Aerosol-Phase Extraction Method for Determination of Ca, K, Mg, and Na in Biodiesel through Inductively Coupled Plasma Optical Emission Spectrometry.

A novel extraction method was developed, optimized, and validated for the elemental analysis of organic samples. The method, called aerosol-phase extraction (APE), is based on nebulization of the extracting aqueous solution (0.1 mol·L nitric acid) on the sample. Extraction was performed at the interface of generated extractant droplets as they entered into contact with the samples. Afterward, the phases were allowed to separate and Ca, K, Na, and Mg were determined in aqueous phase by means of inductively coupled plasma optical emission spectroscopy (ICP-OES). Measurement of aerosol characteristics demonstrated that a water-in-oil emulsion was generated. Therefore, once the aqueous solution was dispersed into the sample, the phases spontaneously separated. Furthermore, the interfacial specific surface area exhibited values on the order of 1 m·mL, hence enhancing the extraction kinetics over conventional extraction methods. Key variables affecting the extraction yield were the nebulization gas flow rate, liquid flow rate, extraction time, acid concentration, nebulizer tip to sample surface gap, and m/m ratio. Once the optimal conditions were selected, the method was applied and validated for the determination of Ca, K, Na, and Mg by ICP-OES in 0.5 mL biodiesel samples with an expanded uncertainty lower than 2%. With the APE method, the extraction time was around 1 min, whereas conventional methods employed to perform this kind of extraction required from 4 to 50 min. Additionally, the APE involved preconcentration of analytes, thus lowering the limit of detection (LOD) to the nanograms per milliliter level (i.e., LODs based on the 3s criterion were 32, 20, 19, and 24 ng·mL for Ca, K, Na, and Mg, respectively). Furthermore, accuracy of quantification of Ca, K, Na, and Mg concentration by APE was not significantly different as compared to that afforded by conventional liquid-liquid extraction. Finally, Ca, K, Na, and Mg contents were determined in four real samples in the 0.5-13 mg·kg range. The obtained results were not statistically different from those encountered with a microwave-based digestion method.