Investigations of 2-alkyl-3-methoxypyrazines in three ladybug species and wine /

Investigations of 2-alkyl-3-methoxypyrazines (2-isopropyl-3-methoxypyra2ine, 2- secbutyl-3-methoxypyrazine and 2-isobutyl-3-niethoxypyrazine) in ladybug species {Coleoptera: Coccinellidae) and wine samples have been conducted. Headspace sampling coupled with gas chromatography-mass spectrometry was used to determine amounts of 2-alkyl-3-methoxypyra2ines in the ladybug species. Hippodamia convergens had the highest amount of alkybnethoxypyrazines, followed by Harmoma axyridis and the least in Coccinella septempunctata. Using a solvent extraction method, the precoccinelline alkaloid was found present in Hippodamia convergens and Coccinella septempunctata but not Harmonia axyridis. Steam distillation followed by a soHd phase extraction method as a sample preparation technique, enhanced detection while the isotope dilution method afforded accurate quantitation of the alkyknethoxypyrazines in the wine samples. Both ladybug-tainted and commercial wine samples were found to contain the 2- alkyl-3-methoxypyrazines. Wine samples prepared in 2001 generally contained higher levels than the corresponding 2003 samples. Levels of the 2-alkyl-3-methoxypyrazines found in the commercial wines ranged from a minimum value of 6 ng/L to 260 ±10 ng/L. Analyses revealed that for both ladybug species and wine samples, the 2- isopropyl-3-methoxypyrazine had the highest concentration, followed by 2-isobutyl- 3-methoxypyrazine and the least being the 2-secbutyl-3-methoxypyrazine. Possible contamination of the wine samples by ladybugs is thoroughly discussed. Furthermore, attempts to remove or reduce the levels of the alkylmethoxypyrazines with molecularly imprinted polymers from wine samples are presented in detail.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.

Developing a numerical inverse-theory-based extraction of orientation-dependent relaxation rates from partially- relaxed spectra

Second-rank tensor interactions, such as quadrupolar interactions between the spin- 1 deuterium nuclei and the electric field gradients created by chemical bonds, are affected by rapid random molecular motions that modulate the orientation of the molecule with respect to the external magnetic field. In biological and model membrane systems, where a distribution of dynamically averaged anisotropies (quadrupolar splittings, chemical shift anisotropies, etc.) is present and where, in addition, various parts of the sample may undergo a partial magnetic alignment, the numerical analysis of the resulting Nuclear Magnetic Resonance (NMR) spectra is a mathematically ill-posed problem. However, numerical methods (de-Pakeing, Tikhonov regularization) exist that allow for a simultaneous determination of both the anisotropy and orientational distributions. An additional complication arises when relaxation is taken into account. This work presents a method of obtaining the orientation dependence of the relaxation rates that can be used for the analysis of the molecular motions on a broad range of time scales. An arbitrary set of exponential decay rates is described by a three-term truncated Legendre polynomial expansion in the orientation dependence, as appropriate for a second-rank tensor interaction, and a linear approximation to the individual decay rates is made. Thus a severe numerical instability caused by the presence of noise in the experimental data is avoided. At the same time, enough flexibility in the inversion algorithm is retained to achieve a meaningful mapping from raw experimental data to a set of intermediate, model-free

QUANTIFICATION AND EXTRACTION OF SURFACE FEATURES FROM DIGITAL TERRAIN MODELS

Digital Terrain Models (DTMs) are important in geology and geomorphology, since elevation data contains a lot of information pertaining to geomorphological processes that influence the topography. The first derivative of topography is attitude; the second is curvature. GIS tools were developed for derivation of strike, dip, curvature and curvature orientation from Digital Elevation Models (DEMs). A method for displaying both strike and dip simultaneously as colour-coded visualization (AVA) was implemented. A plug-in for calculating strike and dip via Least Squares Regression was created first using VB.NET. Further research produced a more computationally efficient solution, convolution filtering, which was implemented as Python scripts. These scripts were also used for calculation of curvature and curvature orientation. The application of these tools was demonstrated by performing morphometric studies on datasets from Earth and Mars. The tools show promise, however more work is needed to explore their full potential and possible uses.