改性凹凸棒土的优化定向制备及对腐殖酸的吸附效果

以天然凹凸棒土为原料,以去除以腐殖酸为代表的天然有机物为目的,研究酸活化、热处理和十八烷基三甲基氯化铵(OTAC)有机改性3种改性方法,进行定向筛选。进一步比较3种方法联合改性凹土后对腐殖酸的吸附效果,确定最优定向改性方法。结果表明,先酸处理后OTAC改性凹土对腐殖酸的吸附效果最好,改性凹土投药量为0.7 g/L时,腐殖酸的去除率可达97%。利用正交实验确定凹土改性的最佳工艺条件、钠化时间和有机改性剂的用量对改性凹土吸附腐殖酸的能力影响显著。改性的最佳工艺条件为:酸浓度3 mol/L,氯化钠浓度0.5 mol/L,钠化时间2 h,改性剂用量为凹土质量的3%,微波改性时间为9 min。单独投加改性凹土时p H值对腐殖酸的吸附效果有重要影响。该方法制备的改性凹土在水处理工艺有良好的应用前景。     

氟苯再生酸氧化过滤—冷却结晶—吸附—减压浓缩净化工艺

为了开发一种氟苯再生酸的资源化利用途径,对某生产氟苯及其系列产品的化工厂排出的废酸进行了研究,提出了氧化过滤—冷却结晶—吸附—减压浓缩的净化工艺,并且在吸附阶段,通过自制改性的活性炭作为吸附剂来对氧化、结晶的酸液进行吸附,COD去除率高达96.8%。同时确定了氧化过滤阶段的最佳工艺条件:废酸/氧化剂为4∶1,温度为110℃,反应时间为120 min,吸附阶段的最佳工艺条件:吸附剂的投加比为10 g·L~(-1),吸附时间为12 h,吸附温度为30℃。结果表明,COD去除率高达99.4%,净化后废酸的硫酸含量达到82.4%。     

新型二级逆流吸附工艺处理模拟含碘放射性废水

为解决除碘吸附剂吸附效率较低的问题,开发出排除吸附剂脱附干扰的新型二级逆流吸附工艺。采用烧杯实验考察吸附剂对自来水中I~-的吸附特性,初始I~-浓度为2.00 mg·L~(-1),90 min达到吸附平衡,且较好符合Langmuir吸附等温式。这种吸附剂吸附I~-后会发生显著的脱附。基于吸附剂的特性和Langmuir吸附等温式,设计出新型二级逆流吸附工艺,并提出该工艺的计算模型,用于预测该工艺出水I~-的浓度。结果表明,该工艺能有效提高模拟放射性废水中I~-的去除效率,其出水I~-的平均浓度为0.150 mg·L~(-1),去除率达到92.5%。计算出水I~-浓度为0.124 mg·L~(-1),去除率为93.8%,实测值与模型计算值接近。与常规单级吸附工艺相比,在相同的吸附剂投加量下,I~-去除率由78.0%提高至92.5%。     

响应面分析法优化造纸污泥吸附剂除磷工艺

以造纸厂废水污泥为原料,采用微波加热法制备造纸污泥吸附剂。利用制备的造纸污泥吸附剂对模拟含磷废水进行了吸附研究,探讨了吸附时间、投加量、pH值、转速和温度等因素对除磷效果的影响,并采用响应面设计法优化吸附工艺条件。结果表明,获得了最佳除磷工艺条件为吸附时间97 min,投加量6.9 g/L,pH=6,转速200 r/min,温度30℃,在此条件下磷的去除率可达99%以上。因此,造纸污泥吸附剂对磷的吸附效果良好,具有重要的实际应用价值。     

氨基化凹土对水中焦性没食子酸的吸附

采用氨基硅烷偶联剂(γ-氨丙基三乙氧基硅烷)改性凹凸棒石黏土(以下简称"凹土")为吸附剂,通过静态吸附研究其对模拟废水中焦性没食子酸的吸附性能。结果表明,γ-氨丙基三乙氧基硅烷改性凹土能有效提高凹土的吸附性能,改性凹土吸附50 mL,浓度为100 mg/L焦性没食子酸较理想的条件为吸附剂用量0.4 g、吸附温度20℃、吸附时间40min、体系pH 5.2。通过静态吸附实验数据计算分析得知,拟二级动力学模型比拟一级动力学模型能更好地描述改性凹土对焦性没食子酸的吸附动力学行为,改性凹土对焦性没食子酸的吸附更符合Langmuir等温式,其饱和吸附量为19.861 mg/g。     

微波法制备工业污泥含碳吸附剂及其除铬性能

为实现工业集中区污水处理厂的脱水污泥(简称工业污泥)的废物资源化,以工业污泥为原料,通过氯化锌浸渍微波辐射法制备污泥炭吸附剂,探讨了制备过程中不同制备条件对污泥炭吸附剂吸附性能的影响,并用于吸附重金属离子铬。实验结果表明,除了微波功率、辐照时间等主要影响因素外,过滤条件、搅拌时间和盛放介质等因素也会影响污泥炭吸附剂的吸附性能,确定了工业污泥炭吸附剂的最佳制备条件是微波功率490 W,辐照时间10.0 min,氯化锌溶液浓度40%,搅拌时间24 h等,并且再生前后活性炭对含铬废水均有较好的处理效果;活性炭的投加量为1.0 g/L,Cr(Ⅵ)初始浓度和振荡速率分别为50 mg/L和100 r/min时,最佳除铬条件为pH、温度和吸附时间分别为2、室温(25℃)和1.0 h,在此条件下,Cr(Ⅵ)的去除率为98.5%,TCr的去除率为86.1%,从而为工业污泥的资源化提供了一条新途径。     

有机酸对成都平原镉污染土壤的淋洗效果

以成都平原某化工厂附近受Cd污染的2种土壤为对象,采用振荡淋洗技术,研究了有机酸在不同浓度、固液比、振荡时间和复合淋洗条件下对重金属Cd的去除效果。实验结果表明:柠檬酸和酒石酸对Cd含量为22.78 mg·kg~(-1)的SLT-01土壤具有更好的去除效果,分别达到73%和62%,而乙酸和草酸的去除能力较低;随着固液比的降低,有机酸对Cd的去除率逐步提高;随着时间的增加,Cd的去除率波动增加;柠檬酸和酒石酸复合淋洗并没有提高Cd的去除率;振荡淋洗前后土壤结构未发生明显变化。综合考虑土壤中Cd的去除效果和成本,选择柠檬酸作为最佳淋洗剂;最佳实验条件:溶液浓度为0.10 mol·L~(-1),固液比为1∶20,淋洗时间为8 h。     

吹脱-沸石吸附法处理荧光粉生产废水研究

研究了吹脱-沸石吸附法处理荧光粉生产废水.正交试验结果表明:氨吹脱工艺中影响NH3-N去除率因素的重要性顺序为:pH＞温度＞气液比.当pH=11、气液比(V/V)=100:1、温度T=40℃、吹脱时间t=120 min,吹脱工艺对荧光粉生产废水中NH3-N的去除率为74.46%.试验确定的沸石吸附单元较佳的工艺参数为:滤速0.04 m/min、接触时间14min、pH=7.5,吹脱-沸石吸附工艺总NH3-N去除率96.04%.试验结果表明再生沸石氨吸附性能稳定,适于高氨氮的荧光粉生产废水处理.     

交联羧甲基玉米淀粉对水溶液中铅离子吸附性能的优化研究

以玉米淀粉为原料,采用先醚化后交联改性工艺合成了交联羧甲基玉米淀粉吸附剂。在单因素试验的基础上,采用Box-Benhnken的中心组合试验设计及响应面分析法,研究了交联羧甲基玉米淀粉吸附剂用量、吸附时间和pH值3因素对水溶液中铅离子吸附效果的影响,得出了吸附剂对铅离子吸附效果的回归模型。结果表明,最佳吸附工艺参数为吸附剂用量0.22 g,pH值为6.6,吸附时间32.9 min,交联羧甲基玉米淀粉对铅离子吸附容量可达44.72 mg/g,铅离子去除率达到98.38%。常温下吸附动力学模型符合Freundlich等温式Q=0.4152C^0.9894。采用0.9 mol/L盐酸溶液作为解析液,铅离子回收率可达97.55%。     

火力发电厂飞灰对抗生素磺胺的吸附性能

研究了吸附时间、飞灰用量、初始溶液pH和振荡频率等因素对飞灰吸附去除水溶液中磺胺的影响,并对其吸附机理进行了初步探讨。研究结果表明,飞灰用量增大有利于提高其对磺胺的吸附去除率。在25℃、振荡频率150 r/min、飞灰用量50 g/L、磺胺浓度4 mg/L条件下吸附10 min,磺胺的吸附去除率可达到92.8%。电厂飞灰对磺胺的吸附符合二级动力学模型,属于单分子层吸附。     

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.     

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.     

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.     

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.