Geochemical markers of soil anthropogenic contaminants in polar scientific stations nearby (Antarctica, King George Island).

The organic contamination of Antarctic soils and terrestrial sediments from nearby of five polar scientific stations on King George Island (Antarctica) was investigated. Gas chromatography-mass spectrometry (GC-MS) was applied to find composition of dichloromethane extracts of soil and terrestrial sediments. The presence of geochemical markers, such as n-alkanes, steranes, pentacyclic triterpenoids, and alkyl PAHs, their distribution types, and values of their ratios indicates the predominating source of organic fossil fuels and products of their refining rather than from the natural Antarctic environment. Fossil fuel-originated compounds well survived in conditions of Antarctic climate over long times thus enabling to characterize geochemical features of source fossil fuel identified as petroleum expelled from kerogen II of algal/bacterial origins deposited in sub-oxic conditions and being in the middle of catagenesis. Both microbial activity and water leaching play an important role in degradation of terrestrial oil spills in the Antarctica climate, and petroleum alteration occurs lowly over long periods of time. Synthetic anthropogenic compounds found in terrestrial Antarctica sediments included diisopropylnaphthalenes, products of their sulfonates degradation in paper combustion, and organophosporus compounds used as retardants and plasticizers.

Monolithic molecularly imprinted polymeric capillary columns for isolation of aflatoxins.

Monolithic molecularly imprinted polymers extraction columns have been prepared in fused-silica capillaries by UV or thermal polymerization in a two-step process. First, a poly-(trimethylolpropane trimethacrylate) (polyTRIM) core monolith was synthesized either by UV or thermal polymerization. Then it was grafted with the mixture of methacrylic acid (MAA) as a functional monomer, ethylene dimethacrylate (EDMA) as a cross-linking agent, 5,7-dimethoxycoumarin (DMC) as an aflatoxin-mimicking template, toluene as a porogen solvent and 2,2-azobis-(2-methylpropionitrile) (AIBN) as an initiator of the polymerization reaction. Different thermal condition of the photografting and different concentrations of the grafting mixture were tested during polymerization. The extraction capillary columns were evaluated in the terms of their hydrodynamic and chromatographic properties. Retention coefficients for aflatoxin B1 and DMC were used for assessment of the selectivity and imprinting factor. The obtained results indicate that the temperature of photografting and concentration of the grafting mixture are key parameters that determine the quality of the prepared MIPs. From the MIP columns characterized by the highest permeability the column of the highest imprinting factor was applied for isolation of aflatoxins B1, B2, G1 and G2 from the model aqueous sample followed by on-line chromatographic separation. The process was performed using a micro-MISPE-microLC-LIF system of a novel design, which allowed for detection of the eluates from the sample preparation part as well as from the chromatographic separation.

Formation of aromatics in thermally induced reactions of chemically bonded RP-C18 stationary phase.

In continuation of the research on the thermally induced chemical transformation of the silica-based chemically bonded stationary phases (C18), the oxidative cleavage of the silicon-carbon bonds with hydrogen peroxide and potassium fluoride was utilized, followed by the gas chromatography coupled with mass spectrometry (GC-MS) study of the resulting products. These investigations allowed determination of the probable structures of certain thermal modification products as the various different alkyl derivatives of the phenylsilane ligands. Apart from aromatic compounds, the products with unsaturated bonds and carbonyl functionalities were found in the analyzed extracts. The analysis of the GC-MS chromatograms reveals that under the applied working conditions, the investigated process runs with relatively low yields.