聚合硅酸钛铝复合絮凝剂的结构及性能

为了克服有机絮凝剂的二次投加及有毒性的缺点,以硅酸钠、硫酸钛、硫酸铝为原料,制备了聚合硅酸钛铝(PTAS)无机高分子复合絮凝剂处理模拟江水。结果表明,在n(Ti+Al)∶n(Si)=1∶3,n(Ti)∶n(Al)=1∶5,模拟江水pH值为5～9.3,絮凝剂投加量为0.3 mmol/L(以金属离子计)时,PTAS对模拟江水的混凝效果最好,除浊率达到92.5%以上。此外,通过X-射线衍射说明聚硅酸与硫酸铝、硫酸钛不是单纯的原料复合;红外吸收光谱显示钛、铝离子及其水解聚合产物可与共存的聚硅酸生成Si—O—Al键和Ti—O—Si键;激光粒度分析表明PTAS在聚合过程中粒度并没有明显变化,但均比聚硅酸粒径大。     

PATS的制备表征及其处理低浊水效能与残留铝控制

以水玻璃、硫酸铝和硫酸钛为原料,采用共聚法制备了聚硅酸硫酸铝钛(PATS)混凝剂。考察了混凝剂处理模拟低浊水的效能和出水残留铝含量,并且运用FTIR、XRD和SEM对混凝剂的结构形貌进行了表征。研究发现,当Al/Ti摩尔比为10∶1,(Al+Ti)/Si摩尔比为1∶2,水体pH为7~9,水体温度为10℃时,合成的PATS混凝剂对模拟低浊水的混凝性能最好,残留铝含量较低,当该混凝剂投量为0.10 mmol·L~(-1)(以金属离子计)时,余浊和残留铝含量分别可达到0.36 NTU和0.022 mg·L~(-1)。结果表明,PATS中存在铝、钛及其水解产物与硅发生相互作用生成的Al—O—Si键和Ti—O—Si键。PATS不是几种原料的简单混合,而是一种无定形共聚物。与聚合氯化铝、聚硅酸硫酸铝相比,PATS具有更好的混凝效果和更低的残留铝含量。     

聚硅酸锌铝的制备及其性能研究

以硅酸钠、硫酸锌、硫酸铝为原料,通过共聚法制备了无机高分子絮凝剂聚硅酸锌铝（PSZAS）,研究了Na₂SiO₃的摩尔浓度、活化时间、Al/Si、Zn/Si 配比及絮凝剂的投加量对絮凝效果的影响,用X-射线衍射（XRD）和电子扫描电镜（SEM）对该絮凝剂的结构及形貌进行了表征。结果表明：当硅酸钠的浓度为0.4 mol/L,硅酸活化时间为2 h,Si∶Al∶Zn=1∶1∶1.5,絮凝剂投加量为20 mL/L废水时,絮凝剂的电中和能力和吸附架桥能力最强,絮凝剂对含H-酸染料模拟废水的絮凝效果最好。     

硫酸钛混凝去除无机砷(Ⅲ)的效能

使用硫酸钛作为混凝剂,研究了混凝去除As(Ⅲ)过程中溶液pH值、混凝剂投加量、砷的初始浓度以及阴离子对除砷效果的影响.硫酸钛的水解沉淀物颗粒等电点为pH =5;当pH =6时,水解沉淀物的粒径最大.在pH =5 ～8范围内,As(Ⅲ)的去除率高且基本稳定;而沉淀物颗粒Zeta电位降低较大.说明水解沉淀物Zeta电位对As(Ⅲ)的去除影响不大.混凝剂投加量为2.5 ～10 mg/L时,As (Ⅲ)的去除率随投加量的增加而显著增加;混凝剂投加量大于15 mg/L时,As(Ⅲ)去除率随混凝剂投加量的增加变化趋于平缓.水中阴离子(硅酸根和磷酸根离子)的存在会降低混凝对As (Ⅲ)的去除效率.     

合成聚硅酸硼镁硫酸铁的正交实验研究

研究了用硅酸钠、硼砂、硫酸镁和硫酸铁为原料,制备聚硅酸硼镁硫酸铁（PSBMFS）混凝剂的方法及合成条件。通过正交实验,考查了硅酸活化pH值、缩聚反应时间和陈化时间等合成条件;同时考察了B/Si摩尔比、Mg/Si摩尔比和Fe/Si摩尔比等影响因素。结果表明：PSBMFS具有良好的混凝性能和脱色效果,能有效去除印染废水中的色度和COD,2种污染因子的去除率分别可达95.9%和67.9%。     

聚硅基复合氯化铁絮凝剂的制备及其在采油废水处理中的应用

采用硅酸钠制备聚硅酸,探讨了活化pH、活化剂、硅酸钠浓度(以SiO_2质量分数计)及聚合温度等因素对聚硅酸稳定性的影响.利用聚硅酸及氯化铁制备聚硅基复合氯化铁(PSiF),并通过正交试验分析了活化pH、Si/Fe(摩尔比)、OH/Fe(摩尔比)、制备时间对PSiF絮凝性能的影响.综合考虑絮凝性能、稳定性以及经济性等因素,确定PSiF适宜的制备条件为SiO_2质量分数2%～3%;活化pH为2～3;Si/Fe为0.50～0.75;OH/Fe为0.50～0.75;制备时间为0.5 h;聚合温度低于25℃.对比PSiF、PAC、FeCl_3对采油废水的处理效果,PSiF除浊、除COD效果以及经济性最好,是一种应用前景广阔的新型絮凝剂.     

强化混凝过程絮体形态对锑(V)去除效果的影响

利用混凝烧杯试验法,考察聚硫酸铁(PFS)强化混凝去除五价锑(Sb(V))过程中不同混凝条件对絮体形态(包括粒度和结构)以及出水水质的影响。结果表明,絮体平均粒径和分形维数的变化主要取决于主导混凝机理,且能通过作用于混凝效果而影响沉后水中悬浮态Sb(V)含量,但对最终除Sb(V)效果(主要为溶解态)的影响极为有限;原水p H和PFS投量对Sb(V)的去除有重要影响,而温度和混凝搅拌强度的作用却较小,并且助凝剂PAM的投加会在一定程度上削弱去除效果。在实际运行中,还需尽量避免沉后水因微小絮体过多影响后续工艺的运行工况及出水水质等。     

聚合铁钛混凝剂对印染废水的处理

采用钛铁矿为主要原料,以硫酸溶出部分铁和钛,并调节Ti/Fe比、碱化度制备高效的新型含钛聚合硫酸铁混凝剂(T-PSF),将其用于分散兰和活性黄2种模拟印染废水的脱色处理并研究其混凝去除机理。实验结果表明,在Ti/Fe为1∶6和碱化度为2.0时,制备出的T-PSF混凝效果最好。T-PSF对分散兰的去除率为94.3%,比FeCl_3的去除率提高53.8%;对活性黄的去除率为34.0%,比FeCl_3提高12.7%。T-PSF处理分散兰和活性黄的最佳投加量均为0.3 mmol·L~(-1),最佳水样初始pH分别为6和8。絮体粒径及结构分析结果表明,T-PSF处理分散兰过程中形成的絮体粒径较FeCl_3大,处理活性黄过程中所形成的絮体粒径较FeCl_3小,但絮体结构均比FeCl_3更密实。结合T-PSF的表征、Zeta电位及絮体特性分析表明,在分散染料去除过程中,T-PSF产生的多羟基钛铁聚合物的电中和及吸附架桥起主要作用;对于活性染料的去除,主要机制为T-PSF水解产生的带正电的多羟基钛铁聚合物的吸附络合作用。     

加药量和水力搅拌速度对雨水混凝效果的影响

为降低分流制雨水中悬浮颗粒物及其他污染物浓度,减轻城市景观河道的水体富营养化程度,对取自泵站的雨水进行混凝沉淀工艺优化实验。以PAC为混凝剂,采用Zeta电位仪、激光粒度仪和iPDA在线监测技术对混凝过程进行监测,考察了混凝剂投加量和水力搅拌速度对絮体形成和分流制雨水处理效果的影响,结果表明,混凝剂投加量和混合水力搅拌速度直接影响絮体Zeta电位和聚沉特性;混合搅拌速度控制混凝反应速率,絮凝速度梯度影响絮体形成粒径。FI曲线特征参数对控制混凝工艺具有指导意义。PAC投加量为35 mg/L,混合阶段搅拌速度800 r/min,搅拌30 s,絮凝阶段采用150、108和60 r/min的转速各自搅拌5 min,沉后水中剩余颗粒总数最少,浊度、COD和总磷去除效果最佳。     

聚硅铝三十(PASC_(30))的制备及混凝效果

制备一种新型的复合聚硅铝三十(PASC30)类絮凝剂,采用Al-Ferron逐时络合比色法测定PASC30系列混凝剂的铝形态以Alc为主,含量均在65%以上。将PASC30系列混凝剂与Al Cl3和PASC13混凝剂进行对比,采用混凝法处理腐殖酸-高岭土模拟废水,考察各混凝剂对废水的浊度、UV254、p H和Zeta电位的影响。结果表明,PASC30系列混凝剂表现出更出色的混凝效果,在低投加量时就能达到Al Cl3和PASC13混凝剂高投加量时的混凝效果。PASC30系列混凝剂对废水的浊度和UV254的最佳去除率分别达到96%和80%以上。随着投加量增大,PASC30系列混凝剂的出水p H不断降低,但是变化范围很小。不同硅/铝比对PASC30的混凝效果也有一定的影响,但是影响不大。     

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.