We investigated the primary biodegradation of different N-imidazoles, imidazolium, pyridinium and 4-(dimethylamino)pyridinium compounds substituted with various alkyl side chains and their analogues containing functional groups principally based on OECD guideline 301 D. For the experiments we used two different types of inocula, a freeze-dried mix of bacteria and activated sludge microorganisms from a wastewater treatment plant. The aim of this study was to improve the knowledge base for the structural design of ionic liquids with respect to an increased biodegradability combined with a reduced (eco)toxicological hazard potential. We found a significant primary biodegradation for (eco)toxicologically unfavourable compounds carrying long alkyl side chains (C6 and C8). In contrast for (eco)toxicologically more recommendable imidazolium ionic liquids with short alkyl ((C6) and short functionalised side chains, no biological degradation could be found. The introduction of different functional groups into the side chain moiety thus offering a higher chemical reactivity did not lead to the expected improvement of the biological degradation. After an incubation period of 24 days for the 1-methyl-3-octylimidazolium cation we identified different biological transformation products carrying hydroxyl, carbonyl and carboxyl groups. Furthermore, shortened side chain moieties were identified indicating the degradation of the octyl side chain via b-oxidation. Moreover, we propose an electrochemical wastewater treatment as part of an alternative disposal strategy for non-biodegradable ionic liquids. We show for the first time that the 1-butyl-3-methylimidazolium cation was completely destroyed within four hours using an electrolysis double-cell (volume = 1.2 L) equipped with electrodes made of iridium oxide (anode), stainless steel (cathode), and a boron-doped diamond-coated bipolar electrode. The products formed electrochemically were easily accessible to biological degradation.

To demonstrate how baseline toxicity can be separated from other more specific modes of toxic action and to address possible pitfals when dealing with hydrophobic substances, the four isothiazol-3-one biocides N-methylisothiazol-3-one (MIT), 5-chloro-N-methylisothiazol-3-one (CIT), N-octylisothiazol-3-one (OIT), and 4,5-dichloro-N-octylisothiazol-3-one (DCOIT) as an example for reactive electrophilic xenobiotics were tested for their cytotoxic effects on the human hepatoblastoma cell line Hep G2, on the marine bacterium Vibrio fischeri, and on the limnic green alga Scenedesmus vacuolatus. In each of the three test systems, toxic effects were observed in a consistent pattern. The two chlorinated compounds and OIT were found to be significantly more toxic than MIT. As compared to baseline toxicants, the small and polar MIT and CIT exhibited pronounced excess toxicity in each of the three test systems that is presumably triggered by their intrinsic reactivity toward cellular thiols. In contrast, OIT and DCOIT showed mainly toxicities that could be explained by their hydrophobicity. Analyzing and comparing these results using the toxic ratio concept and with data that indicate a dramatic depletion of cellular glutathione levels after incubation with DCOIT reveals that for highly hydrophobic substances, baseline level toxicity in an assay for acute toxicity can lead to an oversight of other more specific modes of toxic action that may cause significant effects that might be less reversible than those caused by unreactive baseline toxicants. This possibility should be taken into account in the hazard assessment of chemicals that are both hydrophobic and reactive.