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.     

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).     

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.     

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.     

A note on random walks with absorbing barriers and sequential Monte Carlo methods

In this article, we consider importance sampling (IS) and sequential Monte Carlo (SMC) methods in the context of one-dimensional random walks with absorbing barriers. In particular, we develop a very precise variance analysis for several IS and SMC procedures. We take advantage of some explicit spectral formulae available for these models to derive sharp and explicit estimates; this provides stability properties of the associated normalized Feynman–Kac semigroups. Our analysis allows one to compare the variance of SMC and IS techniques for these models. The work in this article is one of the few to consider an in-depth analysis of an SMC method for a particular model-type as well as variance comparison of SMC algorithms.     

Comparing the mechanical response of di‐, tri‐, and tetra‐functional resin epoxies with reactive molecular dynamics

The influence of monomer functionality on the mechanical properties of epoxies is studied using molecular dynamics (MD) with the Reax Force Field (ReaxFF). From deformation simulations, the Young's modulus, yield point, and Poisson's ratio are calculated and analyzed. Comparison between the network structures of distinct epoxies is further advanced by the monomeric degree index (MDI). Experimental validation demonstrates the MD results correctly predict the relationship in Young's moduli. Therefore, ReaxFF is confirmed to be a useful tool for studying the mechanical behavior of epoxies. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 255–264     

On global stability of a nonresident computer virus model

In this paper, we establish new sufficient conditions for the infected equilibrium of a nonresident computer virus model to be globally asymptotically stable. Our results extend two kind of known results in recent literature.     

Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing

The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384     

Calibration of the complex matrix effects on the sampling of polycyclic aromatic hydrocarbons in milk samples using solid phase microextraction

Solid phase microextraction (SPME), a simple, fast and promising sampling technique, has been widely used for complex sample analysis. However, complex matrices could modify the absorption property of coatings as well as the uptake kinetics of analytes, eventually biasing the quantification results. In the current study, we demonstrated the feasibility of a developed calibration method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in complex milk samples. Effects of the complex matrices on the SPME sampling process and the sampling conditions were investigated. Results showed that short exposure time (pre-equilibrium SPME, PE-SPME) could increase the lifetime of coatings, and the complex matrices in milk samples could significantly influence the sampling kinetics of SPME. In addition, the optimized sampling time, temperature and dilution factor for PAHs were 10 min, 85 °C and 20, respectively. The obtained LODs and LOQs of all the PAHs were 0.1–0.8 ng/mL and 1.4–4.7 ng/mL, respectively. Furthermore, the accuracy of the proposed PE-SPME method for milk sampling was validated by the recoveries of the studied compounds in two concentration levels, which ranged from 75% to 110% for all the compounds. Finally, the proposed method was applied to the screening of PAHs in milk samples.     

Comparison of Multivariate Matching Methods: Structures,Distances, and Algorithms

Abstract

A comparison and evaluation is made of recent proposals for multivariate matched sampling in observational studies, where the following three questions are answered: (1) Algorithms: In current statistical practice, matched samples are formed using “nearest available” matching, a greedy algorithm. Greedy matching does not minimize the total distance within matched pairs, though good algorithms exist for optimal matching that do minimize the total distance. How much better is optimal matching than greedy matching? We find that optimal matching is sometimes noticeably better than greedy matching in the sense of producing closely matched pairs, sometimes only marginally better, but it is no better than greedy matching in the sense of producing balanced matched samples. (2) Structures: In common practice, treated units are matched to one control, called pair matching or 1–1 matching, or treated units are matched to two controls, called 1–2 matching, and so on. It is known, however, that the optimal structure is a full matching in which a treated unit may have one or more controls or a control may have one or more treated units. Optimal 1 — k matching is compared to optimal full matching, finding that optimal full matching is often much better. (3) Distances: Matching involves defining a distance between covariate vectors, and several such distances exist. Three recent proposals are compared. Practical advice is summarized in a final section.