热解特性

为实现城市生活垃圾减量化、无害化和资源化,采用热重分析天平和实验室固定床热解反应器进行城市生活垃圾(MSW)与园林废弃物共热解实验,研究了不同热解终温、松树枝和柳树枝添加比例对热解产物产率影响,并利用气质联用色谱分析仪(GC-MS)对热解油进行表征分析。实验结果表明:MSW、松树枝和柳树枝的热解过程均可以分为3个阶段,主要包括脱水、热解、炭化;MSW、松树枝和柳树枝单独热解时最大失重速率分别出现在321.48、358.23和377.83℃;MSW与松树枝共热解DTG曲线在热解反应第2阶段有2个析出峰,分别在342.32℃和471.48℃,比MSW单独热解时,失重率增加了7.29%。当城市生活垃圾与松树枝、柳树枝的添加量分别为3∶1时,热解液体产物产率明显升高,热解油中醇类、羧酸类、醛类等含氧有机物的含量降低,热值增加,热解油中氧含量降低,且松树枝对共热解焦油的脱氧效果更为显著,热解油品质得到提升。     

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℃。     

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.     

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.     

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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)