多效膜蒸馏技术浓缩回收废水中的二甲基亚砜

利用具有内部潜热回收功能的气隙式多效膜蒸馏(MEMD)组件对含二甲基亚砜(DMSO)的化纤废水进行了浓缩回收研究,考察了料液中DMSO浓度、进料流量、进料温度和膜侧进口温度对膜通量、造水比、分离因子和回收率的影响。结果表明,多效膜蒸馏可以将DMSO废水浓缩至200~300 g/L;初始浓度为6.2 g/L时,造水比和分离因子最高值分别为12.4和76.0;虽然膜通量、造水比和分离因子均随料液浓度增大而下降,但是当DMSO浓度达到200 g/L时,膜通量、造水比、分离因子仍分别高达3.74 L/(m2·h)、7.1、32.1;在整个浓缩过程中,回收率维持在99.6%以上;当DMSO废水浓缩达到150 g/L以上时,含有少量DMSO的渗透液可作为二次料液继续用MEMD过程浓缩。膜组件在连续运行的1个月内保持了良好的操作性能。该实验研究表明,多效膜蒸馏过程可以高效节能地浓缩回收化纤废水中的DMSO。     

膜蒸馏处理糖精钠生产废水

采用直接接触式膜蒸馏(DCMD)工艺处理糖精钠生产废水。分析了经过活性炭吸附预处理前后,膜蒸馏连续循环运行的效果。实验结果表明,未经预处理的废水在膜蒸馏过程中,废水中所含有机物不仅导致膜材料的润湿,引起产水电导率升高及膜孔润湿,促进盐晶体在膜表面附着,使产水通量下降。经吸附预处理后,膜蒸馏过程中产水通量介于10.40～11.24 kg/(m2.h)。吸附预处理能有效减缓产水通量的衰减,提高产水水质。废水经过活性炭预处理后进行膜蒸馏浓缩处理,当浓缩倍数达到5倍时,通量保持在10.55 kg/(m2.h)左右;产水水质稳定,截留率在99.5%以上。研究结果表明,吸附-膜蒸馏工艺可以应用于糖精钠生产废水的回用处理,有明显的应用前景。     

草甘膦母液膜分离的电渗析预处理

研究了用电渗析法去除草甘膦母液中影响膜通量的亚磷酸根,主要考察了pH值、工作电压、反应时间和温度等因素对亚磷酸根去除率的影响,并对电渗析预处理后母液纳滤膜分离的膜通量进行实验验证。实验表明：淡化液、浓缩液流量为30 L/h,pH值约为8.1,工作电压为20 V,反应时间为2 h左右,温度〈30℃时,电渗析对母液中亚磷酸...     

膜蒸馏处理页岩气井压裂返排液

页岩气压裂返排液的有效处理是页岩气开发急需解决的关键环保问题之一。针对新页HF-1井页岩气压裂返排液经预氧化结合湿式氧化(PO-WAO)工艺处理的出水COD不达标、含盐量高等技术难题,采用膜蒸馏处理技术对工艺的出水进行深度处理。通过膜蒸馏单因素和正交实验表明料液温度和冷凝温度对膜蒸馏处理效果影响较大,在料液温度、冷凝液温度、真空度、运行时间分别为80℃、8℃、0.090 MPa和60 min的最佳工艺条件下,膜通量可达1.750 L·(m2·h)-1,出水COD浓度为95.8 mg·L~(-1),出水水质可满足《污水综合排放标准》(GB 8978-1996)中一级排放的要求。膜蒸馏出水中电导率为63μS·cm-1,氯化钠的质量浓度为1.168 0 mg·L~(-1),可有效降低处理后的压裂废液对周围土壤的盐碱化伤害。     

直接接触式膜蒸馏浓缩处理高浓度发酵废液效能

采用直接接触式膜蒸馏工艺(DCMD)浓缩处理高浓度发酵废液,在热侧温度65℃、冷侧温度30℃条件下,连续运行21 h,考察了浓缩过程中产水通量、产水侧COD和TOC浓度变化及蛋白质浓缩效果。结果表明,产水通量随运行时间延长而下降且降速较快,15 h内由17.1 kg/(m~2·h)降至8.9 kg/(m~2·h);经去离子水冲洗,产水通量可恢复至56.1%。产水中COD和TOC浓度随处理时间延长而不断增大。此外,原水与膜蒸馏出水中GC-MS分析结果也表明,随运行时间延长,原水中有更多种类的有机物进入产水侧,主要为挥发性有机物。对膜内表面进行扫描电镜-能谱(SEM-EDS)分析发现,膜内表面有块状沉积物出现,主要成分为有机物,含有少量的无机物。DCMD运行21 h后,废液体积浓缩8.3倍,有用组分蛋白质浓缩6.9倍,COD和TOC的去除率均达95%以上。     

混合无机盐汲取液在城市污水正渗透浓缩技术中的应用

为实现浓缩城市污水以提高其资源化价值,构建了正渗透膜污水浓缩系统,研究了其对南方低浓度城市污水的有机污染物浓缩效果和膜污染特性。结果表明:使用含有1.6 mol·L~(-1) MgCl_2和2.4 mol·L~(-1) NaCl混合汲取液浓缩城市污水时,正渗透膜的水通量可达到27 L·(m~2·h)~(-1);南方城市污水浓缩6倍以上可满足后续资源化处理要求,浓缩后的TOC、COD、总磷、氨氮的平均回收率分别达到96.3%,95.72%,99%和90.4%;浓缩过程中膜污染较轻,采用化学清洗,水通量恢复率较物理清洗更高。以上结果为正渗透浓缩城市污水中混合无机盐汲取液的研究提供参考。     

支撑气膜法脱除／回收垃圾渗滤液中氨氮

利用由微孔疏水性聚丙烯中空纤维制成的工业级膜组件对垃圾渗滤液中氨氮进行支撑气膜法脱除研究,考察了泡沫分离．石灰絮凝等预处理技术对垃圾渗滤液表面张力及COD值的处理效果,在此基础上研究了物料因素和操作因素对膜传质性能的影响,并对该工艺的长期操作稳定性进行了研究。实验结果表明该预处理技术不仅可显著提高垃圾渗滤液的表面张力,还可大大降低其色度和COD值。当进料流量为100L／h、进料氨氮浓度为1000～3000mg／L、硫酸吸收液流量为200L／h、硫酸浓度为6％～10％、温度为20～30℃时,支撑气膜过程（两级膜组件串联）可有效脱除垃圾渗滤液中99％以上的氨氮,同时得到含10％～15％硫酸铵的水溶液作为副产品。工业级支撑气膜组件在连续运行的2个月内保持了良好的传质稳定性。     

粉煤灰基陶瓷微滤膜处理水中悬浮物的抗污染特性

粉煤灰基陶瓷微滤膜是一种新型的廉价无机膜,为研究其抗污染性能,研究了自制的管式膜在处理几种典型料液中的分离性能和渗透性能.考察了过滤不同料液过程中的阻力构成和膜的抗污染特性,并且和文献报道的同类过程中其他膜材料的性能进行了比较.实验进行了2～45 h无反冲、无清洗的连续运行.在过滤粉煤灰悬浮液、高龄土悬浮液和斜生栅藻悬浮液过程中,截留率可以达到100％,过滤阻力低于类似条件下的其他膜材料,在长时间运行后仍能保持较高的通量,表现出良好的抗污染性能.在过滤活性污泥时,截留率达到99.8％,单位压力下过滤通量达到1 170 L/(m·h·MPa).和其他膜材料相比,单位压力下的过滤通量表现出明显的优势.     

旋转填充床中Fenton＋O3氧化降解模拟阿莫西林废水

以旋转填充床（RPB）作为反应装置,研究了Fenton工艺与Fenton＋O3工艺处理模拟阿莫西林废水的效果,考察了FeSO4·7H2O的投加量、温度、旋转床转速、液体流量及pH对C0D去除率的影响。实验表明,Fenton＋O3工艺的COD脱除率及BOD5／COD相对于Fenton工艺分别提升26．7％和140％。该工艺在pH为3、温度为25℃、液体流量30L／h、气体流量2．5L／h、转速800r／min、H2O2的投加量为1mmol／L及Fe2＋投加量为0．4mm01／L的条件下,100mg／L的模拟阿莫西林废水中COD的去除率达到57．9％,BOD5/COD从0增加到0．36,满足后续生化处理要求。     

不饱和聚酯树脂高浓度废水共沸精馏资源化与治理技术

针对不饱和聚酯树脂生产高浓度废水的特点,采用新型共沸精馏技术进行资源化预处理。实验结果表明,共沸精馏几乎将废水中的原料、聚合中间体等有机物全部浓缩于釜液中,釜底浓缩液COD可高达120万mg／L左右,有机物回收率达93％～96％。将COD约120万nq-g／L的釜液以20％比例投入不饱和聚酯树脂合成反应中,制得了一种新型高性能树脂,且树脂的得率由常规生产的93．4％提高至99．77％。对与共沸剂分离后的COD约为1万mg／L的馏出液采用新型多技术协同催化氧化技术进行预处理,使废水B／C由0．021提高至0．3以上;再采用EGSB＋MBBR生化处理和活性炭吸附深度处理,出水可稳定达标排放,并能满足循环冷却水要求。     

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.