V_2O_5共混制备改性活性焦的脱硫性能及机理

以煤为原料、V2O5为添加剂共混制备新型活性焦(V/AC),研究了该活性焦的物理化学特征和脱硫性能,并探讨了改性活性焦脱硫机制。研究表明,改性活性焦的得率随V2O5负载量增加而增加,其脱硫性能均比未改性的活性焦高。当V2O5负载比例为12%时,碘值达到最大,为415 mg/g;其脱硫性能也最高,穿透硫容达到136.42 mg/g炭,比未改性活性焦增加约38.23%。BET结果表明,改性活性焦主要以微孔为主;红外光谱分析显示活性焦表面存在醇、羧酸、酚或醚类官能团。改性活性焦的脱硫机制包括:V2O5在活性焦表面主要以V2O3存在,脱硫时在氧气的存在下转化为V2O5;V/AC吸附、氧化SO2形成具有VOSO4结构的中间体,此中间体与O2反应生成V2O5和SO3,SO3或与H2O结合所成的H2SO4迁移到V2O5周围的微孔中。     

过渡金属浸渍改性ACF去除H_2S研究

为探讨活性炭纤维（ACF）去除恶臭气体H2S的性能,采用过渡金属浸渍改性ACF吸附H2S,揭示出改性ACF前后吸附H2S的性能差异及浸渍剂的浓度和种类对ACF吸附性能的影响。结果表明,通过过渡金属改性后的ACF吸附性能有显著提高,对H2S吸附是物理吸附和化学吸附共同作用的结果,改性后的ACF硫容量大小依次为：5%硝酸铜改性ACF〉5%硝酸钴改性ACF〉5%硝酸锰改性ACF。不同浓度浸渍剂改性后的ACF吸附H2S性能有所不同,硫容量呈现出随着浓度升高先增大后减小的趋势。不同浸渍剂改性后的ACF吸附穿透曲线也不同,穿透时间依次为：TCu-ACF〉TCo-ACF〉TMn-ACF。混合金属溶液改性ACF吸附H2S,5%硝酸铜-3%硝酸钴溶液改性ACF吸附性能最佳,硫容量可达166.7 mg/g;而5%硝酸铜-3%硝酸钴-1%硝酸锰溶液改性的ACF效果最差,硫容量仅为83.3 mg/g。     

改性活性炭纤维吸附脱除气态汞

采用浸渍法对活性碳纤维(ACF)改性,所制得的吸附剂在固定床上进行汞吸附评价。Boehm滴定表明,浓HNO3和H2O2改性后的ACF表面含氧官能团有所增加,含氧官能团的增加有利于汞的吸附。XRF结果表明,ACF经硝酸银浸渍后,银离子被还原成单质银,使其对汞的吸附性能得到改变,并随着硝酸银浓度的增大而增大。ACF经活性MnO2和KMnO4浸渍后,吸附效果均有所提高,穿透时间大大加长,穿透吸附量也大大提高,两者均可达到170μg/g。     

酸性条件下微波改性活性碳纤维对Pb(Ⅱ)的吸附

采用微波辐照的方法,在混酸条件下对活性碳纤维(ACF)进行改性,制备得到一种改性活性碳纤维(M-ACF).通过小试吸附实验考察了微波功率、溶液pH值对M-ACF吸附Pb(Ⅱ)的影响.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、电子能谱(EDX)等技术对ACF和M-ACF进行表征.结果表明,M-ACF表面的羧基等酸性含氧官能团增多,纤维长度变短且表面粗糙化.当M-ACF的投加量为10 mg、含铅溶液初始浓度为50 mg/L、pH为6、吸附时间为24 h、吸附温度为308 K时,M-ACF对Pb(Ⅱ)的吸附量高达248.5 mg/g.吸附过程符合准二级动力学模型和Langmuir等温吸附模型;热力学参数表明吸附为吸热、自发的过程.     

聚丙烯腈基活性碳纤维用于烟气脱硫脱硝

应用聚丙烯腈基活性碳纤维(PAN-ACF)对模拟的工业烟气中的SO2和NO在烟气露点温度以上进行吸附脱除实验。通过改变固定床ACF装载量、反应温度、水蒸气体积分数和O2体积分数,研究了ACF脱硫效率和脱硝效率的变化规律,还研究了同时脱硫脱硝时入口SO2或NO浓度对脱除效率的影响。结果表明:PAN-ACF具有良好的脱硫性能和一定的脱硝能力,其脱硫效率和脱硝效率随着ACF装载量和O2体积分数的增大而升高,随着温度的升高而降低,随着水蒸气体积分数的增大先升高后降低;在同时脱硫脱硝时,SO2对ACF的脱硝反应有明显的抑制作用,而NO对ACF的脱硫反应影响不大。     

过渡金属浸渍改性ACF去除H2S研究

为探讨活性炭纤维(ACF)去除恶臭气体H2S的性能,采用过渡金属浸渍改性ACF吸附H2S,揭示出改性ACF前后吸附H2S的性能差异及浸渍剂的浓度和种类对ACF吸附性能的影响。结果表明,通过过渡金属改性后的ACF吸附性能有显著提高,对H2S吸附是物理吸附和化学吸附共同作用的结果,改性后的ACF硫容量大小依次为：5％硝酸铜...     

改性半焦脱除烟气中SO2的研究

对内蒙工业副产褐煤半焦（比表面积49.187m^2／g,孔容0.0351cm^2／g）,采用加压水热化学活化法,HNO3活化法和高温煅烧相结合的方法制备出半焦烟气脱硫剂,并对脱硫剂的脱硫性能进行固定床活性评价。分析表明,其脱硫效果比较好,转化率维持在50％以上的累计硫容可达24．30％,脱硫时间长达35h,远远高于原料半焦的脱硫效果（硫容为0．68％,时间为1．5h）;同时采用水洗法对脱硫剂进行再生,其再生液可用来制备浓度为9.01％的稀硫酸。     

粉状活性焦在双层滤料颗粒床中的脱硫试验研究

在双层滤料颗粒床模型试验台上对粒径为300～400目的粉状活性焦进行了脱硫试验,研究了温度、O2和水蒸气体积分数、气体流速、再生次数对脱硫效果的影响.试验结果表明.温度为120℃、O2体积分数为8%、水蒸气体积分数为10%条件下,脱硫效果最好;粉状活性焦在双层滤料颗粒床中经过7次重复吸附.达到硫饱和吸附量为66.2 mg/g.粉状活性焦再生试验表明,随着再生次数的增加.粉状活性焦的脱硫性能呈下降趋势.     

新型柱状核桃壳活性炭脱硫动力学

采用以农业废弃物核桃壳为原料,天然软锰矿为添加剂共混制成的新型柱状活性炭进行了不同水蒸气含量下的烟气脱硫实验,利用Bangham和Elovich 2种模型对实验结果进行模拟与比较。实验结果表明,随着水蒸气含量的增加,穿透硫容和时间逐渐增加,并在水蒸气含量为10%时达到最大点,此时硫容为243.0 mg/g。模拟结果表明,2种模型均可以较好地模拟烟气脱硫实验结果,其中Elovich模型具有更高的拟合相关度和准确性。在对Elovich模型加以改进以包含水蒸气影响后,可以更好地描述烟气在不同水蒸气含量下的新型柱状活性炭脱硫情况。     

活性炭纤维负载功能化离子液体的脱硫性能

以等体积浸渍的方法将[C3O1Mim]+[H3CSO3]-(1-(2-甲氧基乙基)-3-甲基咪唑甲磺酸盐)和[C5O2Mim]+[H3CSO3]-(1-(2-甲氧基乙氧基乙基)-3-甲基咪唑甲磺酸盐)负载到活性炭纤维(ACF)上,并对其进行氮气吸附、热重等表征。对ACF固载的离子液体脱硫性能测试,结果表明:在离子液体负载量为10 wt%,模拟烟道气流量为40 m L/min,温度为20℃,SO2体积分数为0.2%条件下,[C3O1Mim]+[H3CSO3]-/ACF、[C5O2Mim]+[H3CSO3]-/ACF吸附量分别为45.34mg SO2/g和60.08 mg SO2/g。经过5次吸附-脱附循环利用,其脱硫效果基本不变,说明[C3O1Mim]+[H3CSO3]-/ACF、[C5O2Mim]+[H3CSO3]-/ACF有良好的再生性能。     

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.