废锌锰电池真空蒸馏法去除汞的研究

废锌锰电池回收利用中的一个关键问题是实现汞的无害化。介绍了使用真空蒸馏装置，通过单因素实验和正交实验，研究蒸馏温度、系统压强和蒸馏时间对去除汞的综合影响；寻找去除汞的最优工艺条件。根据实验结果，使用真空蒸馏的方法处理锌锰电池优化的工艺参数为：蒸馏温度500～600℃，蒸馏时间60～80min，系统压强3000～7000Pa。     

回转窑热解处理废锌锰电池试验研究

利用回转窑装置热解处理废锌锰电池,考察了热解温度、热解时间和载气流速对热解脱汞效果的影响,研究了汞被吸收的规律、尾气的成分以及废锌锰电池的物质形态变化.研究结果表明:在热解温度为690 ℃,热解时间为100min,载气流速为0.06 m3/h的条件下脱汞效果最好.热解时间对脱汞效果影响最大,热解温度次之,载气流速的影响很小.吸收液能完全吸收通过吸收瓶的尾气中含有的汞,其中95%以上的汞以单质形式存在.热解残渣中晶态物质多,金属元素呈低价态.     

利用烧结处理废旧电池的工艺研究

对利用烧结处理废旧电池的工艺进行了试验研究.结果表明,在焙烧温度为400℃、时间为90 min时,汞的去除率可达99%以上;在焙烧温度为1100℃、时间为90 min时,脱锌率可达到95%;将除汞除锌后的电池样添加到烧结原料中,其量为1%时,对烧结矿质量基本没有影响,说明该技术处理废旧电池是可行的,可为我国废旧电池的处理和利用开辟一条新的途径.     

利用烧结处理废旧电池的工艺研究

对利用烧结处理废旧电池的工艺进行了试验研究.结果表明,在焙烧温度为400℃、时间为90 min时,汞的去除率可达99%以上;在焙烧温度为1100℃、时间为90 min时,脱锌率可达到95%;将除汞除锌后的电池样添加到烧结原料中,其量为1%时,对烧结矿质量基本没有影响,说明该技术处理废旧电池是可行的,可为我国废旧电池的处理和利用开辟一条新的途径.     

利用废旧锌锰电池制备光催化剂净化甲苯

针对废旧锌锰电池回收利用难,以及光催化剂 TiO2活性低的问题,以废旧锌锰电池和商业二氧化钛为原料,通过球磨法制备了新型复合光催化剂.在紫外光灯照射下,进行了废旧锌锰电池复合改性TiO2对甲苯的光催化氧化实验,并重点探究空速、光照强度、相对湿度和氧气体积分数等关键实验条件对甲苯净化效率的影响.结果表明,改性后的催化剂对甲苯的净化能力大幅提高;当TiO2与废电池芯粉的质量比为2:1时,催化剂的催化效果最好,甲苯的净化效率提高了近45％;空速越大,催化剂对甲苯的净化效率越低;净化效率随光照强度的增加呈现先增加后保持不变的规律;催化剂在相对湿度为30％的条件下具有最佳的催化活性,氧气体积分数为15％时为净化效率达到最大.本研究结果可为废旧锌锰电池的回收利用提供新的思路.     

真空蒸馏回收镍镉电池中镉金属工艺优化模型研究

利用正交试验的方法对真空蒸馏回收镍镉电池进行工艺研究。通过分析温度、压力、蒸馏时间、打孔数目4个因素对镉金属回收比重的影响,确定了真空蒸馏回收镍镉电池中镉金属的最佳试验条件为温度950℃,压力133Pa,蒸馏12h,打孔4个。并在此基础上建立模型对镉金属回收量进行估算,为镍镉电池回收的中试试验奠定了基础。     

真空蒸馏回收镍镉电池中镉金属工艺优化模型研究

利用正交试验的方法对真空蒸馏回收镍镉电池进行工艺研究。通过分析温度、压力、蒸馏时间、打孔数目4个因素对镉金属回收比重的影响，确定了真空蒸馏回收镍镉电池中镉金属的最佳试验条件为温度950℃，压力133Pa，蒸馏12h，打孔4个。并在此基础上建立模型对镉金属回收量进行估算，为镍镉电池回收的中试试验奠定了基础。     

减压蒸馏耦合微电解处理六硝基二段洗水

通过对六硝基茋(HNS)生产过程中第二段工艺的产品洗涤废水进行水质分析,针对该段废水含有大量吡啶和多种溴代和硝基芳香类化合物的特点,探究了减压蒸馏耦合锌碳微电解法处理二段洗水的效果并优化工艺参数。结果显示,70℃条件下,二段洗水蒸馏至原体积的86.9%时,蒸馏剩余废水TOC去除率为44%,并且此前收集的馏分中吡啶浓度为10%～31.9%(V/V)。减压蒸馏工艺起到收集吡啶同时降低废水TOC的双重作用。减压蒸馏后,残留在废水中的有机物以溴代和硝基芳香化合物为主,采用微电解工艺,其条件优化实验的结果显示,在废水初始pH=1.0,锌投加量为25 g/L,锌碳投加比为1∶1,反应60 min后,废水TOC去除率为33%,采用多级微电解工艺可提高去除效果。     

热解吸对污染土壤中不同形态汞的去除作用

选取贵州省万山矿区的汞污染土壤样品进行不同形态汞的热解吸去除行为研究。研究了热解吸过程中∑Hg的去除效果及动力学,以及温度和时间对污染土壤中不同形态汞的去除作用。结果表明,热解吸修复技术可有效去除土壤中的汞,土壤中∑Hg的热解吸过程符合二级动力学方程。固定热解吸时间在10 min时,随着热解吸温度的升高,土壤中水溶态汞、盐酸溶态汞和碱溶态汞含量呈现先下降后上升再下降的趋势,王水溶汞和盐酸溶态汞始终呈现下降趋势,说明不同形态的汞之间发生了转化。热解吸温度为250℃时,随着热解吸时间的增加,环境风险大的水溶态汞、盐酸溶态汞、碱溶态汞和硝酸溶态汞的去除率大幅增加,土壤的有机质损失较少,说明在低温下,延长热解吸时间,对生物毒性强的形态汞有良好的修复效果,且此温度下处理后的土壤更容易恢复农田耕作。     

超临界CO2回收线路板工艺研究

用正交试验设计进行了超临界CO2回收废弃印刷线路板的实验。以温度、压强、时间和夹带剂为实验因素,通过对实验前后样本在重量、厚度、弯曲强度和断裂强度四方面变化的分析考察了各实验因素对实验效果的影响。实验结果表明,影响超临界CO2法回收印刷线路板的最主要因素为温度、时间和夹带剂,超临界CO2法回收废弃印刷线路板的最佳工艺条件：温度270℃,压强大于7．38MPa,时间3h,夹带剂（水）160mL。实验进一步验证了压强对实验结果的非显著性影响。     

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.