孤立与非孤立城市街道峡谷内污染物扩散

通过求解二维不可压N-S方程、k-ε方程及污染物对流扩散方程,模拟了孤立街道峡谷与非孤立街道峡谷内的流场及交通污染物浓度场.计算结果与风洞试验结果总体趋势一致.非孤立街道峡谷内污染物壁面浓度要大于孤立街道峡谷内的壁面浓度.通过计算街道峡谷建筑屋顶高度处的垂直方向污染物通量,说明了湍流扩散是污染物扩散出街道峡谷的主要原因,其污染物通量总为正,而平均流通量可以为负.非孤立街道峡谷由于平均流流动和湍流流动的总扩散通量减少,造成污染物在街道峡谷内集聚,从而理论上解释了非孤立街道峡谷与孤立街道峡谷污染扩散的差别.     

计算流体力学模拟街道峡谷特征和风向对细颗粒物污染扩散的影响

街道峡谷结构和风向会对街道峡谷内的污染物浓度和扩散特征带来一定影响。利用计算流体力学(CFD)软件,针对街道峡谷高宽比、建筑物间隔(建筑物间空隙与街道总长度的比值)和风向对街道峡谷内细颗粒物扩散的影响进行数值模拟。模拟结果表明,建筑物间隔为20%,风向为北风,风速为3m/s,街道峡谷高宽比分别为1∶2、1∶1和2∶1时,街道中心线距地面1.5m高度细颗粒物最大质量浓度分别位于-19.3、-88.0、-19.3m(以与街道中心点的距离计,正值表示在街道中心点以东,负值表示在街道中心点以西,下同)位置,为37.5、46.4、28.4μg/m3。街道峡谷高宽比为1∶1,风向为北风,风速为3m/s,建筑物间隔分别为0、20%和40%时,街道中心线距地面1.5m高度的细颗粒物最大质量浓度分别位于148.0、-92.3、-186.7m位置,为88.1、31.6、33.7μg/m3。街道峡谷高宽比为1∶1,建筑物间隔为20%,风速为3m/s,且分别处于西风、北风和西南风时,街道中心线距地面1.5m高度的细颗粒物最大质量浓度分别位于165.3、58.0、1.5m位置,为10.6、11.2、16.0μg/m3。可见,CFD模拟近地面污染物扩散时应考虑街道峡谷结构和风向的影响。     

街道峡谷机动车尾气污染扩散模拟与影响因子分析研究

为预测和分析街道峡谷污染物浓度,研究了街道峡谷污染物浓度影响因子.利用重庆市交通干线街道峡谷两侧NOx浓度的监测数据,验证了街道峡谷机动车尾气污染扩散模型--OSPM模型.风速转换系数修正后的OSPM模型的模拟值与实测值的R达0.862 58;风场因子验证了风速转换系数修正后的OSPM模型能较好地模拟重庆市街道峡谷的污染物浓度,一定程度上能满足环境空气质量评价要求.同时,通过分析OSPM模型的影响因子,提出了控制街道峡谷机动车尾气污染状况的建议.     

T型街道内空气流动与污染物扩散特性研究

为研究T型街道峡谷内空气流动与污染物扩散传质的特性,利用数值模拟研究来流风向角(θ)的变化(θ为45°、90°和135°)对T型街道交叉路口内空气流动与机动车尾气污染物扩散传递的影响,并与风洞实验测量数据进行验证。3种湍流模型中,可实现k—ε模型计算的速度相对偏差小于8%,与风洞实验结果一致性最好。结果表明,来流风向角的变化,会造成从街道顶部或侧面进入街道内的气流方向及通量发生改变,从而显著影响T型街道交叉口内及其附近的流动结构和污染物浓度分布。污染物容易在建筑尾流区等流动不畅的区域产生聚集,造成污染浓度偏高。当θ=135°时,T型街道内通风条件最好,街道内行人呼吸高度和建筑临街立面附近污染物浓度水平均相对较低。由于流动结构的改善,T型街道峡谷内的污染水平低于一般街道峡谷。     

道路路障对街道峡谷内污染物扩散的影响

采用数值模拟,研究不同风向角α(α=0°、45°、90°)及道路屏障位置(中间单路障和两侧双路障)对街道峡谷内机动车尾气污染物扩散的影响。数值模拟采用标准κ-ε湍流模型且Sc_t选择0.3时,计算结果与风洞实验结果较好吻合。结果表明,2种路障布置方式可有效降低人行道内污染物浓度,特别是,当α=45°时,污染物浓度最多可降低46.23%。同时,风向角α对街道峡谷内污染物扩散影响较大。当α=90°时,空气流通不良使得污染程度最为严重,且污染集中在背风侧近地面。单路障比双路障布置对污染物扩散影响更大,前者使污染物主要集中在街道中心背风侧,其他位置浓度明显降低;双路障时仅在一定范围内改善人行道内空气品质,但对街道整体污染物分布影响不大。     

主导风向对不规则建筑群街区污染物扩散的影响

以城市道路某段典型的街道峡谷为研究对象,采用ICEM CFD数值模拟技术,分析不同风向对不规则建筑群街区污染物扩散影响。结果表明:(1)北风时,距地10.0m以下范围是污染物高浓度聚集区。与北风工况相比,西北风时街谷内污染物浓度分布变化较大,沿高度截面上升依次呈连续线状→线状和部分团状→断裂团状。(2)随着建筑高度的增加,主干道中的气流绕流作用减弱。通过控制建筑的连续界面诱导街谷中的气流横向绕流,或在临街上游设置合适的开敞空间,以增加来流通风廊道,可有效改善街谷中污染物的扩散。(3)两种风向下每条街道人员停留区内污染物停留时间排序规律相同;不同风向下每条街道人员停留区内污染物停留时间不同,说明风向对每条街道内污染物的影响存在差异,每段街谷内的污染物扩散分布不是孤立系统,而是相互关联的有机整体。     

基于人工神经网络的街道峡谷NO_x浓度的数值模型研究

通过对反向传播人工神经网络的算法和网络结构的研究,发现拟牛顿算法训练速度较快,能够较好地接近误差目标值,同时建立了包括输入层、隐含层、输出层的人工神经网络三层拓扑结构。通过对街道峡谷人工神经网络的训练,模拟计算了街道峡谷NOx浓度分布值。结果显示,训练误差和测试误差比为1.11,训练样本的模拟值与实测值的相关系数为0.93,测试样本的模拟值与实测值的相关系数为0.87,模拟值与实测值的相关系数均高于显著水平为α=0.05与α=0.01所对应检验性表的相关系数临界值。该模型能够用于街道峡谷污染物浓度的模拟计算,具有较好的泛化能力。     

基于人工神经网络的街道峡谷NOx浓度的数值模型研究

通过对反向传播人工神经网络的算法和网络结构的研究,发现拟牛顿算法训练速度较快,能够较好地接近误差目标值,同时建立了包括输入层、隐含层、输出层的人工神经网络三层拓扑结构。通过对街道峡谷人工神经网络的训练,模拟计算了街道峡谷NOx浓度分布值。结果显示,训练误差和测试误差比为1．11,训练样本的模拟值与实测值的相关系数为0．93,测试样本的模拟值与实测值的相关系数为0．87,模拟值与实测值的相关系数均高于显著水平为α=0．05与α=0．01所对应检验性表的相关系数临界值。该模型能够用于街道峡谷污染物浓度的模拟计算,具有较好的泛化能力。     

针对街道峡谷内部气流场的参数化研究

为了建立一个能够快速且可靠地模拟街区尺度交通污染物三维分布的模型以应对实时在线模拟的需求,将城区的最小单位假定为两侧建筑物等高的长街区(街道峡谷),基于CFD模型对街道峡谷内部气流场的模拟结果,对街道峡谷内不同区域的气流(U、V、W 3个分量)与街区几何比例(高宽比HW和长宽比LW)、背景风(u和v 2个分量)的数值关系进行了回归分析。分析结果显示,分量U在非靠近边界的区域与街区几何比例和背景风线性相关性较好;分量V则在靠近地面或顶面的区域;分量W则是在靠近墙面的区域。利用回归分析得到的数值关系构建的参数化方法可以计算得到近似于CFD模型模拟结果的街道峡谷内部气流场。在此基础上,基于高斯模型建立了一个参数化模型,并以黑炭气溶胶BC为例对参数化模型进行评估,评估结果表明,参数化模型具有一定的实用价值。     

防风抑尘网开孔形式对流场的影响

应用CFD模拟软件Fluent 6.2提供的标准κ-ε模型,以流场数值模拟的方法对防风网结构及其网后流场进行流场模拟,研究了防风网开孔形式对物料堆表面速度、压力和湍动能变化的影响。模拟结果表明,物料堆表面风速由料堆底部沿迎风面表面向上逐渐增大,并在物料堆顶部附近出现边界层分离,使得背风面形成速度回流区;物料堆表面的压力由料堆底部沿迎风面表面向上逐渐降低,背风面则变化不大;在物料堆顶部湍动能较大,容易起尘。综合分析各个影响因素,圆形开孔防风网的挡风效果最佳。     

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.