剩余污泥制备活性炭及其应用研究

以城市污水处理厂二沉池排出的剩余污泥为原料,采用不同活化方法制备活性炭,同时对比活化效果,研究了制备工艺条件对污泥活性炭吸附性能及产率的影响。结合比表面积、孔径分布和扫描电镜表征分析,对制备的污泥活性炭的性能进行评价,并探讨了污泥活性炭作为水处理吸附剂的去除效果。结果表明,以ZnCl₂为活化剂制备的活性炭性能较好,其最佳制备条件为：活化温度550℃,活化时间45 min,ZnCl₂浓度40％,固液比1∶2。制得的污泥活性炭的碘吸附值为496 mg/g,产率为51.8％,比表面积为301.4 m²/g,孔体积为0.37 mL/g,微孔体积为0.08 mL/g,平均孔径为5.78 nm。将该产品用于处理城市污水,投加量为0.8％,吸附平衡时间约为60 min时,对COD的去除率为81％,吸附容量为42.53 mg/g。     

磷酸法制备杏核壳活性炭及对Cr（Ⅵ）的吸附

利用饮料厂废弃杏核壳制备活性炭,对含Cr（Ⅵ）废水进行吸附实验研究,达到废物资源化的目的。介绍了活性炭制备过程,用电镜观察活性炭的形貌,并测得碘吸附值为1 354 mg/g。研究杏核壳活性炭吸附含Cr（Ⅵ）废水结果显示,当吸附时间为3 h、溶液pH为3、吸附温度25℃时,活性炭饱和吸附量达12.5 mg/g,有效去除废水中Cr（Ⅵ）。杏核壳活性炭吸附Cr（Ⅵ）符合Langmuir吸附模型（R² =0.9944）和Freundlich模型（R² =0.9462）。对Cr（Ⅵ）的动态去除率可达99.68%。     

草酸钾活化法制备榴莲壳活性炭及其表征

以榴莲壳为原料,选择K2C2O4为活化剂,在自制氛围气中进行化学活化制备活性炭。考察了活化剂/原料浸渍比、活化温度与活化时间对活性炭的碘和亚甲基蓝吸附值及得率的影响。结果表明,制备榴莲壳活性炭的理想条件为:活化剂/原料浸渍比1.5∶1、活化温度800℃和活化时间120 min;此时活性炭的SBET(BET比表面积)、总孔容和微孔孔容分别为1 195 m2/g、0.60 cm3/g和0.41 cm3/g。利用比表面和孔隙度分析仪、场发射扫描电镜(FE-SEM)和傅立叶红外光谱法(FT-IR)对活性炭的孔结构特征、微观形貌和表面官能团进行了表征。FE-SEM观测结果显示榴莲壳活性炭孔隙结构发达,且含有丰富的中孔。     

基于响应曲面法优化生物质污泥活性炭的制备方法

针对传统技术制备污泥活性炭的比表面积不高、吸附值低等不足,通过在污泥中添加核桃壳以改善污泥原料缺陷,研究了活化剂种类、核桃壳加量、活化温度、活化时间、活化剂浓度及浸渍比等影响活性炭吸附能力的制备条件。在优化后的条件下制备出了高吸附性能的生物质污泥复合活性炭。结果表明:选择氯化锌作为活化剂,核桃壳加量20%、活化温度500℃、活化时间60 min、活化剂浓度2.5 mol·L-1、浸渍比1∶2.5为最优化制备条件。制备出的生物质污泥复合活性炭碘吸附值为574.11 mg·g-1,产率为43.93%。     

棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料,以KOH为活化剂,制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能,探讨了浸渍比,活化温度,活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响,并通过静态吸附实验比较了不同条件下制备活性炭对2,4-二硝基苯酚的吸附性能,探讨了典型炭样品对2,4-二硝基苯酚的等温吸附特性。结果表明,KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化,活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min,在此条件下制得的炭样的碘值为1 251 mg/g,亚甲基蓝吸附值为478 mg/g,分别是国家一级品标准的1.25倍与3.54倍;对2,4-二硝基苯酚的Langmuir最大吸附量为747 mg/g,与Freundlich模型相比,Langmuir模型能较好地描述2,4-二硝基苯酚在炭样上的吸附行为,表明制备活性炭样品表面吸附位的能量分布较为均一。     

改性活性炭吸附净化黄磷尾气中的H2S

研究了以Cu²⁺离子活性溶液制备改性活性炭吸附净化黄磷尾气中H₂S的相关问题,考察了改性活性炭制备过程中的浸渍液浓度、干燥温度和焙烧温度的影响,以及温度和氧含量对吸附的影响;并对空白活性炭、改性活性炭吸附前后做SEM表征。研究结果表明,浸渍液浓度0.05 mol/L、干燥温度120℃、焙烧温度250℃为改性活性炭制备的最佳条件;吸附反应阶段较适宜的温度为95℃,氧含量为1%;结合扫描电镜初步表明,改性后的活性炭S容量增加,吸附效果明显。     

“氧化镁/活性炭”新型吸附剂的制备及其对Cr(VI)的吸附研究

以氯化镁和造纸草浆黑液为原料,采用物理活化法制得“氧化镁/活性炭”新型吸附剂,其比表面积（BET）为388.96 m²/g、总孔容积为0.40 mL/g。测定了这种吸附剂对水中Cr(VI)的吸附性能,考察了吸附时间、pH值、吸附剂投加量、初始浓度等因素对Cr(VI)的吸附量和脱除率的影响,研究所得吸附水溶液中Cr(VI)的最佳条件为：吸附时间为120 min,吸附剂投加量为2 g/L,pH值为2。“氧化镁/活性炭”新型吸附剂对Cr(VI)的吸附过程符合Freundlich等温式。     

生物质活性炭的制备及其染料废水中的应用

以城市污水厂活性污泥为原料,用3 mol/L ZnCl2溶液活化,通入水蒸气作活化气制备活性炭吸附剂.实验结果表明,温度为600℃条件下,活化时间为1 h,制得的活性炭其碘吸附值为374.10 mg/g,比表面积为381.62 m2/g,孔容积为0.25 cm3/g,微孔容积为0.11cm3/g.并进一步将生物质活性炭应用于染料废水的处理,考察了吸附时间、活性炭投加量和pH对色度及TOC的脱除效果的影响.室温下,酸性大红GR染料废水初始浓度为300 mg/L,污泥活性炭的最佳投加量为2%(质量分数),吸附15min,废水色度脱除率可达99.6%,TOC去除率可达99.7%,利用等温吸附实验作吸附等温线,吸附等温线可以用Freundlich或Langmuir方程描述.     

核桃壳炭化吸附废水中Cr(Ⅵ)的性能研究

采用氯化锌活化法制备生物质废物硬壳活性炭,工艺条件为:核桃壳与氯化锌溶液质量比为1∶1.5、氯化锌溶液质量分数50%、炭化温度300℃、炭化时间90 min、活化温度600℃、活化时间60 min。对产品比表面积、孔径和表征进行了分析,并探讨了该核桃壳活性炭吸附废水中六价铬的pH值、废水初始浓度、吸附时间、振动转速等影响因素。结果表明:制得的活性炭碘吸附值为1 038.33 mg/g,比表面积为645.36 m2/g,平均孔半径为1.37 nm。当活性炭用量为0.1 g,废水pH=3,吸附接触时间为1 h,取100 mL浓度为50 mg/L的含Cr6+废水时,处理吸附量可达48.57 mg/g。活性炭最大饱和吸附值为80.24 mg/g。吸附符合Langmuir等温模式,吸附等温方程式为Ce/Qe=0.0083+0.0121Ce。     

水枝锦活性炭对孔雀石绿的吸附性能研究

以水枝锦为原料,采用磷酸活化法制备成水枝锦活性炭,通过静态实验研究其对孔雀石绿的吸附性能.考察了水枝锦活性炭投加量、接触时间、pH和孔雀石绿初始浓度对孔雀石绿吸附效果的影响.结果表明,在温度为723 K、活化时间为1 h条件下,水枝锦活性炭得率为36.7%,比表面积为1 223m2/g;在298K、孔雀石绿初始质量浓度为250mg/L、接触270min条件下,水枝锦活性炭的最佳投加量为0.5 g/L,适宜pH为7～12;吸附量随温度的升高而增大,提高温度有利于吸附的进行;水枝锦活性炭静态吸附孔雀石绿的动力学行为符合伪二级动力学方程.静态吸附动力学研究为投加粉状活性炭的吸附池的设计和污水处理装置的运行提供基础信息,对于去除水中孔雀石绿技术的应用具有重要的实际意义.     

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.