LES validation of urban flow,part II: eddy statistics and flow structures

Time-dependent three-dimensional numerical simulations such as large-eddy simulation (LES) play an important role in fundamental research and practical applications in meteorology and wind engineering. Whether these simulations provide a sufficiently accurate picture of the time-dependent structure of the flow, however, is often not determined in enough detail. We propose an application-specific validation procedure for LES that focuses on the time dependent nature of mechanically induced shear-layer turbulence to derive information about strengths and limitations of the model. The validation procedure is tested for LES of turbulent flow in a complex city, for which reference data from wind-tunnel experiments are available. An initial comparison of mean flow statistics and frequency distributions was presented in part I. Part II focuses on comparing eddy statistics and flow structures. Analyses of integral time scales and auto-spectral energy densities show that the tested LES reproduces the temporal characteristics of energy-dominant and flux-carrying eddies accurately. Quadrant analysis of the vertical turbulent momentum flux reveals strong similarities between instantaneous ejection-sweep patterns in the LES and the laboratory flow, also showing comparable occurrence statistics of rare but strong flux events. A further comparison of wavelet-coefficient frequency distributions and associated high-order statistics reveals a strong agreement of location-dependent intermittency patterns induced by resolved eddies in the energy-production range. The validation concept enables wide-ranging conclusions to be drawn about the skill of turbulence-resolving simulations than the traditional approach of comparing only mean flow and turbulence statistics. Based on the accuracy levels determined, it can be stated that the tested LES is sufficiently accurate for its purpose of generating realistic urban wind fields that can be used to drive simpler dispersion models.     

Oxygen tolerance capacity of upflow anaerobic solid-state (UASS) with anaerobic filter (AF) system

In order to investigate the oxygen tolerance capacity of upflow anaerobic solid-state(UASS)with anaerobic filter(AF) system, the effect of microaeration on thermophilic anaerobic digestion of maize straw was investigated under batch conditions and in the UASS with AF system. Aeration intensities of 0–431 m L O2/gvswere conducted as pretreatment under batch conditions. Aeration pretreatment obviously enhanced anaerobic digestion and an aeration intensity of 431 m L O2/gvsincreased the methane yield by 82.2%. Aeration intensities of 0–355 m L O2/gvswere conducted in the process liquor circulation of the UASS with AF system. Dissolved oxygen(DO) of UASS and AF reactors kept around 1.39 ±0.27 and 0.99 ± 0.38 mg/L, respectively. p H was relatively stable around 7.11 ± 0.04. Volatile fatty acids and soluble chemical oxygen demand concentration in UASS reactor were higher than those in AF reactor. Methane yield of the whole system was almost stable at 85 ± 7 m L/gvs as aeration intensity increased step by step. The UASS with AF system showed good oxygen tolerance capacity.     

Exposure reduction of seed treatments through dehusking behaviour of the wood mouse <Emphasis Type="Bold">(</Emphasis><Emphasis Type="Italic">Apodemus sylvaticus</Emphasis><Emphasis Type="Bold">)</Emphasis>

Background, aim and scope  

Seed treatments are widely used on cereals and other annual crops throughout Europe. Most of the formulated pesticide is found on the outside of the seed, the husk. Risk assessments of seed treatments are especially needed for granivorous mice living in the agricultural landscape e.g. for registration using the guidance for risk assessment for birds and mammals (EFSA 2009). The dehusking of seeds before consumption is a known behaviour of these mammals, but so far, no quantitative data on the reduction of exposure of seed treatments by dehusking were published. Therefore, we aimed at providing a first quantitative estimate of this behaviour-related exposure reduction for the wood mouse (Apodemus sylvaticus) with different seed types.     

Triazines in the aquatic systems of the Eastern Chinese Rivers Liao-He and Yangtse

The results of a one-year monitoring program on the two Eastern Chinese River systems, i.e. the Liao-He and the Yangtse, with special emphasis on the presence of triazine herbicides are presented. Sediment, suspended solids and water samples from both rivers were analyzed. Additionally, recovery experiments on the SPE-in-field-enrichment procedure and the extraction methods were performed. The samples were measured by gas chromatography coupled with mass spectrometry, electron capture detection and a newly developed mu-plasma atomic emission detector. A typical result of a one-year monitoring was obtained in case of the Liao-He: During winter, at low water period, low triazine values were found. A similar situation was found in early spring. Highest concentrations of atrazine up to 1600 ng/l were found in late spring in the water samples. Maximum concentrations of atrazine, simazine, propazine, simetryn and prometryn were observed in this season as a result of the actual use of triazines. Finally, after the high water period in autumn the triazine concentrations decreased. Additionally, atrazine adsorbed on sediment (up to 2.8 ng/g) and suspended solids was determined (up to 8 ng/l) during late spring sampling. Therefore, the logarithm of the organic carbon based sorption coefficient of atrazine could be calculated. Low levels of atrazine were measured in the water of Yangtse (up to 18.3 ng/l). The concentrations from all sampling points and sampling stations of a particular sampling date were similar, which indicates a homogeneous distribution of this herbicide. Due to the high discharge rate of up to 79,000 m3/s in case of the Yangtse a considerable mass transport of up to 57.5 kg per day atrazine may take place, even at concentrations below the European drinking water limit of 100 ng/l.     

Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol

The haloalkane dehalogenase LinB from Sphingobium indicum B90A converts β-hexachlorocyclohexane (β-HCH), the most persistent HCH stereoisomer, to mono- and dihydroxylated metabolites. Recently, we reported that LinB also transforms α-, β- and γ-hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. Here, we show that LinB catalyzes the hydroxylation of δ-HBCD to two pentabromocyclododecanols (PBCDOHs) and two tetrabromocyclododecadiols (TBCDDOHs). The stereochemistry of this enzymatic transformation was deduced from XRD crystal structure data of the substrate δ-HBCD and α₂-PBCDOH, one of the biotransformation products. Five stereocenters of δ-HBCD are unchanged but the one at C6 is converted to an alcohol with inversion from S- to R-configuration in a nucleophilic, S_N2-like substitution reaction. Only α₂-PBCDOH with the 1R,2R,5S,6R,9R,10S-configuration is obtained but not its enantiomer. With only two of the 64 PBCDOHs formed, these transformations indeed are regio- and stereoselective. A conformational analysis revealed that the triple-turn motive, which is predominant in δ-HBCD and in several other HBCD stereoisomers, is also found in the product. This shows that LinB preferentially converted reactive bromine atoms but not those in the conserved triple-turn motive. The widespread contamination with HCHs triggered the bacterial evolution of dehalogenases which acquired the ability to convert these pollutants and their metabolites. We here demonstrate that LinB of S. indicum also transforms HBCDs regio- and stereoselectively following a similar mechanism.     

从全局审视EHS系统 避免信息孤岛

本文通过诠释EHS集成解决方案架构的路线图,告诉我们,EHS应被视为生产链和运营流程的一部分,而不仅仅是公司信息化建设中的一座孤岛。公司要想卓越地安全运营,其安全管理信息化就必须从全局去审视,它不仅应像神经元网络一样,具有灵活度和敏捷度,更要渗透到"个人",如此才能创建出公司整体的安全文化。     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of beta-HBCD racemization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD stereoisomers suggest that the presented isomerization mechanism is of relevance for those stereoisomers as well.     

In situ transformations of fine lead oxide particles in different soils

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.