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.     

An expanded conceptual framework for solution-focused management of chemical pollution in European waters

Background

This paper describes a conceptual framework for solutions-focused management of chemical contaminants built on novel and systematic approaches for identifying, quantifying and reducing risks of these substances.

Methods

The conceptual framework was developed in interaction with stakeholders representing relevant authorities and organisations responsible for managing environmental quality of water bodies. Stakeholder needs were compiled via a survey and dialogue. The content of the conceptual framework was thereafter developed with inputs from relevant scientific disciplines.

Results

The conceptual framework consists of four access points: Chemicals, Environment, Abatement and Society, representing different aspects and approaches to engaging in the issue of chemical contamination of surface waters. It widens the scope for assessment and management of chemicals in comparison to a traditional (mostly) perchemical risk assessment approaches by including abatement- and societal approaches as optional solutions. The solution-focused approach implies an identification of abatement- and policy options upfront in the risk assessment process. The conceptual framework was designed for use in current and future chemical pollution assessments for the aquatic environment, including the specific challenges encountered in prioritising individual chemicals and mixtures, and is applicable for the development of approaches for safe chemical management in a broader sense. The four access points of the conceptual framework are interlinked by four key topics representing the main scientific challenges that need to be addressed, i.e.: identifying and prioritising hazardous chemicals at different scales; selecting relevant and efficient abatement options; providing regulatory support for chemicals management; predicting and prioritising future chemical risks. The conceptual framework aligns current challenges in the safe production and use of chemicals. The current state of knowledge and implementation of these challenges is described.

Conclusions

The use of the conceptual framework, and addressing the challenges, is intended to support: (1) forwarding sustainable use of chemicals, (2) identification of pollutants of priority concern for cost-effective management, (3) the selection of optimal abatement options and (4) the development and use of optimised legal and policy instruments.

     

Reply to the comment by D. Guyonnet,on “Comparison on percolation to batch and sequential leaching tests: Theory and data”

Reply to the comment by D. Guyonnet, on “Comparison on percolation to batch and sequential leaching tests: Theory and data”.     

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.     

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.     

Distribution of platinum group elements (Pt, Pd, Rh) in environmental and clinical matrices: Composition, analytical techniques and scientific outlook

Trace concentrations of the platinum group elements (PGE; here: Pt, Pd and Rh) play an important role in environmental analysis and assessment. Their importance is based on 1. their increasing use as active compartments in automobile exhaust catalysts, 2. their use as cancer anti-tumor agents in medicine. Due to their allergenic and cytotoxic potential, it is necessary to improve selectivity and sensitivity during analytical investigation of matrices like soil, grass, urine or blood. This paper summarizes the present knowledge of PGE in the fields of analytical chemistry, automobile emission rates, bioavailibility, toxicology and medicine.     

Substance-related environmental monitoring strategies regarding soil, groundwater and surface water — an overview

Substance-related monitoring is an essential tool within environmental risk assessment processes. The soundness of policy decisions including risk management measures is often directly related to the reliability of the environmental monitoring programs. In addition, monitoring programs are required for identifying new and less-investigated pollutants of concern in different environmental media. Scientifically sound and feasible monitoring concepts strongly depend on the aim of the study. The proper definition of questions to be answered is thus of pivotal importance. Decisions on sample handling, storage and the analysis of the samples are important steps for the elaboration of problem-oriented monitoring strategies. The same applies to the selection of the sampling sites as being representative for scenarios to be investigated. These steps may become critical to handle for larger international monitoring programs and thus trigger the quality of their results. This study based on the work of an IUPAC (International Union of Pure and Applied Chemistry) task group addresses different kinds and approaches of substance-related monitoring of different compartments of soil, groundwater and surface water, and discusses their advantages and limitations. Further important aspects are the monitoring across policies and the monitoring data management using information systems.     

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.