Development of a membraneless extraction module for the extraction of volatile compounds: application in the chromatographic analysis of vicinal diketones in beer.
A membraneless extraction module (MLEM) for the sample preparation of volatile compounds and its use for the chromatographic analysis of vicinal diketones in beer are reported. The extraction process is based on the same principles of gas diffusion (GD) and pervaporation (PV); however it does not use a membrane. This module has a lower chamber where the sample continuously flows, while volatile compounds evaporate to the headspace. Inside the module there is a suspended small reactor, where a small volume of a suitable acceptor solution is placed. This extraction module was tested in the determination of vicinal diketones (VDKs) in beer (CV=5%; LOD=4 microg L(-1)), showing applicability with real samples. Several parameters of the extraction process, such as temperature, sample flow and extraction time, were studied and optimized. This module proved to be a good tool for the sampling of volatile compounds, since the extraction is made without using a membrane avoiding all the robustness problems related with its use.
Voltammetric determination of trace amounts of diacetyl at a mercury meniscus modified silver solid amalgam electrode following gas-diffusion microextraction.
A new approach was developed for the determination of trace amounts of diacetyl in food products using gas-diffusion microextraction (GDME) and subsequent detection by differential pulse voltammetry (DPV) at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE). Diacetyl is a vicinal diketone responsible for the buttery aroma in many fermented foods and beverages. Its determination is important not only for evaluation of the final product quality (note of mention: health related concerns were associated with continuous diacetyl exposure) but also to monitor fermentation. GDME, a technique combining gas-diffusion and microextraction, particularly aimed to volatile and semi-volatile analytes, seemed the best way to selective extract diacetyl. A solution of 0.05% o-phenylenediamine (OPDA) prepared in a Britton-Robinson buffer (pH 5.0) was chosen as the extracting solution. This solution simultaneously extracts, pre-concentrates and derivatizes diacetyl to 2,3-dimethylquinoxaline (DMQ), enhancing the extraction selectivity and making the analyte electroactive. After finding the optimum conditions for the extraction process (10min at 60°C with 1.0mL of OPDA at pH 5.0), the DPV measurements at the m-AgSAE were conducted with a scan rate of 7mVs-1, a modulation amplitude of 50mV and a modulation time of 100ms. Under these conditions, the resulting DMQ could be easily measured at a potential of -0.6V vs. Ag|AgCl (3molL-1 KCl). The amalgam electrode keeps the advantages of classic mercury electrodes, like high sensitivity, while being environmentally friendly. The GDME/m-AgSAE produced suitable method features for the determination of low amounts of diacetyl (as DMQ) in alcoholic beverages, and in fact, to the best of our knowledge, the limit of quantification of 0.18µgL-1 is one of the lowest reported in literature.
Numerical analysis of surface crack propagation in flexible pavements using XFEM and cohesive zone model
Surface initiated (top-down) cracking in the longitudinal direction of pavements has become a predominant mode of failure in thick asphalt pavements. Most previous researchers studied crack propagation using the traditional Linear Elastic Fracture Mechanics (LEFM) method by calculating the stress intensity factor around the crack tip. In this paper, Extended Finite Element Method (XFEM) was used to study the key factors causing surface initiated crack propagation under surface tension and/or shear. A two-dimensional (2-D) finite element (FE) model for a two-lane flexible pavement was built to predict pavement responses and crack propagation potential under various scenarios. It was found that surface tension is the major driving force for crack propagation when the crack is at some distance away from tire loading. The results show that the distance from the location of crack to tire loading, the depth and direction of the crack, and the modulus ratio between the hot-mix asphalt (HMA) layer and the base layer have significant influences on crack propagation under surface tension. On the other hand, this study shows that shear stress can induce surface initiated crack propagation near the loading area as the shear resistance of material becomes low at the high temperature.