Applicability of some mass spectrometric criteria for the confirmation of pesticide residues

This study was initiated to demonstrate the impact of tolerance intervals calculated based on experimental data and standard criteria on the capability to detect and identify pesticide residues by GC-MS in plant extract. The tolerance intervals specified by the current guidelines and standards (EU, EPA, ISO, EC) result in a large number of false negative values. The tolerance intervals calculated based on the actually measured ion ratios at 2 different probability levels did not provide a better estimate. Based on experimental findings a 2-phase procedure for confirmation of pesticide residues is recommended. The first screening phase comprises identification of those pesticide residues that are likely to be present avoiding false negatives as far as possible. Relatively large tolerance intervals, +/-30% of absolute ion abundances ratios, have to be used at this point. When 2 or 3 selected ion ratios are within the established tolerance intervals the residue is confirmed. When the ions detected still indicate the possible presence of a residue the result may be reported as tentatively identified. However, when the result would lead to regulatory action, second confirmatory phase has to be undertaken. This can be achieved with the same GC-MS equipment, by injecting matrix-matched standards of the suspected analyte, in order to compensate for matrix influence on ion ratios. Alternatively, methods using different physico-chemical properties of the compound have to be used. The choice of the technique depends on their availability, time and cost.     

The Development of Highly Fluorescent Hemicyanine and Dicyanoisophorone Dyes for Applications in Dye-Sensitized Solar Cells

Journal of Fluorescence - Ruthenium-based metal complex dyes have been employed extensively in dye-sensitized solar cells (DSSCs) as photosensitizers, but the cost and toxicity of metal complexes...     

Numerical and experimental direct shear tests for coarse-grained soils

The presence of particles larger than the permissible dimensions of conventional laboratory specimens causes difficulty in the determination of shear strength of coarse-grained soils. In this research, the influence of particle size on shear strength of coarse-grained soils was investigated by resorting to experimental tests in different scale and numerical simulations based on discrete element method (DEM). Experimental tests on such soil specimens were based on using the techniques designated as "parallel" and "scalping" to prepare gradation of samples in view of the limitation of laboratory specimen size. As a second approach, the direct shear test was numerically simulated on assemblies of elliptical particles. The behaviors of samples under experimental and numerical tests are presented and compared, indicating that the modification of sample gradation has a significant influence on the mechanical properties of coarse-grained soils. It is noted that the shear strengths of samples produced by the scalping method are higher than samples by the parallel method. The scalping method for preparing specimens for direct shear test is therefore recommended. The micromechanical behavior of assemblies under direct shear test is also discussed and the effects of stress level on sample behavior are investigated.     

Determination of pesticide residues in peaches by using gas chromatography and mass spectrometric detection

ABSTRACT

A multi-residue method using selected ion monitoring mode GC-MSD has been developed for the quantitative analysis of 30 widely used pesticides in fresh peaches produced in Swat Malakand, Pakistan. The planned methodology involved a sample extraction procedure using liquid-liquid partition with acetonitrile followed by a clean-up step based on solid-phase extraction (SPE). Method validation was performed in accordance with European Union guidelines. The European Union criteria (recovery 70–120%, RSD <20%) were met for majority of pesticides. For most of the pesticides, signal-to-noise ratios were good and background-corrected mass spectra often contained sufficient diagnostic to enable identity and confirmation. The limits of quantification (LOQs) were in the range 0.01–1.0 mg/kg. The above method was successfully applied to the analysis of peach samples (n = 30) from the field. Pesticide concentration in real peach samples was compared with the maximum residue levels (MRLs). Pesticide residues were detected in 73% of the peach samples. Most frequent residues were metalaxyl, α-cypermethrin, azoxystrobin, dimethoate, tebuconazol, λ-cyhalothrin and spiromesifin in peach samples.     

A developed high-performance thin-layer chromatography method for the determination of baicalin in Oroxylum indicum L. and its antioxidant activity

JPC – Journal of Planar Chromatography – Modern TLC - A simple, accurate, precise, and specific high-performance thin-layer chromatography (HPTLC) method for the quantitative...     

Analysis of Thermal Flow in a Rotating Porous U-Turn Duct Using Lattice Boltzmann Method

The lattice Boltzmann method is carried out to investigate the heat transfer enhancement in a U-turn duct which is partially filled with a porous media. The porous layer is inserted at the core of the duct and is modeled using the Brinkman–Forchheimer assumptions. In order to validate the results, first a channel flow problem without any porous layer is compared with available data. Second, the porous Couette flow and partially porous channel flow are successfully compared with the studies of other researchers. Then, fluid flow in a clear U-turn duct is studied looking carefully at the velocity, curvature and rotation effects. Finally, the effects of porous layer thickness on the rate of heat transfer and pressure drop are investigated. Parametric studies are conducted to evaluate the effects of various parameters (i.e., Reynolds number, Darcy number, rotation number), highlighting their influences on the thermo-hydrodynamics behavior of the flow. The optimum values of porous layer thickness are presented for specific flow parameters.     

A transition in the spectral statistics of quantum optical model by different electromagnetic fields

In this paper, we have considered the effects of different quantized electromagnetic fields on the spectral statistics of two-level atoms. The Berry-Robnik distribution and the maximum likelihood estimation technique are used to analyze the effect of the mean photon numbers, the two level atoms numbers and also the quantum number of considered states on the fluctuation properties of different systems which are described by different sets of the Dicke Hamiltonian’s parameters. Our results describe the obvious effect of mean photon number on the spectral statistics and show more regular dynamics when this quantity reaches 700. Also, we observed universality in the spectral statistics of considered systems when the number of two level atoms approaches an unrealistic limit (N _A ~ 200) and there are some suggestions about the effect of the quantum number of selected levels and the atom-field coupling constant on level statistics.     

Extraction of ammonia and nitrite using modified magnetite iron oxide nanoparticles before spectrophotometric determination in different water samples

A new analytical approach was developed for the extraction and determination of ammonia and nitrite in environmental water samples involving magnetic solid-phase extraction (MSPE) with magnetite nanoparticles (MNPs) as the adsorbent. The procedure is based on the derivatisation of ammonia based on Berthelot reaction. The obtained indophenol dye was extracted using MSPE and determined spectrophotometrically at 655 ± 3 nm. Nitrite ion is determined after its reduction to ammonia in the presence of Zn/HCl. The main factors that affected the extraction efficiency were studied and optimised. The method gave calibration curves for ammonia with good linearity in the range 10–550 µg L^?1, and correlation coefficients (r) higher than 0.99. The detection and quantification limit was found to be 3.1 and 10.2 µg L^?1, respectively. The method showed good precision and accuracy, with intra- and inter-assay precisions of less than 6.6% at all concentrations. The recoveries ranged 89–105% and 88–105%, for ammonia and nitrite determination, respectively. The method was applied to the determination of the target analytes in real samples.     

Micromechanics of breakage in sharp-edge particles using combined DEM and FEM

By combining DEM （Discrete Element Method） and FEM （Finite Element Method）, a model is established to simulate the breakage of twodimensional sharp-edge particles, in which the simulated particles are assumed to have no cracks. Particles can, however, crush during different stages of the numerical analysis, if stress-based breakage criteria are fulfilled inside the particles. With this model, it is possible to study the influence of particle breakage on macro- and micro-mechanical behavior of simulated angular materials. Two series of tests, with and without breakable particles, are simulated under different confining pressures based on conditions of biaxial tests. The results, presented in terms of micromechanical behavior for different confining pressures, are compared with macroparameters. The influence of particle breakage on microstructure of sharp-edge materials is discussed and the related confining pressure effects are investigated. Breakage of particles in rockfill materials are shown to reduce the anisotropy coefficients of the samples and therefore their strength and dilation behaviors.     

Micromechanics of breakage in sharp-edge particles using combined DEM and FEM

By combining DEM (Discrete Element Method) and FEM (Finite Element Method),a model is established to simulate the breakage of two-dimensional sharp-edge particles,in which the simulated particles are assumed to have no cracks.Particles can,however,crush during different stages of the numerical analysis,if stress-based breakage criteria are fulfilled inside the particles.With this model,it is possible to study the influence of particle breakage on macro- and micro-mechanical behavior of simulated angular materials.Two series of tests,with and without breakable particles,are simulated under different confining pressures based on conditions of biaxial tests.The results,presented in terms of micromechanical behavior for different confining pressures,are compared with macroparameters.The influence of particle breakage on microstructure of sharp-edge materials is discussed and the related confining pressure effects are investigated.Breakage of particles in rockfill materials are shown to reduce the anisotropy coefficients of the samples and therefore their strength and dilation behaviors.