Dispersive liquid–liquid microextraction combined with laser-induced breakdown spectrometry and inductively coupled plasma optical emission spectrometry to elemental analysis

• Environmentally friendly spectrometric method for elemental analysis.
• Combination of DLLME with ICP OES and LIBS.
• Elemental analysis in beverage samples after microextraction procedure.
• Sensitive analysis of liquid sample by LIBS combining it with DLLME.

In this paper, two analytical methodologies based on the combination of dispersive liquid–liquid microextraction with inductively coupled plasma optical emission spectrometry and laser-induced breakdown spectrometry, respectively, were evaluated for simultaneous preconcentration and detection of Cd, Co, Ni, Pb and Zn. The microextraction procedure was based on the injection of appropriate quantities of 1-undecanol and methanol into the sample solution containing the complexes formed between metal ions and 1-(2-pyridylazo) 2-naphtol (PAN). The main experimental factors affecting the complexation and the extraction of metals (pH, PAN concentration, salt addition and extractant solvent and disperser solvent volume) were optimized using a multivariate analysis consisting of two steps: a Plackett-Burman design followed by a Circumscribed Central Composite Design (CCCD). Under optimum microextraction conditions, the analytical features of the proposed methodologies were assessed. Accuracy was evaluated by analyzing two certified reference materials, yielding results in agreement with the certified values. Both methodologies were applied to the analysis of a number of beverage samples.