Ionic liquid solvent bar micro-extraction of CdCl_n^(n-2)- species for ultra-trace Cd determination in seawater

Water analysis of trace metals has been benefited by recent studies on sample preparation by liquid micro-extraction. However, there are still limitations for its application to seawater, such as the need of additives to preserve the sample or the availability of chemical extractants for the selective extraction from highly saline samples. In this work, a three phase solvent bar micro-extraction (3SBME) system containing the ionic liquid trioctylmethylammonium chloride (Aliquat^® 336) has been used for isolation and pre-concentration of Cd from seawater samples, due to its ability for ionic exchange of CdCl_n^(n-2)-. The system was optimized to work at the natural pH of seawater, and conditions for application to real samples were 0.18 M Aliquat^® 336 dissolved in kerosene with 0.25 M dodecan-1-ol as organic solution, 1.5 M HNO₃ as acceptor solution, 60 min extraction time, and 800 rpm stirring speed in the sample. Loss of organic solution into the sample during extraction was evaluated and revealed its dependence on stirring rate and extraction time. Under optimum conditions samples containing Cd 0.09-0.90 nM were pre-concentrated 65 times. GF-AAS was used for metal quantification with a limit of detection of 0.04 nM. Accuracy was successfully evaluated measuring Cd in a seawater certified reference material BCR-403.