臭氧化对垃圾填埋场后期渗滤液的预处理研究

应用自制微孔扩散式接触反应器,考察了不同pH条件下垃圾填埋场后期渗滤液的臭氧化预处理效果.结果表明,渗滤液初始pH值升高,臭氧利用率增大,垃圾渗滤液中COD、腐殖酸的去除速率加快;当初始pH为10时,经臭氧化处理120 min后,模拟废水的BOD5/COD可从初始的0.17提高到0.36,改善了废水的可生化性,同时渗滤液的色度、浊度、腐殖酸和SS也有较高的去除率.     

Ti（Ⅳ）催化臭氧／过氧化氢预处理酸性难降解废水

在Ti（Ⅳ）和过氧化氢存在条件下,考察了臭氧化酸性苯乙酮溶液、硝基苯溶液和垃圾渗滤液（浙江衢州某垃圾填埋场）的预处理效能。结果表明,在pH2．86条件下,单独臭氧化处理对苯乙酮、硝基苯和垃圾渗滤液的COD去除率分别为10．1％、44％和28．6％。BOD,／COD值分别从原来的0．039、0．060和0．085提高到了0．130、0．158和0．174,仍属生化难降解废水。当体系加入Ti（Ⅳ）后,臭氧化苯乙酮和硝基苯的COD去除率分别达到了75．5％和65％,BOD;／COD则提高到了0．679和0．314,可生化性提升明显。对于垃圾渗滤液,只有当体系加入Ti（Ⅳ）和H22后,臭氧化COD的去除率达到66．6％,BOD、／COD提高至0．425。上述结果对酸性难降解废水的处理实际意义非常突出。     

臭氧氧化法处理反渗透浓缩垃圾渗滤液

采用臭氧氧化法处理经反渗透膜处理后的浓缩垃圾渗滤液,考察了反应时间、臭氧投量、pH和温度对COD,色度以及浓缩液中腐殖酸的去除影响,通过BOD₅/COD变化分析了臭氧氧化对浓缩液生化性的提高作用。结果表明：在pH 8.0,温度30℃,臭氧投量5 g/h,反应时间90 min的条件下,浓缩液的COD、色度以及浓缩液中腐殖酸的去除率分别达到67.6%、98.0%和86.1%, BOD₅/COD从0.008提升到0.26,生化性有很大提高。     

铁-碳微电解法预处理老龄垃圾填埋场渗滤液的研究

由于老龄垃圾填埋场渗滤液属于难降解废水，直接生物处理效果不佳。用微电解法预处理老龄垃圾填埋场渗滤液后，结果表明，其COD、NH3-N和色度的去除率最高分别达到74％、79％和97．5％，可生化性也有很大提高，BOD5／CODcr从0．04提高到0．29，为后续的生化处理创造了良好的条件。     

O3／UV预处理磺酰脲类除草剂生产废水的研究

采用O3／UV工艺预处理磺酰脲类除草剂生产废水,考察了初始pH值、臭氧投量、叔丁醇投加等因素对废水处理效果的影响,并初步探讨了该工艺处理废水的反应机理。实验结果表明,在废水初始pH为13．59和臭氧投量为65．08mg／min的条件下,预处理80min后废水COD去除率达63．47％,BOD5／COD由0．03提高至0．56,EC50从11％提高至55％。随着叔丁醇浓度的增加,废水COD去除率明显降低,证明该反应体系有·OH存在;体系中加入MnO2后废水COD去除率下降了16％,氧化效率明显下降,证明该反应体系内中间产物HO2O在O3／UV降解有机废水过程中起到了重要的作用。     

垃圾渗滤液生物处理出水臭氧氧化的研究

对垃圾渗滤液生物处理出水进行了臭氧氧化的研究。研究表明,随着氧化时间的延长,CODCr去除率增大;在碱性条件下进行臭氧氧化。pH越高,CODCr去除效率越高。采用BOD5／CODCr来表征垃圾渗滤液的生物降解性,研究了臭氧氧化前后垃圾渗滤液生物处理出水的生物降解性变化规律,表明臭氧氧化可以提高垃圾渗滤液生物处理出水的生物降解性,但提高的幅度不大。通过色谱-质谱法（GC—MC）对臭氧氧化前后垃圾渗滤液的成分进行分析,结果表明,臭氧氧化前后废水中的主要成分没有发生变化,仍然为难降解物质;臭氧氧化使废水中的部分物质发生了结构上的变化,减少、消失和生成的物质多为可降解物质。     

O3氧化工艺处理黄连素制药废水研究

采用臭氧（O3）氧化法处理含高浓度黄连素和COD的制药废水,探讨了废水初始pH、O3投加量及初始黄连素浓度等因素对O3氧化过程的影响,确定了O3氧化技术处理黄连素制药废水的最佳操作条件。结果表明,O3能够有效分解废水中的黄连素,降低其COD浓度;黄连素浓度为700mg／L、COD为3500mg／L、pH为0．88的废水,进气O3浓度为14．05mg／（L·min）,处理时间为180rain（即投加量为2529mg／L）时,黄连素和COD的降解率分别可达77．46％和41．28％,BOD,／COD比（B／C比）从0．06提高到0．34,增加了4．7倍;随着废水中初始黄连素浓度的升高,废水COD降解率逐渐降低。O3氧化法是一种有效的黄连素制药废水预处理技术,可以大大提高废水的可生化性。     

H2O2协同O3预处理垃圾填埋场后期渗滤液的研究

应用自制微孔扩散式接触反应器,考察了H2O3/O3在不同摩尔比下对垃圾填埋场后期渗滤液的氧化处理效果.结果表明,H2O3/O3的摩尔比对处理效果有明显的影响.在试验范围内,确定H2O3/O3的最佳摩尔比为0.2:1,最佳处理时间为90 min,经过H2O3/O3处理后,垃圾填埋场后期渗滤液的BOD5/COD可从初始的0.17提高到0.36,改善了废水的可生化性,同时渗滤液的色度、浊度、腐殖酸和SS也有较高的去除率.     

臭氧预氧化-BAF工艺深度处理垃圾渗滤液

以广东省江门市垃圾填埋场垃圾渗滤液为研究对象,对经SBR生化处理和聚合硫酸铁混凝后的垃圾渗滤液,采用臭氧-BAF(曝气生物滤池)工艺进行深度处理。该工艺优点在于：臭氧高级氧化技术使大分子有机污染物降解成二氧化碳和水,或者小分子有机污染物,有利于后继BAF的生化处理,且臭氧处理过后废水的色度明显降低,是废水处理的有效方法之一。而后采用曝气生物滤池对垃圾渗滤液进行进一步处理,对COD进一步去除。结果表明,当臭氧的加入量为150 mg/L,BAF停留时间＞4 h,出水COD低于85 mg/L,稳定达到国家GB 16889-1997《生活垃圾填埋污染控制标准》一级排放标准,臭氧氧化法处理每吨垃圾渗滤液的费用为4.8元。     

高铁酸钾预处理垃圾渗滤液

采用自制高纯度高铁酸钾预处理危废填埋场和垃圾焚烧厂的垃圾渗滤液,探讨和分析了处理效果。正交实验表明,高铁酸钾预处理危废填埋场渗滤液COD的最佳条件为:高铁酸钾与COD的初始质量浓度比为0.5、渗滤液初始pH值4.00、反应温度30℃、反应时间40 min,此时COD去除率达71.51%。此最佳条件下高铁酸钾对不同类型垃圾渗滤液的色度、SS、COD、BOD5、氨氮、总磷、重金属离子等污染因子都具有良好的去除效果,危废填埋场渗滤液经高铁酸钾预处理后可以直接进入后续生化处理系统;垃圾焚烧厂渗滤液预处理后其COD为2 861.0 mg/L,经二次预处理也可进入生化处理系统。实验结果表明,高铁酸钾对不同类型垃圾渗滤液都具有良好的预处理效果。     

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.