An on-line system employing switchable-hydrophilicity solvent-based liquid-phase microextraction (SHS-LPME) is described in this work. The method is based on the preconcentration of the species formed between cobalt and the reagent 1-nitroso-2-naphthol (NN), with subsequent detection by digital image colorimetry. The system's operation begins with the on-line mixture of sample, switchable solvent, and an alkaline agent in a reaction coil. Then the mixture is transported to an extraction chamber. The introduction of a proton donor leads to the passage of the solvent to its hydrophobic form, which allows phase separation. The rich phase is then directed to a glass tube, where detection is performed. Octanoic acid, sodium carbonate, and sulfuric acid were used as the extraction solvent, the alkaline agent, and the proton donor, respectively. Under optimized conditions, the method presented a detection limit of 0.8 μg L⁻¹ and an enrichment factor of 41. The precision obtained was 4.8% (20 μg L⁻¹). The accuracy of the method was tested by the analysis of Tomato Leaves certified reference material (NIST 1573a). The method was applied to the determination of cobalt in food, dietary supplements, and water samples. The method is presented as a green alternative and very accessible to the determination of cobalt in the analyzed samples.

In this work, an efficient in situ solvent formation microextraction (ISFME) was combined with stopped-flow injection spectrofluorimetry (SFIS) for the determination of copper. In the proposed approach, thiamine was oxidized with copper(II) to form hydrophobic and highly fluorescent thiochrome (TC), which was subsequently extracted into ionic liquid as an extractant phase. A small amount of an ion-pairing agent (NaPF₆) was added to the sample solution containing a water-miscible ionic liquid ([Hmim][BF₄]) to obtain a hydrophobic ionic liquid ([Hmim][PF₆]), which acted as the extraction phase. After centrifuging, phase separation was performed and the enriched analyte was determined by SFIS. ISFME is an efficient method for separation and preconcentration of metal ions from aqueous solutions with a high ionic strength. Variables affecting the analytical performance were studied and optimized. Under optimum experimental conditions, the proposed method provided a limit of detection (LOD) of 0.024μgL⁻¹ and a relative standard deviation (RSD) of 2.1%. The accuracy of the combined methodology was evaluated by recovery experiments and by analyzing certified reference material (GBW 07605 Tea). Finally, the proposed method was successfully applied to copper determination in water and food samples.