沸石生物联合吸附再生工艺中溶解性有机物的特性变化

利用三维荧光技术(EEM)和凝胶过滤色谱法(GFC)研究了沸石生物联合吸附再生(ZCS)工艺中溶解性有机物(DOM)在系统中的变化规律.结果表明,生活污水DOM中主要的荧光物质有类蛋白质(荧光峰A和B)和类腐殖质(荧光峰C),经ZCS工艺处理后,荧光峰B较峰A的强度降低更多,说明类蛋白质的组成结构发生了变化;荧光峰C削...     

改良型AO法组合工艺中有机物的三维荧光分析

采用三维荧光(EEM)光谱技术,对上海竹园第二污水处理厂改良型AO法组合工艺运行过程中的各种溶解性有机物(DOM)进行分析,并对比研究传统好氧活性污泥法曝气池出水和A/O脱氮工艺硝化池出水DOM的EEM光谱的迁移变化特性.结果表明,各种DOM中主要的荧光物质有类蛋白质(荧光峰A和B)及类腐殖质(荧光峰C),经改良型AO法组合工艺处理后,荧光峰的强度降低了14％～60％,同时类蛋白质和腐殖质的结构也发生了变化;腐殖酸溯源表明DOM中的腐殖酸以微生物代谢产生的带有荧光基团的腐殖酸类为主.     

生物吸附-多级A/O-活性焦组合工艺对污水中氮磷及有机污染物的去除

利用生物吸附(biological absorption,AB)-多级缺氧/好氧(anaerobic/oxic,A/O)-活性焦滤池组合工艺对城市污水进行处理研究。结果表明:该组合工艺出水COD、TN、TP平均浓度为20、8.5、0.25 mg·L~(-1),对COD、TN、TP平均去除率为95%、76.5%、80%,3个工艺段对有机污染物的平均去除率分别为55%、26%、14%。其中生物吸附段主要去除粒径较大的颗粒态有机物,多级A/O段可以去除进水中53%左右溶解性有机物;活性焦滤池利用活性焦丰富的中孔结构有效吸附多级A/O出水中难生物降解的芳香类及环烷类有机物。该组合工艺能实现高标准出水、高效脱氮除磷、能源节约、资源回收,是具有良好应用前景的污水处理工艺。     

城市污水处理过程中DOM的三维荧光光谱及紫外谱图特性

利用三维荧光光谱法和紫外分光光度法对城市污水处理过程中溶解性有机物(DOM)的光谱特性等进行研究。结果表明,污水中的类蛋白质物质较易被降解,类腐殖酸物质属于较难生物降解物质。且在λ_(Ex)/λ_(Em)为(290~295)nm/(325~330)nm处出现新荧光峰,推测其可能是溶解性微生物代谢产物或是被原荧光峰覆盖的难降解有机物所发射荧光形成的。FI值在2.03~2.16,表明DOM主要是生物来源且芳香度较低。紫外谱图在190~230 nm和250~290 nm分别存在着明显的吸收带和吸收平台。在好氧处理后,紫外谱图中的吸收带发生了红移且其吸收强度逐渐增大。通过SUVA、UV_(253)/UV_(203)值和Zeta电位在生物处理过程中的变化,表明DOM经过生物降解,芳香构造程度化逐渐增大,所含苯环的取代程度降低,逐渐稳定。污水处理过程中TOC、UV_(254)与λ_(Ex)/λ_(Em)位于(230~235)nm/(340~350)nm的类蛋白质所发射的荧光强度、荧光峰荧光强度和之间均有很强的正相关性。     

几种腐殖填料生物滤池COD去除效能比较研究

分别采用腐殖垃圾、泥炭、煤炭等腐殖填料及河沙构筑生物滤池,处理模拟废水,比较研究其COD去除效能及降解特征,为工艺填料改性提供理论依据。几种填料的扫描电镜分析图显示腐殖垃圾及泥炭以团聚体三维空间结构为主;煤炭与河沙表面粗糙程度较小,且主要由颗粒状物质构成。稀释平板涂布法分离出各生物滤池中发挥主要作用的微生物共3种,各系统菌落数量有差异,但种类相同。3种腐殖填料生物滤池在进水有机物浓度为500 mg/L及1000 mg/L时均有较理想的有机物去除效率。3种腐殖填料生物滤池中泥炭构筑的腐殖填料生物滤池有机物比降解速率最小,因而微生物比增长速率最小,微生物增长和自身氧化最易趋向于动态平衡,对应的饱和水力渗透系数最大,滤池最不易发生堵塞,最有利于腐殖填料生物滤池长期稳定运行,证明泥炭是一种优良的生物介质。     

切削液废水处理过程中溶解性有机物分子质量分布和光谱特征的转化规律

以隔油-混凝沉淀-水解酸化-好氧共代谢为组合工艺处理切削液废水,探究各处理单元对不同种类有机物的转化规律和去除能力;对各处理单元出水中的溶解性有机物(DOM),采用超滤膜法进行分子质量分级,应用紫外-可见吸收光谱、三维荧光光谱等方法对各单元出水及其滤后液进行了分析。结果表明,隔油池出水DOM分子质量主要分布在1 kDa小分子质量区间和100 kDa的大分子质量区间,分子质量占比分别为46.04%、42.79%,混凝沉淀对大分子质量的DOM有较好的去除效果,混凝沉淀出水、水解酸化池出水、好氧池出水的DOM主要分布在1 kDa区间。切削液废水处理过程中出现5个荧光峰,其中峰A和峰B可能为多环芳香烃和杂环化合物的混合物;峰C为石油类;峰D可能是废切削液中滋生的微生物和细菌的细胞物质及其分泌物或单环芳香烃;峰E可能为杂环化合物或多环芳烃类腐殖酸。经一级处理(隔油和混凝沉淀)后峰A和峰B的去除率分别为60%和35%;峰C和峰D去除率均大于99%。经二级处理(水解酸化和好氧共代谢),峰A和峰B的去除率分别为23%和48%。该工艺流程对切削液废水中的有机物有较好的去除效果,石油类、COD、TOC、BOD_5的总去除率可达99.99%、98.81%、98.74%、99.78%,达到了《污水排入城镇下水道水质标准》中的B级标准。     

O_3-BAC工艺臭氧优化和有机物分子质量分布研究

为了确定3种工艺:混凝-沉淀-砂滤-后臭氧-生物活性炭滤池(工艺Ⅰ)、预臭氧-混凝-沉淀-砂滤-生物活性炭滤池(工艺Ⅱ)和预臭氧-混凝-沉淀-砂滤-后臭氧-生物活性炭滤池(工艺Ⅲ)中臭氧的最优投加量和投加方式,采用动态实验进行了不同工况下有机物的去除效果研究,并从臭氧利用率的角度对3种工艺进行比较。同时,为了明晰工艺Ⅲ中各个单元对有机物的去除机制,研究了各处理阶段的有机物分子质量分布情况。结果表明,工艺Ⅲ在最佳工况下出水水质最优,但单位臭氧利用率较低,单位臭氧去除CODMn、TOC分别为0.92 mg/L和0.55 mg/L。该工艺中预臭氧可显著降低有机物分子质量水平,混凝沉淀砂滤主要去除分子质量3 k Da的有机物,后臭氧则将大分子有机物进一步氧化为分子质量3k Da的有机物,后者通过生物活性炭滤池得到有效地去除。因此,通过臭氧和生物活性炭的联用,能够有效去除有机物,是一种适宜的饮用水深度处理工艺。     

光谱与呼吸图谱联用判定河流污染状态与自净能力

河流污染状态一般采用化学水质或生物等指标单独描述,目前尚缺少简便易行且可同时从化学与生物角度进行定量描述的指标。针对这一问题,采用三维荧光光谱、紫外吸收光谱与呼吸图谱联用的分析方法研究了纳污河、自然水体与污水处理厂各处理单元水样的溶解性有机物(DOM)的空间分布特征与河流微生物的呼吸特征。结果表明,光谱法可快速对河流有机污染物的种类进行辨别,而呼吸图谱具有识别河流自净能力的特点,其中类色氨酸(T峰与D峰)、类酪氨酸(S峰)、腐殖质(C峰)、富里酸(A峰)是指示不同污染程度的重要指标。通过呼吸图谱与荧光光谱联用(T峰)可快速对污染程度和自净能力进行区分,从而为河流的管理与自净能力的恢复提供参考。     

不同垃圾渗滤液组合处理工艺中DOM的变化特征

为了快速表征垃圾渗滤液处理过程中有机物的特性变化,分别采用紫外光谱和三维荧光光谱对2种垃圾渗滤液处理工艺不同单元溶解性有机物(DOM)的变化进行了系统分析。结果表明,二级RO和厌氧+好氧+MBR+NF+RO工艺对渗滤液COD和NH3-N的去除率分别为98.7%、99.0%和98.8%、98.6%。随着处理过程的进行,2个处理工艺中DOM的SUVA254、E253/E203分别由0.74、0.33和0.46、0.12下降至0.015、0.014和0.010、0.012,有机物的芳香性和不饱和性下降,脂肪链芳香烃化合物开始增加。不同处理阶段渗透液DOM三维荧光光谱表明,随着处理过程的进行,类富里酸和类蛋白物质的含量逐渐下降,芳构化程度开始降低。其中二级RO系统对渗滤液中类富里酸物质的去除效果较好,而厌氧-好氧-MBR-NF-RO工艺中,类酪氨酸物质主要通过微生物降解去除,NF和RO膜对类富里酸和类腐殖酸物质的截留效果较好。     

化学混凝-两级BAF工艺处理低温城市污水中试研究

以大庆东城污水处理厂进水为实验原水,采用化学混凝-两级曝气生物滤池(BAF)组合工艺进行现场中试研究(12 m3/d),重点考察了在化学混凝的强化作用下,曝气生物滤池工艺对低温城市污水中有机物、氮和磷等污染物的净化效能。实验结果表明,单独采用两级曝气生物滤池工艺,当原水COD、NH3-N、TN和TP的平均浓度分别为45...     

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.