N-dealkylation of amines during water disinfection - Revealing a new direction in the formation of disinfection by-products.

Among numerous disinfection by-products (DBP) forming during aqueous chlorination nitrogen containing species are of special concern due to their toxicological properties. Nevertheless, corresponding reaction products of these natural and anthropogenic compounds are not sufficiently studied so far. An interesting reaction involves dealkylation of the substituted amine moiety. Here we present the results of the comparative study of one-electron oxidation and aqueous chlorination of several aliphatic and aromatic amines. The reaction products were reliably identified with gas chromatography - high resolution mass spectrometry (GC-HRMS), high pressure liquid chromatography - electrospray ionization high resolution mass spectrometry HPLC-ESI/HRMS), and electrochemistry - electrospray ionization high resolution mass spectrometry (EC-ESI/HRMS). Certain similarities dealing with the formation of the corresponding aldehydes and substitution of alkyl groups at the nitrogen atom for hydrogen were shown for the studied processes. The mechanism of the substituted amines' aqueous chlorination involving one-electron oxidation is proposed and confirmed by the array of the observed reaction products. Alternative reactions taking place in conditions of aqueous chlorination, i.e. aromatic electrophilic substitution, may successfully compete with dealkylation and produce major products.

Polycyclic aromatic hydrocarbons in the snow cover of the northern city agglomeration.

Sixteen priority polycyclic aromatic hydrocarbons (PAHs) were qualitatively and quantitatively assessed by high-performance liquid chromatography with fluorescence detection in snow samples collected at 46 sites of Arkhangelsk as a world's largest city above 64 degrees north latitude. The average, maximum and minimum PAH concentrations in snow were 168, 665, and 16 ng/kg, respectively. The average toxic equivalent value in benzo(a)pyrene units was 3.6 ng/kg, which is three-fold lower than the established maximum permissible concentration and considered an evidence of a low/moderate level of snow pollution with PAHs. The pollution origin was assessed using specific markers based on PAHs ratios in the studied samples. The pyrogenic sources of PAH emission were predominate, whereas the significant contributions from both transport and solid fuel combustion were observed. Benzo(a)pyrene concentrations are highly correlated with the levels of other PAHs with higher molecular weights.