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。     

双酚A和典型类固醇环境激素迁移转化研究进展

近年来有关环境激素污染的认知、研究与防治已经开始受到全球的重视,其中双酚A(BPA)和类固醇是环境中检出频率较高的几种环境激素.国外有关BPA和类固醇环境激素的调查和其迁移转化的研究已经广泛展开,但我国仍处于起步阶段.综述了国内外BPA和两种典型类固醇激素17β-雌二醇(E2)和17α-乙炔基雌二醇(EE2)的研究进展,介绍了其基本性质、用途、危害、环境中浓度和其迁移转化规律;指出为了阐明BPA、E2和EE2在环境中危害,有关其吸附、生物降解和光降解等迁移转化规律,及各迁移转化过程之间协同作用与相互影响的研究还有待于进一步深入.     

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。     

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。     

生物炭对双酚A和17α-乙炔基雌二醇在土壤中吸附的影响

研究了添加生物炭对土壤吸附双酚A(BPA)和17α-乙炔基雌二醇(EE2)的影响。结果表明:BPA和EE2在添加生物炭前后的土壤中的等温吸附线都能被Freundlich模型很好地拟合,所有等温吸附线都呈现出非线性(非线性参数n在0.40~0.79之间),且添加生物炭之后吸附参数KF显著增大。根据等温吸附线,在污染物的平衡浓度为0.01 mg·L-1时,添加4%生物炭后,BPA和EE2的土水分配系数(Kd)分别提高了2.6和3.0倍,此时生物炭对土壤吸附BPA和EE2的贡献度分别达到72.5%和88.5%。进一步研究发现,添加生物炭使土-水吸附系统的p H及溶解性有机质浓度(DOC)升高,这对污染物在土壤中的吸附分别表现为一定的抑制和促进作用。添加生物炭对土壤吸附EE2的促进效果优于BPA,这主要是由于EE2比BPA具有更强的疏水性。     

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。     

腐殖酸对生物炭吸附水环境中雌激素的影响

以玉米秸秆为原料,通过500℃限氧裂解制备生物炭(记为500BC),并采用批量吸附实验对比500BC及腐殖酸负载后生物炭(记为500BC-HA)对于水环境中两种雌激素(双酚A(BPA)和17α-乙炔雌二醇(EE2))的吸附性能及作用机制。结果表明,腐殖酸分子可阻塞部分500BC孔隙,使500BC的孔径、孔容及比表面积下降,负载腐殖酸后,500BC的比表面积由8.43m~2/g减小至4.40m~2/g,孔径从26.1nm减小至3.2nm,孔容由0.018cm~3/g下降至0.001cm~3/g;与500BC相比,500BC-HA对BPA、EE2的吸附能力均明显降低,一方面是因为腐殖酸分子占据了500BC表面的吸附点位并堵塞部分孔隙,使其吸附能力降低,另一方面腐殖酸负载后引入更多的含氧官能团,使500BC表面疏水性降低,与雌激素间的疏水作用减弱。腐殖酸负载质量浓度为0～10mg/L时,增加负载质量浓度对500BC吸附性能影响明显,当负载质量浓度大于10mg/L时,腐殖酸在500BC表面达到饱和,继续增加负载浓度对500BC的吸附性能不再产生影响。     

三种藻类引发水中17α-乙炔基雌二醇的光降解实验研究

研究了普通小球藻、铜绿微囊藻和柱孢鱼腥藻3种藻类引发水中17α-乙炔基雌二醇(EE2)的光降解.结果表明,在250 W高压汞灯(HPML,nm)的照射下,一定藻浓度下,EE2的光降解率可达19%-20%.另外,还研究光强、藻悬浮液浓度和EE2初始浓度等对EE2光降解速率的影响,发现在本实验体系中,光通量大、藻浓度高及EE2初始浓度低有利于提高EE2的光降解速率.     

改性陶粒对水中内分泌干扰物的吸附去除

用CTMAB(十六烷三甲基溴化铵)对陶粒进行改性.实验研究了陶粒改性前后对5种内分泌干扰物EDCs(美托洛尔MTP、磺胺甲噁唑SMZ、卡马西平CBZ、对氯苯氧异丁酸CA、17α-乙炔基雌二醇EE2)的吸附特性.结果表明,CTMAB改性处理对陶粒的孔结构和表面性质都有影响,有效吸附的孔径所占比例和陶粒表面极性升高;室温条件下,EDCs初始浓度和吸附剂浓度均为1 mg/L时,实验用改性陶粒和陶粒达到吸附平衡的时间基本相同,均为5 min左右;改性陶粒能提高大部分EDCs的吸附量,5种内分泌干扰物混合物一起吸附时存在竞争,其中SMZ和MTP竞争力强,CA最弱;吸附机理包括表面物理吸附和分配作用.实验研究拟为改性陶粒应用于水中痕量污染物的处理提供理论依据,支撑保障饮用水处理达标的目的.     

污水颗粒尺寸分布对深度过滤中雌激素去除的影响

采用两根平行运行的小试下向流砂滤柱以研究雌酮(E1)、雌二醇(E2)和炔雌醇(EE2)的去除与污水中悬浮颗粒粒度分布(PSD)的相互关系。研究表明,80%雌激素以溶解状态吸附在悬浮颗粒之上。平均粒径与颗粒的比表面积呈指数函数关系(R20.9)。随着滤池进水中悬浮颗粒平均粒径从1.493μm增至226.784μm,E1、E2和EE2在固相的吸附率分别从58.8%、56.3%和60.0%降至7.0%、1.3%和4.0%。砂滤池中雌激素的去除率与进水悬浮颗粒的平均粒径呈负相关,并可以用对数曲线拟合(R~20.9)。砂滤池因拦截了活性污泥絮体因而具有一定的生物活性,使得部分E2被生物降解(p0.05)。E1和EE2因其相对稳定以及砂滤池较短的水力停留时间而无显著的生物降解证据(p0.05),其去除主要依靠砂滤池所拦截的细微颗粒的絮体吸附作用。     

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.     

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.     

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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.