Use Of Diffusion Controlled Preconcentration Systems With Chemically Immobilized Coatings For The Determination Of Atmospheric Nitric Acid

Abstract

A new coating procedure for different diffusion controlled preconcentration methods (tubular denuder, annular denuder, diffusion screen) is described for the determination of nitric acid in air. In this study, a silanization reaction is applied to obtain a chemically fixed coating with an end placed functional NH₂-group, which can be used as a sink to collect acidic compounds from air. This coating must be carried out only once and can be used for a long time. The denuders, coated with this procedures, were compared with conventionally coated NaF denuders.     

Measurements Of Biogenic Hydrocarbons And Their Atmospheric Degradation In Forests

Abstract

An analytical procedure for the sampling and quantitative determination of biogenic hydrocarbons in the atmosphere is presented. The method is based on the adsorptive preconcentration of the hydrocarbons using Tenax TA/Carbopack B filled sampling tubes followed by thermodesorption of the trapped compounds and gas chromatographic analysis. To avoid losses of the biogenic alkenes as a consequence of their reaction with ozone on the adsorbents during the sampling step, an ozone scrubber is used in front of the adsorption tubes. Diurnal variations of the monoterpene- and ozone-concentrations are determined at different heights in and above a forest stand (coniferous and deciduous trees) in the Vosges (Col du Donon, 760 m a.s.l.) in order to elucidate the importance of terpene-oxidation reactions on the formation of peroxidic products in forest air.     

Automatic Headspace Sampling for Determination of Ethylene Dibromide Residues in Cereals

Abstract

The possibility was investigated to apply a commercially available automatic head-space sampler in trace analysis of ethylene dibromide (EDB, 1,2-dibromoethane), in cereals.

Samples of rice and wheat flour were thermostatted in closed vials at 70[ddot]C for 30min. The top gas was then automatically introduced into a gas chromatograph equipped with an electron capture detector. Quantitation was performed using external standards (untreated samples spiked with solutions of EDB in N,N′-dimethylacetamide).

The relative standard deviation of the method was 3.4% for rice and 4.5% for wheat flour, at a residue level of 0.008 mg/kg. The detection limit was 0.001 mg/kg (the official EC residue tolerance is 0.01 mg/kg).

Preliminary experiments with other fumigants were carried out as well.

The headspace technique in question has the following advantages over other methods for determining EDB residues in cereals: 1. No sample pre-treatment like extraction, steam distillation, purge and trap etc.; 2. Automated sample handling; 3. “Clean” chromatograms.     

BP神经网络在呼叫中心抽检评估中的应用

为了提高抽样检验的检出率,基于对某运营商呼叫中心服务质量管理现状的分析,提出利用BP神经网络对客服代表输出的话务质量进行风险评估和预判分类的方法。经过Matlab仿真平台的模拟实验,确定风险因子和风险等级,并进行数据归一化处理,建立数学模型,得到结论:BP神经网络技术应用于呼叫中心服务质量风险评估和抽样检验领域是可行的、有效的。基于该方法,可以将呼叫中心服务质量抽样检验的检出率从传统方法的5.3%提高到现在的9.23%,提高了质检人员的工作效率。     

The aliasing‐phenomenon in visual terms

In a recent paper it was shown that the aliasing phenomenon, which leads to a severe identification problem in the estimation of stochastic differential equations, can be overcome by using a polygonal (or higher) approximation for the time paths of the exogenous variables. This work attempts to visualize the problem and presents several simulated trajectories of a continuous time AR(2)‐process (Ornstein‐Uhlenbeck‐process) together with the observationally equivalent structures. Furthermore it is shown that aliasing can even change the analytical properties of the time paths of the system: whereas the first component of the Ornstein‐Uhlenbeck‐process is differentiable, the trajectories of the aliasing structures are continuous, but not differentiable any more.     

Evolutionary variational inequalities with a volterra term

The mathematical model of the injection molding process is characterized by evolutionary inequalities with an elliptic principal part and a Volterra term. Existence and uniqueness of the solution of these problems are derived by means of an argument based on the Banach fixed point theorem. Regularity results are obtained by using the penalty and Rothe method. The results can be considered as a starting point for the numerical treatment and for the application to injection molding.     

On the signal degradation induced by the interpolation and the sampling rate reduction in aeroacoustics hybrid methods

Taking place within more extensive work that focuses on hybrid methods in aeroacoustics, the present study is devoted to the data transfer operations that are to be performed between two stages of a hybrid calculation. More precisely, the article focuses on two typical operations that usually accompany such data transfer, which are (i) the sampling rate reduction and (ii) the interpolation of the unsteady perturbations to be transmitted from one stage to the other. First part of the paper analyzes the two main issues of such operations, which are the spuriousing and the aliasing phenomena. For doing so, the usual notions of the interpolation theory are revisited before they are synthesized within an original approach. The here proposed formalism allows to understand better both the spuriousing and the aliasing phenomena, as well as to accurately predict the impact of the latter on the data to be transmitted in terms of signal degradation. Second part of the paper provides an illustration and a validation of these theoretical developments via a direct application to a typical aerodynamic noise problem (aeroacoustic emission by a 2D cylinder cross flow). There, it is further shown how the here proposed formalism can help in improving aeroacoustics hybrid calculations by predicting (and thus possibly minimizing) the bias to be induced on the acoustic extrapolation stage because of the aliasing and/or spuriousing effects inherited from the sampling rate reduction and/or interpolation of CFD data—which is likely to occur in any hybrid scenario. Copyright © 2012 John Wiley & Sons, Ltd.     

Reaching multi‐nanosecond timescales in combined QM/MM molecular dynamics simulations through parallel horsetail sampling

We report an enhanced sampling technique that allows to reach the multi‐nanosecond timescale in quantum mechanics/molecular mechanics molecular dynamics simulations. The proposed technique, called horsetail sampling, is a specific type of multiple molecular dynamics approach exhibiting high parallel efficiency. It couples a main simulation with a large number of shorter trajectories launched on independent processors at periodic time intervals. The technique is applied to study hydrogen peroxide at the water liquid–vapor interface, a system of considerable atmospheric relevance. A total simulation time of a little more than 6 ns has been attained for a total CPU time of 5.1 years representing only about 20 days of wall‐clock time. The discussion of the results highlights the strong influence of the solvation effects at the interface on the structure and the electronic properties of the solute. © 2017 Wiley Periodicals, Inc.     

An improved Sampling Strategy for the Measurement of VOCs in Air,Based on Cooled Sampling and Analysis by Thermodesorption-GC-MS/FID

Abstract

Reliable and comprehensive sampling methods are required to obtain accurate data for VOC concentrations in air samples. The major drawback of the adsorption tube sampling method, widely employed in environmental studies, is the fact that C₂ compounds are usually not trapped quantitatively.

The focus of this work was thus to improve sampling based on adsorption tubes packed with Molsieve and Carbosieve. To improve the sampling efficiency for the C₂ compounds, a cooling device, based on Peltier cooling was constructed, which could be operated at a temperature down to ?30°C.

Experiments under laboratory and field conditions were carried out to study the influence of the sampling temperatuie on the recovery of ethane and ethene as the most volatile VOCs. The results clearly demonstrate the need for a cooled sampling device for the analysis of C₂ compounds in air. Under the investigated conditions, the recoveries with ambient temperature sampling were only in the range of 38–46% for ethane and 33–59% for ethene respectively, in comparison to the cooled sampling device. These findings are only valid for the described conditions and can change significantly with temperature and concentration. A generalisation of the recovery is thus very difficult to give.

The use of the sampling device for a field study is reported, where samples were collected simultaneously at three different altitudes in a diurnal profile on the slope of the Schulterberg mountain in Tyrol (Austria).