Analysis of residual ionic liquids in environmental samples: development of extraction methods

Ionic liquids (ILs) are nowadays emerging as alternative green solvents for various technological applications. In this context, their environmental impacts need to be assessed, and relatively simple and reproducible analytical techniques are required in order to do this. These must be applicable not only to different natural matrices but also to the very low concentrations likely to be present in environmental systems. Moreover, in the case of solid environmental samples, liquid-solid extraction procedures are prerequisite for gaining further insight into IL distribution in these matrices. This paper reports on extraction methods for isolating IL residues from a number of plants, seeds and soils. The efficiency of five organic and inorganic acids in these extractions ranged from 70.2% to 83.5%, depending on the matrix and acid used. IL recovery rates were highest for phosphoric and trifluoroacetic acids. Recoveries of alkylimidazolium IL from all the plant matrices increased with alkyl chain length. The inference from this study is that IL polarity and steric hindrance both influence the mechanism of their sorption onto the plant matrix, which has a significant impact on the extraction efficiency. Saturated ammonium chloride mixed with a large quantity of methanol was the most effective solvent for extracting soil-bound ILs. The extraction efficiency is inversely proportional to the distribution coefficients of particular soils: the higher the value of K(d), the lower the recovery rate. Both methods of extraction were validated for their analytical performance parameters.