重组基因酵母技术分析城市污水A~2/O工艺处理前后雌激素类化合物活性

采用重组基因酵母技术分析城市污水经厌氧—缺氧—好氧(A2/O)工艺处理前后雌激素类化合物活性。酵母经过雌激素类化合物激活,产生β-半乳糖苷酶,通过测定β-半乳糖苷酶活性能可以判断污水中雌激素类化合物活性。结果表明,原污水水样与酵母培养液体积比为5.000时,雌激素类化合物活性与摩尔浓度为10-8 mol/L的雌二醇(E2)相当;经过污水处理厂A2/O工艺处理后,雌激素类化合物活性下降,但仍具有潜在的环境与健康风险。     

A2O工艺中雌激素的行为变化和去除机理

研究了厌氧-缺氧-好氧(A2O)活性污泥工艺对生活污水中天然雌激素雌酮(Estrone,E1)、17β-雌二醇(17β-Estradiol,E2)以及17α-乙炔基雌二醇(17α-Ethynylestradiol,EE2)的去除性能。在对COD、N和P具有良好去除效果的前提下,对E1、E2和EE2的去除率可分别达到92.7%、100%和62.7%。通过对各反应单元内3种雌激素的物料平衡分析,表明A2O工艺对雌激素的去除主要发生在厌氧段和好氧段。以失活污泥作为对照组,好氧硝化过程中雌激素去除的小试实验发现,好氧过程中E1、E2的去除主要依靠生物降解作用,而EE2的去除则主要依赖于活性污泥对其的吸附作用。     

长江、嘉陵江(重庆段)源水有机提取物的类雌激素活性评价

为了解长江、嘉陵江(重庆段)源水有机提取物的类雌激素活性，分别于夏季和冬季采用GDX—120大孔树脂对位于城区上、中、下游5个断面长江、嘉陵江(重庆段)源水进行有机物的浓缩提取。用体外MCF—7细胞增殖试验检测有机提取物的类雌激素活性。结果显示，源水有机提取物均具有类雌激素活性。其类雌激素活性中、下游均高于上游，丰水期高于枯水期。     

A^2O工艺中雌激素的行为变化和去除机理

研究了厌氧-缺氧-好氧（A2O）活性污泥工艺对生活污水中天然雌激素雌酮（Estrone,E1）、17β-雌二醇（17β-Estradiol,E2）以及17α-乙炔基雌二醇（17α-Ethynylestradiol,EE2）的去除性能。在对COD、N和P具有良好去除效果的前提下,对E1、E2和EE2的去除率可分别达到92.7%、100%和62.7%。通过对各反应单元内3种雌激素的物料平衡分析,表明A2O工艺对雌激素的去除主要发生在厌氧段和好氧段。以失活污泥作为对照组,好氧硝化过程中雌激素去除的小试实验发现,好氧过程中E1、E2的去除主要依靠生物降解作用,而EE2的去除则主要依赖于活性污泥对其的吸附作用。     

胶体迁移及其对典型类固醇雌激素的吸附

研究胶体自身的可迁移性和对污染物的可吸附性能够为地下环境中胶体对污染物的携带迁移作用提供重要依据。通过动态柱实验和静态批实验研究二氧化硅胶体、伊利石胶体和胡敏酸胶体在饱和多孔介质中的可迁移性以及对雌酮和雌二醇的吸附作用。结果表明:不同胶体在饱和多孔介质中的可迁移性有所差异,胡敏酸胶体和二氧化硅胶体分别在石英砂柱和河砂砂柱中迁移性最强,而伊利石胶体在2种多孔介质中的迁移性均较弱;准二级动力学模型对胶体吸附雌激素的数据拟合效果最好,吸附速率的控制因素可能包括表面吸附、化学络合等;Langmuir模型对胶体吸附雌激素的拟合效果较Freundlich模型更好,推测胶体对雌激素的吸附为单层吸附,3种胶体对雌酮和雌二醇的最大吸附量分别为90.09～3 333 mg?kg~(-1)和116.28～2 000 mg?kg~(-1)。因此,胶体的可迁移性和对雌激素的吸附作用能够为胶体影响雌激素在地下环境中的迁移提供理论指导。     

重金属离子对生物炭吸附水环境中雌激素的影响

以小麦秸秆为原料制备生物炭(BC),采用批量吸附实验研究BC对水环境中雌激素双酚A(BPA)、17α-乙炔基雌二醇(EE2)的吸附行为,并选用模型污染物菲作对比,探讨了重金属离子(Cu~(2+)、Cd~(2+)、Pb~(2+))对BC吸附雌激素的影响和作用机制。结果表明:BC对污染物的最大吸附能力为菲BPAEE2,其主要吸附机制为疏水性作用、π—π电子供受体作用、孔隙填充作用等。在重金属离子存在条件下,BC对污染物的吸附明显降低,一方面是因为重金属离子与BC表面含氧官能团发生络合作用竞争吸附点位;另一方面是因为重金属离子可与周围水分子之间形成三维水合金属离子进行孔隙堵塞。Pb~(2+)对BC吸附能力的抑制作用最弱,这主要是因为Pb的水合离子半径最小,孔阻塞和竞争作用最弱。     

气相色谱—质谱分析5种雌激素类物质的衍生化方法优化

选取5种雌激素类物质雌酮(E1)、雌二醇(E2)、17α-雌二醇(EE2)、雌三醇(E3)、双酚A(BPA)为研究对象,在气相色谱(GC)—质谱(MS)联用分析方法的基础上,对衍生化试剂和衍生化反应条件进行了优化。结果表明,使用含有1%(质量分数)三甲基氯硅烷(TMCS)的N,O-双(三甲基甲硅烷基)-三氟乙酰胺(BSTFA)联合吡啶作为衍生化试剂,加热条件为烘箱70℃加热40min时,衍生化产物单一且灵敏度高。采用此优化方法得到5种物质的平均加标回收率为98.0%~104.3%,相对标准偏差(RSD)为0.4%~12.5%,可为环境中5种雌激素类物质的分析测定提供参考。     

芳香类污染物的厌氧生物降解研究

综述了国内外芳香类污染物厌氧降解的研究进展,详细阐述了含氮芳香类、氯代芳香类和酚类污染物厌氧降解的微生物类群与机理.提出了芳香类污染物生物降解今后发展方向的重点是共基质条件下生物降解性研究、厌氧-好氧条件下的生物降解性研究、高效工程菌和固定化细胞技术应用研究、构建基因工程菌和遗传学研究等技术领域.     

高效液相色谱-二极管紫外阵列/荧光串联测定雌激素的方法及污水处理厂对雌激素的去除特性

建立了高效液相色谱-二极管紫外阵列(PDA)/荧光(FLD)串联法测定雌酮(E1)、雌二醇(E2)、乙炔雌二醇(EE2)、雌三醇(E3)和双酚A(BPA)5种典型雌激素的方法,并利用该方法测定了某城市污水处理厂5种雌激素的分布情况及去除特性。研究结果表明,二极管紫外阵列/荧光检测器对5种雌激素的检出限在4.30~9.54μg·L~(-1)之间,定量限在12.90~28.62μg·L~(-1)之间。5种雌激素日内精密度的相对标准偏差小于6.86%,日间精密度相对标准偏差小于9.47%;对100、500和1 000 ng·L~(-1)3个浓度的5种雌激素经富集浓缩后测定的加标回收率在62.8%~96.0%之间,方法符合痕量分析要求。利用该方法对城市某污水处理厂雌激素的含量进行测定,结果表明污水处理厂进水中5种雌激素的总浓度为3 073.1 ng·L~(-1),其中雌三醇(E3)的浓度最大,占5种雌激素总量的40.1%。出水中5种雌激素的总浓度为124.7 ng·L~(-1),5种雌激素的总去除率为95.9%。不同处理单元对雌激素的去除效率存在明显差异,生物处理单元对5种雌激素的去除效果最好,5种雌激素的去除率在73.6%~96.6%之间;一级处理工艺和消毒工艺对雌激素的去除效果较差。     

抗生素类污染物对活性污泥生物毒性测定方法的筛选与评价

尽管衡量化学物质生物毒性的标准方法很多,但关于环境中抗生素类污染物的生物毒性及其对污泥活性影响的科学数据较少。以磺胺和四环素两类作用机理和作用谱带不同的抗生素为研究对象,分别用发光细菌法、脱氢酶活性法、生长抑制法及呼吸速率法进行了抗生素类污染物生物毒性测定方法的筛选与评价。结果表明,发光细菌标准方法中30min的作用时间太短,延长作用时间不仅导致各种抗生素的EC50值大幅度降低,同时毒性排列顺序也发生了改变;以活性污泥为对象的脱氢酶活性和呼吸速率抑制实验的EC50值与抗生素类物质对敏感致病菌的MICs相比异常高,不适宜于作为单独方法准确评估抗生素类污染物的生物毒性。生长抑制实验中,活性污泥混合菌种增殖生长对磺胺类抗生素敏感,而假单胞杆菌对四环素类抗生素敏感。不同方法测定抗生素毒性的灵敏度顺序是发光细菌(24 h)>生长抑制(7 h)>呼吸速率(24 h)>脱氢酶活性(24 h)。用标准方法评价抗生素类污染物的生物毒性,可能导致对抗生素排放到水环境中所带来的风险估计不足。     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.