Mg/Al/Fe水滑石的焙烧产物对F~-的吸附

采用共沉淀法合成Mg-Al-Fe类水滑石,并通过不同焙烧温度制得焙烧类水滑石。采用XRD,FT-IR,SEM等方法进行了吸附材料表征。研究了焙烧温度,吸附剂投加量,吸附时间,吸附初始p H值,吸附动力学,吸附等温线、吸附热力学等因素对Mg-Al-Fe类水滑石及其焙烧产物吸附F-的效果。研究表明,500℃焙烧类水滑石吸附效果最好,0.2 g吸附剂是最佳投加量值,在p H变化范围为3~8内吸附量基本无变化。研究结果表明,焙烧水滑石吸附符合准二级动力学曲线,反应活化能为E_a=14.63 k J/mol。反应基本符合Langmuir吸附等温模型。△G~0为负值表明该反应是一自发进行过程。高温有利于吸附反应进行。     

含铝活性炭污泥对磷的吸附特性研究

考察了粒径、pH、温度、磷初始浓度等因素对含铝活性炭污泥吸附磷的影响,确定了其吸附过程的热力学和动力学参数。结果表明,含铝活性炭污泥吸附磷的最佳条件为污泥粒径取1.000~2.000mm,温度取25℃,无需调节pH,磷初始质量浓度小于50mg/L。Langmuir方程或Freundlich方程均可以描述含铝活性炭污泥吸附磷的吸附等温线。热力学参数标准吉布斯自由能变(ΔGθ)0J/mol、标准吸附焓变(ΔHθ)0J/mol、标准吸附熵变(ΔSθ)0J/(mol·K)表明,含铝活性炭污泥吸附磷为自发的、吸热的、熵增的过程。吸附动力学研究表明,拟二级动力学模型能够模拟含铝活性炭污泥对磷的吸附过程。     

Mg/Al/Fe复合氧化物吸附去除水体中氟化物的研究

采用水热法合成了不同铁掺杂量的Mg/Al/Fe型类水滑石(MAF),根据X射线衍射(XRD)的测定结果,铁存在一个最佳投加量,铁的掺杂量过大则会导致水滑石的层状结构被破坏。通过扫描电镜(SEM)和比表面分析仪(BET)研究了MAF焙烧后的复合金属氧化物(CMAF)的结构和性能,并考察了CMAF对水中氟离子的吸附性能。与CMA相比(铁掺杂量为零),CMAF对氟离子的吸附去除效率明显提高(最大吸附容量75.2 mg/g),整个吸附过程可以用Langmuir吸附等温线更好地描述。通过XRD测定和晶格参数计算,CMAF的结构由吸附前的复合氧化物恢复到层状水滑石结构,表明氟离子在水滑石重构过程中作为层间阴离子进入到水滑石内部,从而达到较高的除氟效率。     

磁性水滑石快速吸附水体中Cu(Ⅱ)离子

为了探究磁性水滑石对水体中Cu(Ⅱ)离子的去除效果,利用四氧化三铁对水滑石进行磁化,用扫描电子显微镜、X射线衍射仪和傅里叶红外光谱仪表征磁性水滑石。然后,探究磁性水滑石在不同吸附温度、时间、pH、投加量等条件下去除模拟废水中Cu(Ⅱ)的性能。结果表明,磁性水滑石对Cu(Ⅱ)最大吸附量为32.36 mg/g,吸附动力学结果表明,磁性水滑石对Cu(Ⅱ)的吸附在前90 min基本完成。溶液保持pH 5.6~6.5时,磁性水滑石对Cu(Ⅱ)有良好的吸附效率。磁性水滑石可以再生循环利用3~4次。实验证明,磁性水滑石是一种良好的Cu(Ⅱ)吸附剂。     

煅烧的水滑石同时去除水体中砷和氟

为探讨水滑石类材料对水体中氟、砷离子的同时去除效果,采用共沉淀法合成(Mg∶Al=2∶1)纳米类水滑石(LDHs),用傅立叶转换红外光谱、电子扫描透射电镜、X射线晶体衍射等手段对合成的材料进行了表征,并研究纳米材料在不同初始浓度、pH、吸附时间、阴离子干扰条件下其同时除砷氟性能。结果表明,煅烧后的水滑石(LDOs)对砷最大吸附量为51.02 mg/g,对氟最大吸附量为36.63 mg/g。吸附动力学实验表明,煅烧水滑石对砷的吸附在前6 h内基本完成,对氟的吸附在前10 h内基本完成。砷氟共存溶液保持pH=4~10及pH=6~8时,水滑石分别对砷、氟保持良好的吸附效率。对比不同阴离子对水滑石共除砷氟效率的影响,水滑石除砷速率受到阴离子影响力大小为:HPO2-4CO2-3NO-3Cl-SO2-4;水滑石除氟速率受到阴离子影响力大小为:CO2-3HPO2-4SO2-4Cl-NO-3。材料再生循环利用4次后,对砷和氟的吸附效率均能达到90%以上。实验结果表明,所合成的水滑石是一种优秀的能共除砷氟的吸附剂。     

焙烧态锂铝水滑石对水中氟离子吸附性能研究

采用尿素水热法合成了不同摩尔比的锂铝水滑石(Li/Al LDHs),经480℃煅烧后制备出焙烧态锂铝水滑石(Li/AlLDOs)。研究了Li/Al LDOs对水中氟离子的吸附性能,分别考察了吸附时间、吸附温度和pH等因素对吸附效果的影响,并对吸附机制进行了探讨。结果表明,Li/Al LDOs吸附水中氟离子的行为符合准二级动力学方程,吸附等温数据符合Freundlich吸附等温方程,pH对吸附效果影响较大。X射线衍射分析表明,水滑石样品经历了物相转变及重构过程,Li/Al LDOs可有效去除水体中的氟离子。     

磁性Ca/Al水滑石对挥发性脂肪酸的吸附性能

污水脱氮除磷处理过程中使用的液态碳源存在投加量难以控制以及容易影响出水水质、增大处理费用等缺点。针对此现状,采用超声辅助法以超顺磁性铁氧体材料对制备的Ca/Al水滑石进行复合改性合成磁性Ca/Al水滑石,研究以其作为载体对挥发性脂肪酸(VFA)的吸附提取性能,考察了磁性Ca/Al水滑石吸附剂剂量、吸附时间和转速对VFA吸附效果的影响,并通过均匀实验设计,采用响应面法优化吸附提取参数。结果表明:当吸附剂剂量为16 g·L~(-1),吸附时间为50 min,转速为70 r·min~(-1)时,该材料对VFA的理论最大吸附效率为95.7%。由于材料自身具有磁性特性,经提取后的混合液在外加磁场的作用下,能够实现磁性Ca/Al水滑石的快速回收。同时,将回收再生后的磁性Ca/Al水滑石对VFA的吸附提取性能进行了研究,发现在吸附解吸3次循环后仍然有很好的吸附效果。表明利用该磁性Ca/Al水滑石提取VFA是可行的,为后续将其作为固态可控外加碳源的研究奠定了基础。     

磁性水滑石/生物炭复合材料的制备及其对水溶液中磷的吸附性能

以芦苇秸秆生物炭为基体,制备了磁性水滑石/生物炭复合材料(Fe3O4-Mg/Al-LDH/BC)。考察不同pH、Fe3O4-Mg/Al-LDH/BC投加量、初始磷浓度、吸附时间以及反应温度对Fe3O4-Mg/Al-LDH/BC吸附磷的影响。结果表明:Fe3O4-Mg/AlLDH/BC对磷的吸附符合准二级动力学模型和Freundlich模型,吸附过程是自发的吸热反应。在最佳的实验条件下(Fe3O4-Mg/Al-LDH/BC投加量为5.0g/L,磷初始质量浓度为20 mg/L,pH为6.0,温度为30℃,吸附时间为120 min),Fe3O4-Mg/AlLDH/BC对磷的去除率可达99.24%,该材料是一种新型高效的磷吸附材料。     

铁交联累托石处理工业镀锌废水试验研究

介绍了铁交联累托石的制备 ,研究了交联累托石对含锌废水的处理。结果表明 :当交联累托石的用量为 1 2g/L废水、pH =4、常温搅拌吸附 90min时 ,Zn2 + 由 12 2 5mg/L降为 0 97mg/L ,达到国标GHZBI 1999地表水质量一级标准。累托石对Zn2 + 吸附符合Freundlich等温吸附 :Γ =0 34C0 492 3 ,动力学试验表明 :吸附反应为一级反应方程 :lnCt=lnC0 -0 340 6t,其相关系数r =0 95 18,试验测得其热力学函数为 :ΔH =1 91kJ/mol,ΔS =6 90J/mol·K ,ΔG =- 0 16kJ/mol,说明该吸附过程可自发进行     

CoFe_2O_4/MgAl-LDO吸附水中的Cr(Ⅵ)

采用水热法、共沉淀法合成Co Fe2O4/Mg Al-LDH,于高温下焙烧4 h后,制备出同时具有高吸附性能和磁分离性能的镁铝复合氧化物(Co Fe2O4/Mg Al-LDO),研究其对水中Cr(Ⅵ)的吸附效果。采用X射线衍射(XRD)、红外光谱(FTIR)等技术对吸附剂进行表征。通过序批实验考察了焙烧温度、溶液初始p H值、吸附时间、温度等因素对Co Fe2O4/Mg AlLDO吸附Cr(Ⅵ)的影响。结果表明,当焙烧温度在450~550℃之间、溶液初始p H=2~6时,吸附剂对Cr(Ⅵ)均具有较好的吸附效果,且吸附反应在90 min内达到平衡。Co Fe2O4/Mg Al-LDO吸附Cr(Ⅵ)过程符合准二级动力学和Langmuir等温吸附模型,当温度为318 K时,理论饱和吸附容量为98.04 mg/g。热力学研究结果表明,该吸附过程为自发的、吸热反应过程。     

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.