Coupling dispersive liquid-liquid microextraction to inductively coupled plasma atomic emission spectrometry: An oxymoron?

Coupling dispersive liquid-liquid micro-extraction (DLLME) to inductively coupled plasma atomic emission spectrometry (ICP-AES) is usually troublesome due to the limited plasma tolerance to the organic solvents usually employed for metal extraction. This work explores different coupling strategies allowing the multi-element determination by ICP-AES of the solutions obtained after DLLME procedures. To this end, three of the most common extractant solvents in DLLME procedures (1-undecanol, 1-butyl-3-methyl-imidazolium hexafluorophosphate and chloroform) have been selected to face most of the main problems reported in DLLME-ICP-AES coupling (i.e., those arising from the high solvent viscosity and volatility). Results demonstrate that DLLME can be successfully coupled to ICP-AES after a careful optimization of the experimental conditions. Thus, elemental analysis in 1-undecanol and 1-butyl-3-methyl-imidazolium hexafluorophosphate extracts can be achieved by ICP-AES after a simple dilution step with methanol (1:0.5). Chloroform can be directly introduced into the plasma with minimum changes in the ICP-AES configuration usually employed when operating with aqueous solutions. Diluted inorganic acid solutions (1% w w-1 either nitric or hydrochloric acids) have been successfully tested for the first time as a carrier for the introduction of organic extractants in ICP-AES. The coupling strategies proposed have been successfully applied to the multi-element analysis (Al, Cu, Fe, Mn, Ni and Zn) of different water samples (i.e. marine, tap and river) by DLLME-ICP-AES.