萃取精馏法分离醋酸-水的研究

采用萃取精馏法从醋酸水溶液中分离回收醋酸是一新的研究方向,而适宜溶剂的筛选是研究关键.本实验以高沸点含氮类有机化合物作为醋酸-水萃取精馏的候选溶剂,采用平衡组分分析法对溶剂进行了实验筛选.结果表明,溶剂的引入使体系的相对挥发度有较大程度的提高,其中N-甲基乙酰胺(NMA)使水对醋酸的相对挥发度提高最多,为4.75.因此实验确定NMA为最优溶剂,并进行了醋酸-水萃取精馏的工艺实验.与普通精馏结果对比表明,以NMA为溶剂的萃取精馏法分离醋酸-水的效果非常显著,研究结果对开发环保型的醋酸-水分离新工艺具有重要意义.     

萃取精馏法分离醋酸-水的研究

采用萃取精馏法从醋酸水溶液中分离回收醋酸是一新的研究方向,而适宜溶剂的筛选是研究关键.本实验以高沸点含氮类有机化合物作为醋酸-水萃取精馏的候选溶剂,采用平衡组分分析法对溶剂进行了实验筛选.结果表明,溶剂的引入使体系的相对挥发度有较大程度的提高,其中N-甲基乙酰胺（NMA）使水对醋酸的相对挥发度提高最多,为4.75.因此实验确定NMA为最优溶剂,并进行了醋酸-水萃取精馏的工艺实验.与普通精馏结果对比表明,以NMA为溶剂的萃取精馏法分离醋酸-水的效果非常显著,研究结果对开发环保型的醋酸-水分离新工艺具有重要意义.     

间歇好氧硫酸盐废水处理系统微生物区系解析

应用PCR-DGGE(polymerase chain reaction-denaturing gradient gel electrophoresis)技术和16S rDNA序列测定对间歇好氧硫酸盐废水处理工艺的微生物群落结构进行了研究.采集味精厂好氧池原始污泥以及实验室内间歇好氧工艺驯化后不同条件下的活性污泥样品,通过基因组DNA的提取、PCR扩增和DGGE分离,初步分析了各污泥样品的微生物群落多样性,结果表明,PCR-DGGE方法可以在一定程度上反映工艺以及操作条件对微生物群落结构的影响.通过DGGE反复分离纯化及割胶回收,DGGE检验为单一条带后进行测序并提交到GenBank数据库比对,结果表明,间歇好氧硫酸盐系统中优势菌株大多数为未培养细菌,来源于不同的污染环境,具有重要污染物降解的生态功能,其中包括与硫酸盐还原菌(Desulfobulbus propionicus)在系统发育上非常接近的菌株.     

聚丙烯中空纤维膜生物反应器净化复合芳香族VOCs

采用中空纤维膜生物反应器(HFMBR)去除气态复合苯系物。挂膜后期,生物反应器的去除效率可以稳定达到80%左右(去除能力(EC)≥225 g/(m3.h))。研究了中空纤维膜生物反应器处理对于单一二甲苯以及混合二甲苯的性能,并且发现HFMBR对于去除单一二甲苯和混合二甲苯都有明显的效果,去除效率均达到90%以上;表明二甲苯之间竞争效应带来的相互抑制作用小。在低浓度的情况下,单一二甲苯和混合二甲苯的去除能力呈线性增加,在高浓度阶段,去除能力增加变缓。比较了混合二甲苯与甲苯联合降解,发现两者之间存在相互抑制作用,但相比传统生物反应器有明显的改善。与传统生物过滤系统比较而言,膜生物反应器有着很好的应用前景。     

曝气生物滤池与地下渗滤系统工艺脱氮除磷

以生活污水为研究对象,考査了曝气生物滤池和地下渗滤系统组合工艺脱氮除磷的性能。工艺运行过程中,曝气生物滤池只考虑COD和氨氮的去除把总氮和总磷的去除分离到地下渗滤系统中。实验结果表明,曝气生物滤池和地下渗滤系统组合工艺有良好的脱氮除磷能力。滤速为0.6 m·h~(-1),气水比为5:1,反冲洗周期为7d时,曝气生物滤池达到最佳运行状态,对C0D、氨氮、TN、TP的去除率分别达到85.3%、83.5%、30%、56%。为了提高TN、TP的去除率,地下渗滤系统采用间歇的方式运行个周期连续进水12 h,放空12 h进水为曝气生物滤池出水,水力负荷为5 cm·h~(-1),对COD、氨氮、TN、TP的去除率分别达到41.3%,62.8%、81.3%,82%。     

中空纤维膜生物反应器处理二甲苯废气

采用中空纤维膜生物反应器(HFMB)去除气态二甲苯,研究比较了不同进口浓度、停留时间以及悬浮液中生物量对二甲苯净化效果的影响。实验结果表明:随着进口浓度的增加二甲苯净化效率先升高后平稳,生化降解能力(EC)则明显升高;随着停留时间的增加,二甲苯的净化效率明显增加。实验发现最佳的实验条件是:悬浮液循环速率50 L/h,pH值介于6.5到7.5之间,溶解氧6 mg/L左右,停留时间tR=8.8 s;二甲苯的处理效率可达到92%以上。结果还显示二甲苯净化效率随悬浮液循环流速的变化而波动不大,进口二甲苯的组成对净化效率也有一定的影响。与传统的生物法相比,膜生物反应器可以实现气相和液相的分离以及减少占地面积,具有很好的发展前景。     

间歇运行式生物滴滤池处理油漆废气中试研究

为研究间歇运行式生物滴滤池对油漆生产厂废气净化能力,建立一座中试规模生物滴滤池（BTF）,接种降解菌群,采用8 h/d运行方式净化某油漆厂包装车间废气,并用PCR-DGGE技术揭示BTF细菌群落结构与工艺运行条件间的联系。油漆厂包装车间废气中挥发性有机物（VOCs）主要为甲苯、乙苯、混合二甲苯（间、对和邻二甲苯）,BTF对甲苯、乙苯、混合二甲苯最大去除率分别为88.8%、83.7%和86.3%。DGGE分析显示,BTF稳定运行时,主要优势菌相对丰度较为稳定（F,P>0.05）,其细菌多样性显著低于启动期（F,P>0.05）;同时,下层填料细菌多样性高于上层填料,其细菌结构变化也较上层明显;另外,提升培养液浓度至2倍和4倍对菌群结构亦无显著影响。     

吸附浓缩-催化燃烧工艺处理低浓度大风量有机废气

对已运行的有机废气治理工程运行情况的进行分析研究,并对采用吸附浓缩-催化燃烧工艺处理低浓度大风量的有机废气工程中的各项数据进行监测,得出其最佳条件为:吸附时间18 h,空床气速0.8 m/s,吸附容量1.9%;解吸温度100~120℃,解吸时间4 h。该工程实例的监测结果表明,催化燃烧的TVOC去除效率保持在99%以上,同时,该工艺对废气中甲苯、二甲苯和TVOC的总去除率分别能达到98.3%、99.6%和97.7%。     

含二甲胺工业废水的回收及再利用技术研究

为了消除工业二甲胺废水带来的巨大污染,使其达到回收利用的目的,利用精馏技术,采用BH型高效填料作为分离介质,连续从废水中脱除二甲胺,并将塔顶二甲胺提浓。结果表明,采用本技术可使塔顶二甲胺提浓至47%(质量百分含量),达到满足40%二甲胺水溶液质量要求的目的;塔釜二甲胺含量降低至≤50 mg/L,此水可作皮革工业生产回用水。由于含二甲胺废水经处理后可以全部回收利用,表明该高效精馏技术用于清洁生产中具有可靠性和实用性。     

响应曲面法优化微波修复二甲苯污染土壤工艺参数

目前土壤污染问题得到越来越多的关注,污染土壤修复技术的研究更加受到重视。通过单因素和响应曲面法优化实验,研究了含水率、处理量、辐照时间和微波功率对二甲苯去除效果的影响,并且对不同敏化剂的作用进行了实验研究。结果表明,微波功率、辐照时间和含水率对二甲苯的去除率均有显著影响。模型优化结果显示,微波修复二甲苯污染土壤的最佳工艺参数为:微波功率530W,辐照时间3.4min,含水率32%,去除率可达到79.75%,实验验证结果与预测值之间相对误差为1.89%。活性炭在反应过程中主要起吸附作用,粉煤灰的添加对二甲苯的去除有非常显著的作用,去除率最高可达到98.42%。     

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.