生物质废弃物催化裂解制备富氢燃气实验研究

由生物质废弃物催化裂解制取氢气是一种可再生的制氢方法，本研究采用2段加热管式反应器，前段装生物质，后段装催化剂，用以研究生物质催化裂解制取氢气的特性，并提出潜在氢产率的概念对生物质制氢的经济技术可行性进行深入的分析。测试的3种生物质废弃物为：松木粉、木质素和纤维素，测试温度为600～700℃。实验结果表明，加入催化剂后3种物料的产氢率从5．48～15．06g／kg增加到12．94～37．73g／kg；催化剂对潜在产氢率的影响较小，加入催化剂前后的变化范围为：36、25～98、86g／kg到37．40～116．98g／kg。生物质废弃物催化裂解产氢率与相同温度下空气-水蒸气气化的氢产率相当，实验结果证明，生物质废弃物催化裂解是一种有效的制氢方法。     

生物质催化气化制取富氢燃气的研究

以流化床为反应器 ,探讨了一些主要参数如 :反应器温度 ,水蒸气 ,当量比ER以及催化剂对气体成分、氢产率和潜在氢产率的影响。实验所用催化剂为白云石和镍基催化剂。在实验条件范围内 ,氢产率为 2 2— 83g/kg生物质 (湿基 ) ,潜在氢产率为 115— 2 2 3g/kg生物质 (湿基 )。结果表明 ,较高的反应器温度 ,适当的水蒸气添加量可以有效提高氢的产出 ;白云石和镍基催化剂可使产品气中的氢含量提高 10 %以上。     

生物质催化气化制取富氢燃气的研究

以流化床为反应器，探讨了一些主要参数如：反应器温度，水蒸气，当量比ER以及催化剂对气体成分、氢产率和潜在氢产率的影响。实验所用催化剂为白云石和镍基催化剂。在实验条件范围内，氢产率为22—83g／kg生物质(湿基)，潜在氢产率为115—223g／kg生物质(湿基)。结果表明，较高的反应器温度，适当的水蒸气添加量可以有效提高氢的产出；白云石和镍基催化剂可使产品气中的氢含量提高10％以上。     

温度和水蒸气流量对烟秆高温气化的影响

利用上吸式固定床反应器,对烟秆进行了水蒸气气化实验,在617~1 435℃的温度范围内研究了温度及水蒸气流量对气化特性的影响。结果表明,当气化温度低于917℃时,升高温度可同时促进均相和非均相产氢反应的进行,产氢率随着温度升高而迅速上升。当温度上升到917℃时,非均相反应已进行得足够充分,潜在产氢率达到最大值,碳转换率超过0.8。当温度超过917℃后,温度升高对产氢的影响主要体现为促进均相反应进行,产氢率上升变缓。温度达到1 327℃时,均相反应速率足以使气体在反应器内反应完全,因而升高温度不再有助于提高产氢率,产氢率最大值为0.97m~3/kg。水蒸气流量增加能够促进气化产氢反应与水蒸气扩散,同时会缩短气体停留时间、降低局部温度,因此,随着水蒸气流量增加,产氢率先升高后降低,在917℃时烟秆气化的最佳水蒸气流量为15.7 g/min。结果可以为生物质高温气化制氢的研究提供参考。     

废弃物生物质液化制取生物油的研究进展

废弃物生物质处置不当引起的环境污染与潜在资源浪费已引起了广泛关注,而废弃物生物质液化制取生物油是解决有机废弃物污染及其能源化再利用的一种新技术。在对多糖、木质素、蛋白质、油脂等生物质大分子聚合物的液化机制阐述分析的基础上,讨论了温度、加热速度、粒径、压强、停留时间、液固质量比,特别是催化剂以及还原气和供氢剂等反应条件或参数对生物油的影响机制,最后介绍了生物质液化油的物理化学性质以及该技术存在的若干问题。     

温度和底物浓度对混合菌群木糖厌氧生物产氢的影响

为了获得混合菌群利用木糖进行厌氧发酵产氢的最佳条件,通过批次实验,对中温(35℃)和高温(55℃)下混合菌群利用不同浓度木糖(10~50 g/L)厌氧发酵产氢系统进行了研究。结果表明,35℃下系统累积产氢量和最大氢气产率在底物浓度30 g/L时获得,乙醇和乙酸为主要产氢副产物,但继续提高底物浓度会造成系统VFAs的积累与p H下降,不利于木糖代谢产氢;而55℃下累积产氢量和氢气产率随底物浓度升高持续增长,乙醇为系统主要产氢副产物,VFAs累积量较少。高温下,虽然最大氢气产率和底物木糖降解量比35℃下的低,但有利于获得较为稳定的氢气产量,产氢系统在高底物浓度下也可保持较高的木糖降解率和较为稳定的p H,有利于木糖代谢产氢。     

典型农业废弃物干式厌氧发酵产氢影响因素的研究

以5种典型农业废弃物(猪粪、鸡粪、秸秆、餐饮垃圾和厨余垃圾)为研究对象,采用干式厌氧发酵产氢技术,研究不同初始pH、温度对产氢潜力和代谢途径的影响。结果表明,当中温、初始pH为7.0时,餐饮垃圾产氢效果最佳,最大累积产氢量为261.96mL,最大产氢速率为15.18mL/h,氢气体积分数最大值为64.61%;当中温、初始pH为6.0时,秸秆产氢效果最好,最大累积产氢量为254.41mL,最大产氢速率为24.50mL/h,氢气体积分数最大值为65.54%。5种农业废弃物干式厌氧发酵产氢的代谢途径均以丁酸型发酵为主。     

生物质快速热裂解主要参数对生物油产率的影响

以松木木屑为原料,在自制的小型流化床上,开展了生物质热裂解温度、生物质粒径和进料速率对生物油产率的影响实验研究.结果表明,在热裂解温度分别为450、475、500、525和550℃条件下,当热裂解温度为500℃时,生物油产率最高,平均产率达到53.33%(质量百分比).反应温度越高,炭产量越低,不可冷凝气体产量越高,气体发热值越高;粒径＜1 mm的生物质其粒径对生物油产率影响不大;生物质进料速率增加时,生物油产率增加.本研究为生物能的利用提供了新的途径.     

厌氧序批式反应器产氢

以啤酒厂废水处理厂UASB中的厌氧污泥为种泥,葡萄糖为基质,研究了厌氧序批式反应器产氢。控制反应器内pH为4.0～4.5,温度为（36±1）℃,水力停留时间为8 h,当进水葡萄糖浓度为4 000 mg/L,容积负荷为12 kg/（m3.d）条件下,该厌氧序批式反应器实现了连续高效厌氧产氢。生物气中的氢气含量约为48%～53%,基质产氢率为1.1 mol/mol葡萄糖,COD去除率为15%～25%,最大比产氢速率为84.5 mol/（kg VSS.d）。液相末端发酵产物中乙醇和乙酸的含量占液相末端发酵产物总量的80%以上,表明该反应器内进行的是乙醇型发酵厌氧产氢。厌氧序批式反应器完全可以实现连续高效厌氧产氢,比较适用于日处理量较小的高浓度含糖废水。     

生物质快速热裂解主要参数对生物油产率的影响

以松木木屑为原料,在自制的小型流化床上,开展了生物质热裂解温度、生物质粒径和进料速率对生物油产率的影响实验研究.结果表明,在热裂解温度分别为450、475、500、525和550℃条件下,当热裂解温度为500℃时,生物油产率最高,平均产率达到53.33%（质量百分比）.反应温度越高,炭产量越低,不可冷凝气体产量越高,气体发热值越高;粒径＜1 mm的生物质其粒径对生物油产率影响不大;生物质进料速率增加时,生物油产率增加.本研究为生物能的利用提供了新的途径.     

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.     

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.