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。     

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。     

添加秸秆对废橡胶/塑料共热解制油特性的影响

针对难降解类垃圾资源化处理的难题,利用固定床系统对废弃橡胶/塑料以不同比例掺混进行了共热解制油实验,研究掺混燃料中添加少量秸秆对共热解特性的影响。结果表明,橡胶和塑料共热解,较各自热解的得油率和油发热量增加,橡胶/塑料比例2∶3~3∶2时,制油收益率最佳;添加秸秆,能够促进热解反应提前进行,进一步提高得油率和油发热量同时提高了固体残渣的热值,则制取热解油的收益率明显提高。橡胶/塑料比例4∶1的混合燃料,添加秸秆共热解获得了最高得油率,油发热量为39.93 MJ/kg。     

城市生活垃圾热解重整制合成气计算分析

基于热化学平衡对热解重整制取合成气工艺进行了建模分析,考察了垃圾收到基水分M_(ar)、干燥基灰分A_d、热解装置入口垃圾含水率和合成气燃烧比例对能量转化率、干合成气产率、干合成气低位热值、合成气组分等的影响。结果表明:该工艺对于收到基低位热值大于6.7MJ·kg~(-1)的生活垃圾可以产生标况下低位热值高于5.3 MJ·m~(-3)的干合成气;垃圾收到基水分和干燥基灰分的增加会大幅降低能量转化率、干合成气产率和低位热值。     

餐厨垃圾中典型组分的裂解液化特征研究

利用实验室规模的实验装置管式加热炉进行餐厨垃圾热解实验,实验分析了反应温度对餐厨垃圾热解产物分布的影响,米饭、白菜、猪肉、塑料和纸5种原料在最佳温度下可实现热解油质量产率的最大化,分别为45.02%、24.55%、61.19%、73.77%和24.86%。其中,米饭和白菜热解油含水率较高,可达到30%~40%,将含水率降到15%后,测定热值分别为25.51 MJ/kg和17.75 MJ/kg。塑料和纸混合热解时,塑料热解过程的放热效应可缩小纸的热解温度区间,增加热解油产量。红外光谱分析厨余热解油包含多种含氧有机物。通过气质联用仪(GC-MS)分析塑料热解油和塑料与纸混合热解油在180℃以下蒸馏出的液相产物,主要组分为烷烃和烯烃,从成分和热值分析,与汽油、柴油相近。     

润滑油废白土的热解处理

以润滑油废白土为原料,利用电热解法,研究了热解终温、加热速率和CaO添加量对热解产物的影响。实验结果表明:热解终温对热解产物的影响最为显著。随着热解终温的升高,不凝气产量和产油率均迅速增加。当热解终温达到600℃时,其增加的速率逐渐缓慢增大。当控制热解终温为800℃、加热速率为16℃/min、CaO添加量为0.5%时,富氢气体产量为189.2 L/kg,气体中主要成分为H2和CH4,其含量分别为27.97%和41.64%;热解残渣含油率和重金属溶出物均低于标准规定值,热解油产率为10.98%,回收率为38.94%,其主要成分为汽油、柴油和重油3部分组成,分别含19.13%、31.35%和49.52%。     

炼焦煤尾煤催化热解制取富氢燃料气

以炼焦煤原煤、尾煤为研究对象,采用微量热重、常量固定床实验装置对其在热解过程中的质量变化和气相产物进行了对比分析。考察了温度、6种催化剂（CaO、MgO、Fe、Ni、NaOH、A1）及其添加比例对炼焦煤尾煤热解制取富氢燃料气的影响。结果表明,尾煤中富集的无机矿物质对热解制取富氢燃料气有促进作用,单位尾煤热解H2产率要比原煤高出1．93％。温度是影响尾煤热解产气的重要参数,热解终温的上升有利于H2产量的提高,随终温800℃升高到950℃H,产量增长了32．59mL／g。在催化热解实验中,除Al和MgO对尾煤热解有抑制作用外,CaO、Fe、Ni及NaOH均对尾煤热解产H2有促进作用,以CaO和Fe效果最为明显。并且不同添加比例的CaO和Fe对热解制取富氢燃料有一定的影响。     

城市生活垃圾填埋初期有机质演化规律研究

为阐明生活垃圾填埋初期有机质演化规律,于填埋场打井采集填埋1～3年3个不同时期垃圾样品,用水浸提制备水溶性有机物(DOM)。采用红外光谱、同步荧光光谱及紫外光谱,对浸提液中DOM的结构和演化特征进行了研究。结果显示,生活垃圾中含有脂肪类、蛋白类、糖类及木质素类物质,在填埋初期,有机质中的脂肪类、蛋白质类、糖类及木质素类物质均发生了降解,羧基、氨类及水溶性芳香结构物质减少,DOM分子量降低。研究结果表明,垃圾填埋初期有机质以降解为主。     

TiO_2/MCM-41的制备及对含油污泥热解过程的影响

利用溶胶-凝胶法合成了不同钛含量的MCM-41负载二氧化钛的催化剂(TiO2/MCM-41),采用红外光谱、扫描电镜、N2-吸附脱附和X-射线衍射对催化剂的结构进行了表征,并首次将其应用于含油污泥热解过程中,利用气质联用质谱仪对回收的油气品质进行了分析。结果表明,添加TiO2/MCM-41能将含油污泥热解油的回收率由76.04%提高到83.88%,热解温度降低21℃,还能改善热解油品质。     

生活垃圾和玉米秆混合热解动力学及产物分布

为探讨生活垃圾和玉米秆共热解过程中的协同关系和产物分布,采用热重分析仪对生活垃圾、玉米秆及其混合物进行了热解实验研究,并进行动力学计算。结果表明,混合热解可分为脱水、热解、炭化、焦催化气化4个阶段,前3个阶段与单独热解过程类似,第4个阶段与单独热解相比失重明显增加,表明混合热解过程中存在协同效应;混合物热解的实际活化能为28.492 k J/mol,低于单独热解及其混合物热解理论活化能,可见混合热解利于热解反应进行。为明晰混合热解对热解反应的促进作用,利用固定床热解实验,研究了混合比例对产物产率和热解气各组分产率的影响。结果表明,在不同混合比例下,固液实际产率低于理论值,而气体实际产率则比理论值高;混合物料热解气中H2、CH4、CO2产量均高于其理论值,而CO产量却相反,低于其理论值。     

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.     

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.     

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.     

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 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.