中水回用中平板膜的污染机理分析

采用间歇式生物反应器，对模拟小区生活污水的人工配水进行了生物处理；然后，在操作压力为0．1MPa，搅拌速度为300r／min条件下，选用膜生物反应器中常用的聚醚砜（PES，切割分子量分别为2万、1万和5千）、聚丙烯腈（PAN，切割分子量为20万）、聚偏氟乙烯（PVDF，切割分子量为20万）超滤平板膜和聚醚砜（PES，孔径为0．1μm）、聚丙烯腈（PAN，孔径为0．1μm）、聚偏氟乙烯（PVDF，孔径为0．1μm）微滤平板膜在实验室用死端超滤器上分别对活性污泥悬浮液进行了过滤并探讨了和间歇式生物反应器组合在一起用于中水回用的效果，结果表明：每种组合处理后的出水水质为COD〈50mg／L，NH3-N〈10mg／L，SS为0mg／L，浊度为0NTU，都达到了中水回用的水质标准（CJ25．1．89），其中生物反应器分别与PES超滤膜（5千、1万、2万）和PAN（20万、0．1μm）膜组合时，对COD的去除率较高，但所有组合对NH3-N、TOC去除率及膜的渗透通量都相差不大。此外，根据恒压堵塞过滤定律对膜的污染机理进行的研究证实：对于微滤膜和PAN（20万）超滤膜而言，由滤饼过滤过渡到完全（标准）堵塞，再到滤饼过滤；但对于PVDF（20万）和PES（2万）超滤膜，则由标准堵塞过渡到完全堵塞，再到滤饼过滤；PES（5千、1万）超滤膜的污染机理相对简单，整个过程以滤饼过滤为主。     

超滤膜深度处理染整废水的膜污染机理

实验采用不同规格和材料的超滤膜进行染整二级尾水分离实验,对超滤膜污染机理及影响因素进行了分析。实验采用红外光谱分析了聚醚(PES)膜、聚砜(PSF)膜和聚醚酰亚胺(PEI)膜3种超滤膜材料,对比了污染前后膜面的接触角以及不同切割分子量对膜通量及出水水质的影响,并利用线性化的Herman堵塞模型拟合了不同分子量超滤膜的堵塞模型,初步探讨了超滤膜的污染机理。实验结果表明,膜材料表面亲水性基团的多少与初始膜通量大小成正比,出水COD值随超滤膜切割分子量减小而减小。切割分子量同为2 000 Da的3种超滤膜中,PES膜的处理效果最佳,出水COD平均值为47.81 mg/L;PEI膜通量最高,平衡通量可达50 L/(m2.h);切割分子量为1 000、10 000的超滤膜堵塞机理符合滤饼过滤模型,100 000的超滤膜堵塞机理更接近于完全堵塞模型;1 000的聚醚砜材质膜(PES)更适合此类废水的深度处理。     

颗粒物粒径和有机物分子量对超滤膜污染的影响

采用不同孔径和截留分子量的膜对原水进行预过滤,研究不同粒径的颗粒物和不同分子量的有机物对膜污染的影响。结果表明,随着预过滤膜孔径或截留分子量的减小,原水中浊度、CODMn、DOC和UV254的去除率逐渐提高,超滤膜运行的跨膜压力(TMP)比直接过滤原水时降低;经孔径为1.2μm和0.45μm的膜预过滤后,超滤膜运行的TMP仍上升较快,而经过截留分子量为100 kDa及以下膜预过滤后,膜污染比较缓慢。对膜阻力构成分析的结果表明,随着预过滤膜孔径或截留分子量的减小,超滤膜运行过程中的表面饼层阻力逐渐减小,堵孔阻力也有明显降低,但预膜滤不能有效降低膜的吸附阻力。超滤膜表面的扫描电镜观察结果表明,经过截留分子量在100 kDa及以下的膜预过滤后,超滤膜表面比较干净,此时的膜过滤阻力主要来源于吸附和堵孔阻力。     

中空纤维微滤膜污染及阻力分析

选用0.1μm的PVDF中空纤维内压式微滤膜组件,在死端微滤工况下,研究了酵母(平均粒径5.3 μm)和高岭土(平均粒径0.7μm)体系在浓度和压力变化时的污染机理及过滤阻力、膜渗透通量的变化规律性.通过恒压堵塞定律积分式的具体形式与实验数据的拟合及根据堵塞过滤定律计算的结果都表明:死端微滤时,酵母体系和高岭土体系均符合滤饼过滤机理.     

超滤-膜接触臭氧氧化技术处理印染废水

采用超滤与膜接触臭氧氧化组合工艺处理印染废水二级生化出水,对超滤膜切割分子量、膜接触反应器膜长、臭氧浓度、气体流量和产水速率等工艺条件进行优化选择,并对该组合工艺的处理效果进行了研究。通过系列实验确定的优化参数为:超滤膜切割分子量100 kDa,膜接触反应器膜长2 m,臭氧浓度10 mg·L~(-1),气体流量0.6 L·min~(-1),产水速率1.4 L·h~(-1)。连续运行8 d,平均COD由131 mg·L~(-1)降到70 mg·L~(-1),平均色度由130度降到20度,平均浊度由11 NTU降到2.3 NTU,B/C值也由0.167提高到0.244。     

中空纤维微滤膜污染及阻力分析

选用0．1μm的PVDF中空纤维内压式微滤膜组件，在死端微滤工况下，研究了酵母（平均粒径5．3μm）和高岭土（平均粒径0．7μm）体系在浓度和压力变化时的污染机理及过滤阻力、膜渗透通量的变化规律性。通过恒压堵塞定律积分式的具体形式与实验数据的拟合及根据堵塞过滤定律计算的结果都表明：死端微滤时，酵母体系和高岭土体系均符合滤饼过滤机理。     

改性PES膜在MBR中膜阻力分析及膜污染机理研究

以聚醚砜(PES)、醋酸纤维素(CA)和纳米二氧化钛(TiO2)为膜材料,采用L-S相转化法制备共混改性PES膜。在24℃、0.2 MPa的操作条件下,制得的PES膜纯水通量为300 L/(m2.h)左右,CA改性PES膜为660 L/(m2.h)左右,TiO2改性PES膜为840 L/(m2.h)左右。通过膜生物反应器中膜阻力的测定,表明膜污染主要由浓差极化层及凝胶层引起的;通过活性污泥对膜污染机理的研究,判断出污泥的过滤过程基本符合沉积过滤定律。在MBR中运行时,改性PES膜稳定通量高于未改性膜,总阻力低于未改性膜;TiO2改性膜稳定通量高于CA改性膜,总阻力低于CA改性膜;通过扫描电镜分析,改性PES膜沉积层的厚度均比未改性膜薄,TiO2改性膜沉积层厚度小于CA改性膜,表明改性膜的抗污染性能提高了,TiO改性膜抗污染性能更优。     

膜基材对动态膜生物反应器性能的影响研究

选用5种滤布作为动态膜生物反应器(DMBR)的膜基材在相同操作条件下进行对比实验,考察反应器运行周期、反冲洗前后过滤压力、膜通量的恢复情况,分析DMBR进出水水质.结果表明,应用DMBR处理模拟生活污水,其中孔径为24μm的涤纶短纤滤布组成的DMBR对COD、氨氮和总氮的去除率分别为90%、80%和48%以上;运行周期...     

不同超滤膜过滤天然有机物的膜污染特性研究

超滤膜的截留分子量、天然有机物的分子量分布以及两者之间的相对关系对于膜污染以及过滤阻力的组成有很大的影响。MWCO140kDa、70kDa、30kDa、10kDa、4kDa和1kDa的超滤膜过滤10mg/L腐殖酸溶液和未名湖湖水的试验结果表明,在过滤初始时刻就发生了膜污染,膜的截留分子量越大,膜污染越显著。在长期过滤的过程中,截留分子量>10kDa的超滤膜的过滤阻力受到膜污染的控制,膜孔堵塞和膜面形成凝胶层是造成膜污染的主要原因;当膜的截留分子量≤10kDa时,过滤阻力主要由膜本身固有的阻力决定,膜污染影响较小。不同浓度、类型的腐殖酸溶液和不同种类的超滤膜过滤试验数据分析表明,当膜对腐殖酸分子的截留率超过40%时,膜污染的程度会逐渐减小,过滤阻力将由膜本身固有的阻力控制。     

陶瓷膜污染过程分析与膜清洗方法优化

采用膜孔径为50 nm的陶瓷膜错流过滤方式,对碱性高浓度有机洗涤废水进行9个周期的膜通量衰减及反向脉冲清洗再生实验研究.通过设计膜污染阻力构成实验,测算膜污染总阻力及其构成比例.实验结果表明,膜固有阻力比例较低,浓差极化污染较弱,Rt和Rc+Rirt污染阻力稳定性较高,膜堵塞形式兼有孔内堵塞和滤饼过滤;选择质量分数0.1％的稀盐酸和0.2％的草酸溶液膜清洗效果均较好,清洗时间为3 min,脉冲时间和频率为3 s/5 s.     

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.     

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.     

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.     

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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)