固废拆解场污染土壤中多环芳烃降解菌的筛选鉴定与降解特性

以腐植酸(HA)溶液为吸附剂、从受多环芳烃污染的土壤中分离出来的降解菌制成为生物修复剂,以多环芳烃(PAHs)萘、菲、芘、荧蒽、苯并蒽、苯并芘为土壤污染物,对PAHs污染土壤进行修复实验。目的是筛选与分离吸附于HA的PAHs降解菌,研究HA与降解菌的协同效应对PAHs的降解效率的影响。用经过HA吸附的PAHs富集分离培养出1株高效降解菌株,命名为Tzyx3,鉴定其为解脂耶氏酵母菌(Yarrowia lipolytica)。15 d后,土壤中萘、菲、芘、荧蒽、苯并蒽、苯并芘的降解率分别为90.7%、91.0%、74.7%、86.9%、84.7%和74.7%,表明Tzyx3和HA在PAHs污染土壤中存在协作关系,Tzyx3能够直接利用HA对土壤中的多环芳烃进行降解。     

盐环境下降解菌群对芘的降解特性研究

以芘为多环芳烃(PAHs)的代表物,利用1.0%盐度的无机盐培养基从石油污染土壤中富集出高效嗜盐PAHs降解菌群。通过DNA测序鉴定,菌群中对芘起重要降解作用的是Rhodanobacter、Pseudomonas、Mycobacterium,3者碱基比例达到31.82%。14d内,萘、菲、荧蒽、芘、苯并[a]芘5种PAHs的挥发损耗均可忽略不计。筛选得到的菌群降解芘的最佳条件为:酵母粉质量浓度为120mg/L,盐度不超过1.0%,无需额外添加甲基-β-环糊精。筛选出的降解菌群对芘的最佳降解条件可用于降解萘、菲、荧蒽和苯并[a]芘等其他PAHs,但随着PAHs环数增加,分子量增大,降解率降低。在最佳条件下降解14d时,萘、菲、荧蒽、芘、苯并[a]芘5种PAHs的降解率可分别达100.00%、85.48%、51.92%、56.28%、50.45%。     

八羟基喹啉改性膨润土预处理养殖废水

以八羟基喹啉为改性剂,天然膨润土为原料,制备一种新型吸附剂,并将其应用于养殖废水的预处理中。确定了改性膨润土的最佳制备条件:土液比为4 g/L,改性剂浓度为0.3 g/L,改性时间为50 min,改性温度为50℃。并以扫描电镜方法对改性膨润土行进表征:八羟基喹啉已经有效进入层间,改变了膨润土的性状,提高了吸附效果。优化了改性膨润土处理养殖废水的工艺条件:投土量为1 g/L,pH为4,搅拌时间为30 min,搅拌速度为350 r/min,沉淀时间为40 min。在此优化条件下,改性膨润土对养殖废水的COD去除率最高可达79.18%,且吸附动力学结果满足二级动力学模型。     

低温等离子体净化尾气中的颗粒相多环芳烃

利用低温等离子体(NTP)净化车用柴油机尾气中的颗粒相多环芳烃(PAHs),基于电晕放电的原理,设计了NTP发生装置。使用色谱质谱联用仪分析经过NTP净化前后柴油机尾气中颗粒相多环芳烃的含量,观察NTP对颗粒相多环芳烃的净化效果。结果表明,颗粒相小分子量PAHs除菲、蒽外,其他4种多环芳烃的含量显著增加,其中萘、苊变化率达1130.4%和758.57%;大分子量PAHs除苯并(ghi)芘外,多环芳烃的含量降低达80%以上;NTP对柴油机尾气中颗粒相多环芳烃含量及毒性当量的净化率分别达58.4%和82.8%。     

改性玉米秸秆对废水中Cr(Ⅵ)的吸附性能研究

对经碱处理和醚化接枝的改性玉米秸秆吸附剂进行了结构表征、吸附条件优化、吸附动力学及吸附等温线研究。结果表明,对于200mg/L的Cr(Ⅵ)废水,改性玉米秸秆吸附剂最佳吸附条件:吸附剂投加量为1.0g,反应温度为40℃,pH=3,反应时间为300min。吸附过程服从准二级动力学方程,吸附等温线符合Langmuir模型。     

磁性壳聚糖/膨润土复合吸附剂吸附Cu~(2+)

以膨润土、壳聚糖、Fe_3O_4为原料,制备了在外加磁场作用下能实现快速固液分离的磁性壳聚糖/膨润土复合吸附剂。利用SEM、XRD、VSM、FTIR等分析手段对复合吸附剂的形貌及微观结构进行了表征。通过静态吸附实验研究了复合吸附剂对Cu~(2+)的吸附性能,探讨了溶液初始p H值、吸附剂投加量、吸附时间和吸附温度等对Cu~(2+)吸附效果的影响。结果表明,壳聚糖和Fe_3O_4均已负载到膨润土上。复合吸附剂吸附Cu~(2+)的效果随溶液p H值和吸附剂投加量的增加而增加,并最终趋于稳定;当吸附剂投加量为7.2 g/L、p H值为6、Cu~(2+)初始浓度为30 mg/L时,Cu~(2+)的去除率可达98.5%。吸附动力学和吸附等温线数据分别较好地符合准二级动力学模型和Langmiur吸附等温模型。热力学参数表明,吸附是自发、吸热的过程。     

UV-Fenton催化氧化法对采油废水中多环芳烃的处理效果

针对采油废水中含有多环芳烃种类多且较难去除的特点,采用UV-Fenton技术对采油废水中多环芳烃的处理效果进行了研究,通过正交实验和单因素实验,研究了在254 nm波长紫外光照射下,Fe2+投加量、H2O2投加量、pH值和光照时间对水样中多环芳烃中的菲和芴处理效果的影响。实验结果显示,处理初始浓度为1 000μg/L的菲、芴时,反应的最佳工艺条件为:Fe2+浓度为1.8 mmol/L、H2O2投加量为0.15 mmol/L、pH值为4、光照时间1.25 h。在此条件下,菲和芴的去除率可达71.9%。     

改性牡蛎壳对低磷浓度水体的净化性能研究

为寻求经济、高效的生态浮床除磷基质,以牡蛎壳为对象,通过等温吸附、吸附动力学和吸附剂投加量影响实验对比研究了经不同温度热处理的改性牡蛎壳对低磷浓度水体的吸附性能。结果表明:相比Langmuir方程,Freundlich方程能更好地模拟天然及改性牡蛎壳对总磷的等温吸附行为;相对于伪一级动力学和Elovich方程,牡蛎壳对总磷的吸附动力学过程与伪二级动力学方程更为吻合。热处理温度对总磷的吸附效果产生明显影响,650℃改性牡蛎壳的吸附性能最优。牡蛎壳投加量对总磷去除效果影响也较为显著,当投加量增至20g/L时,天然牡蛎壳、250℃改性牡蛎壳、500℃改性牡蛎壳、650℃改性牡蛎壳的总磷去除率分别可达到51.27%、62.50%、88.27%和99.69%。当投加量为8g/L时,650℃改性牡蛎壳对总磷的去除率已高达90%左右。总体而言,650℃改性牡蛎壳的总磷吸附效果最好,可优先选为生态浮床除磷基质。     

粉煤灰井下填充时PAHs对地下水环境的影响

模拟平煤集团矸石电厂以及焦煤集团演马电厂粉煤灰井下填充过程,设计了静态浸泡和动态淋溶实验,并以固相萃取-气相色谱/质谱联用方法,测定了溶出液中的16种多环芳烃含量.实验结果表明:溶出液中主要的PAHs物质是萘、苊、芴、菲、蒽,均为4环以下的多环芳烃类物质,其含量较低,其中菲和蒽的总含量较高,说明在粉煤灰井下填充过程中,多环芳烃类污染物能够从粉煤灰中迁移至水体,并对地下水环境造成一定的影响.     

多环芳烃在淮河、黄河和卫河沉积物上的吸附及解吸行为研究

以淮河沉积物上多环芳烃的吸附研究为主线,以黄河、卫河沉积物为比对,研究菲和芘在3种河流沉积物上的吸附和解吸行为,重点考察吸附剂有机质组分、环境温度、吸附时间和共存物等因素对吸附的影响,找出可以用来预测这3条河流沉积物对多环芳烃吸附作用的模式。结果表明,菲和芘在3种河流沉积物上的吸附均呈非线性,可用Freundlich方程拟合,属放热反应、物理吸附。同一吸附质的有机碳归一化分配系数(Koc)数值相近,说明吸附剂有机质组分对吸附起主导作用;吸附能力随着吸附时间延长而增加,并与吸附质疏水性成正比;多环芳烃共存,有竞争吸附现象;辛醇/水分配系数可用来预测3种河流沉积物对多环芳烃的吸附作用;解吸存在滞后现象,吸附质疏水性强、吸附剂有机质含量高的体系,解吸滞后现象更加明显。     

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.     

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.     

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.     

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 and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

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.