As（V）在金红石TiO2颗粒表面吸附特性及机理

通过静态动力学和热力学吸附实验,研究了温度、共存离子以及溶质的初始浓度对As（V）在金红石TiO2颗粒表面吸附的影响,探讨了As（V）在金红石TiO2颗粒表面吸附特性及机理。结果表明,在As（V）初始浓度为10mg／L,pH为7的条件下,25℃时的吸附量0．41mg／g高于30℃时的吸附量0．31mg／g,As（V）在金红石TiO,上的吸附为放热过程。CaCl2和MgCl2的添加对As（V）在金红石TiO2表面吸附起到明显的促进作用。T=25℃,Ca2＋或Mg2＋浓度为10mmol／L时,As（V）吸附量分别为0．64和0．56mg／g,Ca2＋比Mg2＋对As（V）吸附促进作用强。As（V）在金红石TiO2的吸附等温线符合Frendlich方程,Lagergren二级动力学方程能较好地描述As（V）在金红石TiO2颗粒表面吸附的动力学过程。     

蛭石在非缓冲与缓冲体系中的Zn~(2+)、Cd~(2+)吸附行为研究

探讨了蛭石分别在非缓冲体系与缓冲体系中的Zn2+、Cd2+吸附行为,比较了2个体系中Zn2+、Cd2+的平衡吸附量(qe),qe与平衡液相离子浓度(ce)、qe与ce和吸附剂浓度(W0)之比(ce/W0)的对应关系。结果表明,在非缓冲体系与缓冲体系中,在3个W0水平上,Zn2+、Cd2+都具有其独立的qe—ce等温吸附曲线,而qe与ce/W0具有良好的相关性,在3个W0水平上的qe—ce/W0等温吸附曲线基本拟合在一起,即在qe—ce/W0等温吸附曲线中均基本消除了吸附剂浓度效应;加入缓冲溶液的传统方法并不能消除W0对离子吸附效果的影响;缓冲体系中,大量的其他阳离子参与Zn2+、Cd2+的竞争吸附,从而使得Zn2+、Cd2+的qe相对降低;缓冲体系的qe—ce、qe—ce/W0等温吸附曲线与非缓冲体系相比,线性形式更为明显,缓冲体系的qe—ce/W0等温吸附曲线中,qe与ce/W0的对应关系没有非缓冲体系中的好。     

Zr—Fe双组分复合除砷吸附剂的优化制备及性能评价

实验发现,铁氧化物或铁的羟基氧化物对As（V）有较好的吸附性能,而锆氧化物或锆水合氧化物则对As（Ⅲ）有优异的吸附选择性,但其使用的pH通常要在〉9的条件下。通过简单的共沉淀法制备了Zr-Fe双组分复合吸附剂,在制备过程中通过优化制备条件如：沉淀剂浓度、金属离子总浓度、金属离子配比、反应温度、反应时间及吸附剂价格等因素,最终合成出了对As（V）和As（Ⅲ）都具有良好吸附能力的吸附剂。这种吸附剂在中性条件下对As（V）和As（Ⅲ）的最大吸附量为62mg／g和118mg／g。     

利用质子化的水杨醛接枝壳聚糖吸附水中硫酸根

以水杨醛（邻羟基苯甲醛）接枝壳聚糖为基础制备出质子化改性壳聚糖,研究其对硫酸根离子（SO24-）的吸附性能。通过静态吸附实验进行了吸附条件的优化以及吸附等温方程研究,用扫描电镜（SEM）和红外光谱（FTIR）对产物进行了表征,并对吸附机理进行了初步探讨。优化的吸附条件为：吸附时间为40min,SO24-溶液初始浓度500mg／L,pH值为5．0,反应温度为35℃;吸附等温方程研究表明,吸附过程符合Langmuir型,吸附容量为107．53mg／g。SEM和红外光谱分析表明：SO24- 主要是被吸附到壳聚糖的氨基上的。     

污泥衍生吸附剂对铅离子的吸附机理研究

研究了化学活化法热解制取污泥衍生吸附剂的工艺过程，得出相应工艺条件。利用污泥衍生吸附剂吸附溶液中重金属离子Pb^2＋，得到动力学模型。实验结果表明：（1）该吸附过程分为3个阶段：初始阶段（t≤20min）、过渡阶段（20min〈t≤30min）和后期阶段（t〉30min），满足线性方程dC／dt=kC；（2）该吸附过程的吸附活化能E=26，5kJ／mol，吸附频率因子A=6900s^-1。整个吸附过程为扩散吸附，吸附传质速度由孔隙扩散阶段和内表面吸附共同控制。     

厌氧颗粒污泥吸附去除废水中Hg^2＋的研究

在实验室条件下,以静态、序批的方法研究了厌氧颗粒污泥对废水中Hg^2＋的吸附特性及环境条件对其吸附能力的影响,并通过红外光谱和能谱对比手段,初步探讨了厌氧颗粒污泥吸附Hg^2＋的机理。结果表明,厌氧颗粒污泥对Hg^2＋的吸附过程符合准二级吸附动力学模型,其吸附等温线与Freundlich型拟合得较好（R^2=0．9933）;pH是影响吸附的重要因素,在pH值为3～8的范围内,吸附量较大,最大为64．64mg／g,当pH值大于8或小于3时,吸附量逐渐下降;温度对吸附也有一定的影响,但影响程度不明显。红外光谱和能谱分析表明,厌氧颗粒污泥表面功能基团对Hg^2＋的络合作用是吸附的主要机理,这些基团包括-CH、-CH2、-CH3、P—H、C=0、C-N、P=0、S=0及=C—H,同时在吸附过程中还存在一定的离子交换吸附。     

铜离子对厌氧氨氧化脱氮效能的影响

接种厌氧氨氧化（Anammox）污泥,通过序批式实验研究了Cu^2＋对Anammox脱氮效能的影响。实验结果表明,当溶液中Cu^2＋≤1mg／L时,对Anammox生物系统有刺激作用,可增强微生物活性,促进Anammox反应的进行：1mg／L〈Cu^2＋≤101iltg／L对脱氮效能无明显抑制,脱氮系统处于稳定状态;Cu^2＋〉10mg／L对Anammox脱氮效能有抑制作用,Cu^2＋浓度越大,毒性越强,抑制现象越明显。Cu^2＋对Anammox菌的半抑制浓度（C1,50）为23mg／L。实验结果还表明,Anam—mox污泥对Cu^2＋具有吸附能力,经过一段时间后固液相将处于一种动态平衡。Cu^2＋为1mg／L时最大氮去除速率能达到Cu^2＋浓度为0mg／L时的3倍。     

Ru-TiO2光电极对亚甲基蓝的光电催化降解

采用阳极氧化法制备Ru—TiO2光电极,以该电极为工作电极,石墨作对电极,饱和甘汞电极为参比电极,对亚甲基蓝溶液的光电催化降解进行了研究。结果表明：煅烧温度600oC,掺杂1％Ru的Ru-TiO2光电极催化活性最好;以紫外灯（125W）为光源,当外加偏压0．2V,pH为5时,Ru-TiO2光电催化亚甲基蓝120min可使其完全脱色;亚甲基蓝的光电催化降解遵从Langmuir—Hinshelwood动力学模型,测得其反应速率常数k：0．781mmol／（L·min）,吸附常数K=0．225L／mmol。     

硬硅钙石吸附焦化废水氨氮的动力学性能研究

用纳米级吸附材料硬硅钙石,对焦化废水的氨氮进行脱氮试验研究,结果表明,硬硅钙石对废水中氨氮的吸附平衡时间为180min,吸附等温线符合Freundlich和Langmuir方程,吸附等温式为qe=0．4345Ce^0.3269和qe=0.0745Ce/1＋0.0283Ce,1/n=0.3269,在0．1～0．5之间,可以作为焦化废水氨氮的吸附剂使用,计算单层吸附的最大吸附量为2.6357mg／g。当每100mL水样中投加量为2.5g时,硬硅钙石与活性炭对焦化废水氨氮平衡吸附量分别为1．35mg／g和1．60mg／g,对氨氮的去除率分别为45．55％和47．25％,两者处理效果的差异不断减小。     

污泥活性炭的表征及其对Cr（Ⅵ）的吸附特性

以城市污水处理厂污泥为原料,采用磷酸活化一微波热解法制备得到污泥活性炭,并将其用于吸附水溶液中的Cr（Ⅵ）。分别采用元素分析仪（VarioELcube）、比表面积孔径分布测定仪（ASAP2020）、扫描电镜（SEM）和傅里叶红外光谱（FT—IR）等仪器对原污泥及污泥活性炭的表面组成和结构进行表征,探讨污泥活性炭的孔隙结构参数和表面化学性能。通过静态吸附实验,考察了溶液初始pH,接触时间,初始Cr（Ⅵ）浓度对污泥活性炭吸附Cr（Ⅵ）效果的影响,并探讨了污泥活性炭去除Cr（Ⅵ）的机理。实验结果表明,pH越低吸附效果越好,吸附平衡时间为100h。不同温度下吸附过程均符合Langmuir等温吸附模型,30℃时最大吸附容量为27．55mg／g;吸附动力学过程符合准二级速率方程（R2〉0．99）;污泥活性炭对Cr（Ⅵ）的去除是一个吸附-还原耦合的过程。     

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.     

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.