Fully-Automated Fluorimetric Determination of Aluminum in Seawater by In-Syringe Dispersive Liquid-Liquid Microextraction Using Lumogallion

A sensitive and selective automated in-syringe dispersive liquid-liquid microextraction (DLLME) method is presented. It was successfully applied to the determination of aluminum in coastal seawater samples. The complete analytical procedure including sampling, buffering, reaction of the analyte with fluorescence reagent lumogallion (LMG), extraction, phase separation, and quantification was completely automized and carried out within 4 min. DLLME was done using n-hexanol as an extracting solvent and ethanol as a dispersing solvent in a 1:8 v/v percent mixture. The Al-LMG complex was extracted by an organic solvent and separated from the aqueous phase within the syringe of an automated syringe pump. Two devices were specially developed for this work. These were (a) the fluorescence detector and accompanying flow cell for the organic phase enriched with the reaction product and (b) a heating device integrated into the holding coil to accelerate the slow reaction kinetics. The limits of detection (3 sigma) and quantification (10 sigma) were 8.0 +/- 0.5 nmol L-1 and 26.7 +/- 1.6 nmol L-1, respectively. The relative standard deviation for eight replicate determinations of 200 nmol L-1 Al3+ was <1.5%. The calibration graph using the preconcentration system was linear up to 1000 nmol L-1 with a correlation coefficient of 0.999. Ambient concentrations of samples were quantifiable with found concentrations ranging from 43 to 142 nmol L-1. Standard additions gave analyte recoveries from 97% to 113% proving the general applicability and adequateness of the analyzer system to real sample analysis.