Development of Analytical Methods for  Determination Azaarenes and Azaarones in Environmental
                                             Matrices


                                            Jan Brulík

A new method for the analysis of azaarenes and their degradation products (azaarones) was
developed, optimized and validated using liquid chromatography coupled with atmospheric pressure
photo ionization tandem mass spectrometric detection (LC-APPI/MS/MS). The presences of azaarenes in
environmental significant concentrations were proofed in soil, sediment, water, air and biota.
Additionally an unknown part of the azaarenes is biologically or photochemically oxidized in the
aquatic environment to azaarones. The concentrations of azaarones measured in sediments are higher
than the concentrations of parental azaarenes. Studies have shown that although generally the acute
toxicity is decreasing from azaarenes to azaarones, some of the azaarones have much lower toxic
effect concentrations than azaarenes, in fact comparable with PAHs. Thus for the evaluation of the
total toxic pressure of polyaromatic compound influent water and benthic organisms is necessary
evaluated not only the PAHs, but also the azaarenes and azaarones present in the environment. In
our project seventeen compounds of azaarenes and azaarones were analyzed in sediment samples. All
compounds were analysed simultaneously in multi reaction monitoring (MRM) mode. Soxhlet extraction
was used for the extraction of analytes from sediments. The low limits of quantification of
azaarenes and azaarones were reached with low matrix interferences. The method was tested on real
sediment samples from Dutch rivers Rhine in Rotterdam and Western Scheldt near Antwerp and the
results were compared with previous studies. To our knowledge, this is the first time showing the
possibility of measurement non-polar polyaromatic hydrocarbons together with polar azaarenes and
their degradation products azaarones simultaneously with sufficient sensitivity and accuracy using
LC/MS/MS. The method was further used for measurement sediment samples collected in period
1996-2011 in Dutch Waddensee and spatial and temporal trends of azaarenes and azaarones in sediment
were determined. It was shown that the chemical quality of environment in Wadden Sea is determined
mainly by the quality of water by rivers Rhine and Scheldt which influent Wadden Sea through the
sea streams in North Sea, through the contamination in Ijsselmeer in the Netherlands and with river
Ems, Weser and Elbe flowing directly to Wadden Sea in Germany. Thanks to the low sediment exchange
in Wadden Sea the pollution from those sources is accumulated in this area.