Development of a Dispersive Liquid-Liquid Aerosol Phase Extraction Method for the Quantification of Ag, Cd, Cu, Ni, and Pb in Seawater by Inductively Coupled Plasma Optical Emission Spectroscopy.

The dispersive liquid-liquid aerosol phase extraction (DLLAPE) method was applied for the determination of Ag, Cd, Cu, Ni, and Pb in seawater samples by inductively coupled plasma optical emission spectroscopy (ICP-OES). Key parameters such as sample pH and extractant concentration were systematically evaluated, with ammonium ,'-diethyldithiophosphate (DDTP) identified as the optimal chelating agent. Optimal extraction conditions were achieved at pH 2.5 for Ag, Cu, Ni, and Pb, while Cd extraction efficiency was found to be pH independent. The extractant concentration did not greatly improve the extraction efficiency. Furthermore, the influence of nebulizer gas flow rate and extraction time was evaluated, achieving the maximum extraction yield at 0.6 L min and 120 s, respectively. The method was evaluated for accuracy and bias through recovery studies, and the results showed that most elements had recovery rates close to 100% with relative standard deviation values in between 3 and 9%. However, in the case of Ag and Ni, 1.184 and 1.089 correction factors were, respectively, applied to compensate for the bias. Moreover, the procedural limits of quantification (pLOQs) found for Ag, Cd, Cu, Ni, and Pb were 0.4, 0.14, 0.2, 0.2, and 0.2 μg L, respectively. The in-house validation of the method provided expanded uncertainty values lower than 6% for all elements except for Ag (16.6%). Finally, the application of the method to real seawater samples from coastal areas in Alicante and San Juan (Spain) confirmed its suitability for trace metal analysis in complex marine matrices, underscoring its potential for environmental monitoring and research.