镍基催化剂对污泥微波热解制生物气效能的影响

为实现污水污泥减量化、无害化及资源化的目标,在微波热解污水污泥基础上,进行了镍基催化剂对制取生物气效能影响的研究。采用元素分析对污泥元素进行检测,气/质联用分析(GC-MS)和气相色谱(GC)对热解生物气的组成和含量进行测定。实验结果表明,镍基催化剂的添加对微波热解污水污泥制取生物气有较大促进作用。5%添加量与800℃热解终温条件下具有最佳催化效果:生物气中H2、CO产量最大,H2产量由29 g/kg增加到35.8 g/kg,提升23.4%,CO产量由302.7 g/kg增加到383.3 g/kg,提升26.6%;同时催化剂还能提高热能利用效率,降低热解终温,即5%添加量在700℃热解终温时可达到空白800℃时的产气效果;镍基催化剂主要在500~600℃时发挥催化作用,加快了H2和CO的释放。微波热解污泥制取的生物气具有产量大、富含H2与CO等优点,可推动污水污泥的资源化进程。     

污泥连续式微波热解制备生物气

采用升温迅速的微波能作为热源,利用自主设计微波设备对含水率为82%(m/m)的湿污泥进行高温热解实验。采用单因素实验法,探究热解终温、停留时间、活性炭添加量对污泥热解生物气组分和含量的影响规律,确定连续式运行的最佳工况条件:热解终温900℃,停留时间50 min,活性炭添加比例为30%,热解功率1 600 W;在此基础上进行连续12h微波高温热解实验,共热解污泥56 kg,产生生物气32.26 kg,热解油10.98 kg,固体残渣12.66 kg,产气转化率高达57.8%,生物气组分H_2+CO含量高达67%,热解产物具有良好的工业利用价值。污泥热解生物气中H2S浓度超标10倍以上,而NH_3浓度未超标,硫化氢的去除技术研究值得关注。     

城市有机垃圾热解过程中NH_3、H_2S和HCl的析出特性

为了对城市有机垃圾热解过程中NH_3、H_2S和HCl的析出特性进行研究,采用箱式气氛炉在500~800℃热解终温下进行热解实验。热解过程中产生的NH3、H2S和HCl分别用硼酸溶液、乙酸锌-乙酸钠溶液以及Na OH溶液吸收,并分别采用分光光度法和滴定法进行量化。实验结果表明:NH3-N、H2S-S和HCl-Cl的析出率随着温度的升高而增加,热解终温为500、600、700和800℃时,NH3-N的析出率分别为39%、40%、30%和44%,H_2S-S的析出率分别为18%、22%、25%和26%,HCl-Cl的析出率分别为68%、71%、76%和85%;热解终温控制在700℃有利于减少NH3-N的析出,低温热解(500℃)有利于减少H2S和HCl的析出;热解炭中S和Cl的残留率随着热解终温的升高而降低,终温800℃时的残留率分别为41%和5%。     

含油污泥微波热解工艺条件优化现场实验研究

采用自主设计的30 kW大功率微波设备开展了含油污泥微波热解的现场实验,考察了吸波剂种类和添加量、热解终温、微波辐照时间、污泥处理量等对微波热解处理效果的影响.结果表明,污泥热解残渣可以作为吸波剂提高含油污泥的微波热解处理效果,综合考虑热解效果和成本,其较佳的添加量为5％(质量分数),此时污泥的除油率可达99.84％;随着热解终温的升高,污泥的除油率逐渐升高,当热解终温达到500℃时,处理后污泥的含油率降为0.200％(质量分数,下同),满足《农用污泥中污染物控制标准》(GB 4284-84)的限值标准(石油类限值为0.3％(质量分数));微波辐照时间对含油污泥的热解效果影响较显著,当微波辐照时间达到180 min时,处理后污泥含油率仅为0.230％;含油污泥处理量低于20 kg/次时,单位质量含油污泥完成热解消耗的电量随着处理量的增加而减少,而超过20 kg/次时,耗电量随着处理量的增加而增加,因此本实验所用设备较经济的含油污泥处理量为20 kg/次.     

城市干污泥热解气化

针对包头市南郊污水处理厂污水污泥,采用先热解后对热解残渣进行气化的方法探讨城市污泥的有效利用方式。污泥热解实验取升温速率(20~60℃·min-1)和终温(400~600℃)作为影响因素,得出各热解产物产率的变化规律。结果表明,污泥热解在终温为600℃时失重率达到57.53%,焦油产率在450℃达到峰值。污泥残渣的气化分别以水蒸气和CO2作为气化剂,探讨了800~1 000℃范围内的气化产品气组分变化规律。以水蒸气为气化剂时,污泥热解残渣的可制备富氢产品气,产品气中H2体积分数随着反应温度的增加而增加,1 000℃时H2含量可达68.83%,H2+CO含量达到81.36%,低位热值为9.18 MJ·Nm-3。以CO2作为气化剂时,产品气中富含CO,温度越高CO含量越高,1 000℃时到达最大值53.84%,产品气低位热值为7.25 MJ·Nm-3。     

城市污水处理厂恶臭污染源调查与研究

以H2S和NH3为主要监测指标,对广州一大型生活污水处理厂主要恶臭源H2S、NH3的排放浓度进行了8个月的连续监测.结果表明,该污水厂恶臭成分H:S的排放浓度为0.01-22 mg/m',NH,排放浓度为0～0.67 mg/m3.同时,污水厂各处理单元由于其功能和运行条件不同,所产生的恶臭气体成分也不完全一样,在污水进水区段恶臭污染物以H2S为主,其中格栅井H2S浓度最高.其中沉砂池、格栅和污泥浓缩池的H2S、NH3排放浓度呈夏秋季节高、冬春季节低的特征,与季节变化的气温有明显的相关性.对恶臭排放影响因素的研究表明,污水水温越低则H2S和NH3的排放浓度越低,此外,降雨可以显著降低污水处理厂恶臭污染物的排放浓度.     

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%。     

微波干化热解湿污泥的失重和升温特性及残渣分析

为研究湿污泥的微波热解特性,将湿污泥与颗粒活性炭(微波吸收剂)以5∶1的重量比例均匀混合,在300~1 600 W区间取11种不同的微波功率进行热解,同时测量样品的重量和温度。研究表明,添加活性炭的湿污泥在微波功率小于400 W只能加热到90℃,完成污泥脱水。随着微波功率增大,样品失重加快,升温速率和最终温度都增大。微波功率大于800 W样品在1 000 s内加热到300℃,实现快速升温和热解。此时污泥升温有2个峰值,第1个在100℃左右代表水分析出,第2个峰值随着功率增大而提前,代表污泥残渣由于良好的微波吸收能力在微波下迅速升温。推测污泥介电损耗系数在微波加热过程中先因水分蒸发而减小,后因继续升温而增加,有效促进样品吸收微波和二次升温。污泥的重量消减率在微波功率大于600 W时保持在75%左右。污泥热解残渣的碳氢氮元素含量先受到水分析出,后受到低温裂解释放氨气和胺氮类的影响。     

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。     

市政污泥热解产油影响因素及产物应用特性

利用外热式固定床反应器,研究终温、反应时间、升温速率等因素对市政污泥热解产油率的影响,并对产物特性进行了讨论。结果表明,热解终温及反应时间显著影响焦油产率,500℃是适宜的污泥热解温度,焦油产率达24.74%,温度继续升高则半焦缩聚反应强烈,热解气产率大幅增加,焦油产率基本恒定;在10℃·min~(-1)的升温速率条件下,热解终温500℃,维持20 min,焦油产率可达到平衡;升温速率对焦油产率的影响不显著,热解反应达到平衡时,不同升温速率条件下,焦油产率相似;污泥焦油组分与中低温煤焦油相近,具备提酚、制燃料油和特种油品的潜力;污泥半焦灰分高,固定碳含量低,具有一定热值,比表面积较发达,掺混燃烧、制备吸附剂是其重要的潜在利用方向。     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.