PVDF/PVA改性超滤膜抗污染特性的微观作用力评价分析

使用动态过滤法对聚偏氟乙烯(PVDF)超滤膜进行改性,得到PVDF/聚乙烯醇(PVA)改性膜。系统考察了改性前后PVDF超滤膜表面的微观结构变化,使用原子力显微镜结合自制的—COOH、—OH官能团探针,定量测定了改性前后超滤膜与官能团之间的作用力变化特点,并进行了富含—OH、—COOH官能团的典型有机物海藻酸钠(SA)及腐殖酸(HA)的膜污染实验。结果表明,与PVDF基膜相比,PVDF/PVA改性膜表面粗糙度增大,接触角有效降低;—COOH、—OH官能团与PVDF/PVA改性膜之间的作用力远远小于—COOH、—OH官能团与PVDF之间的作用力。在相同的膜污染运行时间内,改性膜的通量衰减速率及衰减幅度皆小于相应PVDF膜的通量衰减速率及衰减幅度。说明改性膜有效降低了膜-污染物之间相互作用力,提高了膜的抗污染能力,微观作用力评价方法可利用于揭示膜污染本质。     

用微观作用力解析无机离子对腐殖酸的膜污染行为影响

基于Na+、Ca2+离子在天然水体中的普遍存在及对超滤膜有机污染行为的影响,本研究主要考察了不同离子条件下腐殖酸(HA)对PVDF超滤膜污染行为的影响机理。使用原子力显微镜结合自制的膜材料及污染物探针定量测定了不同离子条件下PVDF-HA及HA-HA之间的相互作用力,同时进行了相应的膜污染实验及定量研究腐殖酸的去除效果。结果表明,PVDF-HA及HA-HA之间的相互作用力大小与膜污染速率及污染幅度呈正相关关系。一价Na+离子通过电荷屏蔽可降低HA表面的带电量,对HA膜污染行为及PVDF-HA及HA-HA之间作用力的影响并不明显。二价Ca2+离子通过电荷中和作用大幅度降低了HA表面的有效带电量,使得PVDF-HA及HA-HA之间的粘附力增大,加剧了膜污染速率。而过多的Ca2+离子会加剧HA之间的聚合,降低了HA进入膜孔内的机率,虽然会短暂的增加腐殖酸的去除效率但无法从根本减轻膜污染。     

溶液对蛋白质污染膜的清洗效果分析

采用牛血清蛋白(BSA)代表有机物,自行开发了聚偏氟乙烯(PVDF)膜片,结合耗散型石英晶体微天平(QCM-D),考察不同NaCl浓度条件下BSA在PVDF膜面的微观解吸行为及吸附层结构特征;并使用原子力显微镜测定相应离子条件下与膜污染行为相关的微观作用力大小,综合膜性能恢复实验,解析NaCl溶液对有机物污染膜的清洗机理.结果表明:随着NaCl离子浓度的从1增加到300 mmol·L~(-1),PVDF与羧基官能团之间的相互作用力逐渐减小,BSA污染层松散度逐渐增大;同时引入大量的水合Na~+离子进入BSA污染层内部,破坏BSA污染层内部的静电吸引力和氢键,进而破坏吸附层结构,伴随着BSA污染膜的通量恢复率随着NaCl离子浓度的增加而大幅度提高。     

天然有机物对PVDF超滤膜的污染行为及AFM表征

为了进一步研究各类型污染物对自制PVDF超滤膜的污染机制,分别采用DAX-8,XAD-4型吸附树脂将西安市灞河水分为亲水性、强疏水性及弱疏水性组分,考察了天然有机物(NOM)对膜通量衰减的影响、污染层的表面粗糙度和结构、各类型污染物与膜之间黏附力。实验结果表明:(1)3种组分对PVDF膜的污染程度为亲水性组分强疏水性组分弱疏水性组分;(2)污染后膜表面粗糙度大于新膜表面粗糙度,膜表面污染层粗糙度越大,膜通量越容易恢复;(3)过滤初期,膜与污染物之间的力占主导作用,且亲水性污染物-PVDF膜之间的力强疏水性污染物-膜弱疏水性污染物-膜;(4)过滤后期,污染物与污染物之间的力占主导作用,且亲水性污染物之间力强疏水性污染物弱疏水性污染物。     

混凝对正渗透过程中抗生素去除特性及膜污染的影响

为探明混凝预处理对正渗透去除抗生素的影响以及混凝对后续膜处理的影响,选用PAC、FeCl_3、Al_2(SO_4)_3对正渗透原料液进行混凝预处理,考察了混凝预处理对正渗透水通量、NaCl返混通量、抗生素截留率及膜污染的影响。结果表明:混凝预处理对正渗透过程中膜污染程度的影响由原料液中HA残留量以及Zeta电位共同决定;经混凝预处理后,原料液中腐殖酸残留量越多,正渗透过程中所形成的滤饼层越厚,原料液Zeta电位绝对值越低,形成的滤饼层越密实。滤饼层的形态影响正渗透的浓差极化作用,进而影响正渗透的运行特性及抗生素的截留效果,同时决定了膜清洗的难易程度。     

钙离子存在下胞外聚合物及其模拟溶液在膜污染中的差异

针对膜生物反应器膜污染的问题,为探究模拟物质替代实际物质的可行性,以胞外聚合物(EPS)及其模拟溶液(BSA+SA)为研究对象,对比了钙离子(Ca~(2+))存在下胞外聚合物及其模拟溶液在膜污染中的差异,考察了EPS-Ca~(2+)和BSA+SA-Ca~(2+)在粒径分布、官能团、流变特性和膜污染行为等方面的差异。结果表明:Ca~(2+)使得溶液粒径变大,且EPS-Ca~(2+)的平均粒径大于BSA+SA-Ca~(2+)的平均粒径;不同官能团与Ca~(2+)发生作用导致红外光谱中特征峰发生偏移;BSA+SA-Ca~(2+)水胶体系结构更稳定,随着应变的增大,胶体结构被破坏的程度较轻;在微滤过程中,相同操作条件下,BSA+SA-Ca~(2+)的膜污染现象更为严重。进一步采用Hermia过滤模型拟合发现,EPSCa~(2+)和BSA+SA-Ca~(2+)分别对中间堵塞模型和滤饼层过滤模型的拟合程度最高。上述结果可为膜污染过程中胞外聚合物及其膜污染机理研究提供参考。     

曝气对管式MBR膜污染及临界通量影响

采用管式膜微滤高岭土悬浊液,考察了恒通量下曝气对膜污染的影响,并对不同膜面气体流速下跨膜压力和膜污染周期变化进行了研究,此外,采用阶梯通量法对临界通量进行了测定。结果表明,曝气可显著减缓膜污染,延长膜污染周期,同时提高膜的临界通量;随着膜面气体流速由0.067 m·s~(-1)提升至0.251 m·s~(-1)时,膜污染平均速率由0.366 k Pa·h~(-1)降低至0.104 k Pa·h~(-1),膜污染周期由8 d延长至31 d,临界通量由8~10 L·(m~2·h)-1提高至22~26 L·(m~2·h)-1。此外,通过惯性模型分析发现,膜的临界通量与膜面混合流速呈良好的线性关系,R~2=0.98;但随着膜面气体流速的增加,悬浊液中高岭土粒径逐渐变小,并且通过膜表面污染阻力构成分析发现,膜表面不可逆污染阻力由13.9%提高至31.6%,这不利于膜污染控制。     

膜探针的制备及PVA/PEG/PVP在膜污染过程中的作用

为了进一步研究膜的抗污染性能,介绍了一种新型膜探针技术。将二氧化硅颗粒黏附在探针尖端,并将含不同添加剂的铸膜液涂覆于二氧化硅表面以制成一种改性膜探针。采用原子力显微镜测量不同改性膜-污染物和污染物-污染物之间的黏附力。实验结果表明:膜-污染物之间的黏附力远大于污染物-污染物之间的黏附力;膜对二级出水(effluent organic matter,Ef OM)通量的衰减幅度与膜-污染物之间黏附力正相关,与污染物-污染物之间黏附力的相关性不明显;(3)膜通量的恢复率与膜-污染物黏附力大小负相关。     

盐类对模拟胞外聚合物(EPS)膜污染的影响

实验旨在研究盐类对模拟胞外聚合物(EPS)溶液在超滤和微滤过程中膜污染影响,通过添加与无添加盐类的模拟溶液的比较,研究盐类对EPS膜过滤在死端过滤过程的影响。实验考察了不同模拟溶液的膜通量衰减情况和滤饼比阻,并利用Hermia模型对实验数据进行拟合分析验证膜污染机理。实验结果表明,在超滤过程中,Ca2+和Al3+能在一定程度上提高膜通量,降低滤饼比阻,延缓膜污染;在微滤过程中,两者的添加反而降低了初始通量,添加Ca2+后滤饼比阻值反而有所增大;Na+对超/微滤过程影响很小。通过Hermia模型拟合分析发现,在超滤过程中,添加盐和无添加的溶液均以滤饼堵塞机理为主,而在微滤过程中则是以中间堵塞和滤饼堵塞机理为主。     

亲疏水性溶解性有机物对聚偏氟乙烯超滤膜污染行为

选用模拟亲疏水性有机物及实际二级处理水中的亲疏水性有机物,分别进行了聚偏氟乙烯(PVDF)超滤膜污染实验.并测定了不同污染物与膜及污染物间的作用力,分析亲/疏水性有机物对PVDF超滤膜的污染行为.结果表明,膜-污染物及污染物间相互作用力是控制膜污染行为的主导因素.亲水性有机物与PVDF超滤膜之间的相互亲和力较强,致使运行初期膜通量的大幅度下降,是PVDF膜的优势污染物.但是,针对实际污染物,运行后期,疏水性有机物之间较强的相互作用力使得其取代了亲水性有机物,成为膜的优势污染物.此外,模拟亲疏水性有机物的膜污染变化规律与实际亲疏水性有机物相似,表明使用模拟污染物可一定程度上预测实际废水中相应性能污染物的膜污染行为.     

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.