Hyphenation of single-drop microextraction with laser-induced breakdown spectrometry for trace analysis in liquid samples: a viability study

In this work, an analytical methodology based on single drop microextraction (SDME) followed by Laser-Induced Breakdown Spectrometry (LIBS) has been tested for trace metal determination in liquid samples. By this method, analytes in the samples were extracted into a small volume of toluene as ammonium pyrrolidinedithiocarbamate (APDC) chelates. After that, the analyte-enriched toluene was dried on a solid substrate and, finally, the resulting solid residue was analyzed by LIBS. Analyte extraction by the SDME procedure was optimized for the first time by using a multivariate optimization approach. Under optimum SDME conditions, analytical figures of merit of the proposed SDME-LIBS methodology were compared to those of the direct LIBS analysis method (i.e., without the SDME procedure). An estuarine water certified reference material was analyzed for method trueness evaluation. The results obtained in this study indicate that SDME-LIBS methodology leads to a sensitivity increase of about 2.0-2.6 times the ones obtained by LIBS. Detection limits of SDME-LIBS decrease according to the obtained sensitivity improvement, reaching values in the range 21-301 mu g kg(-1) for the analytes tested. The measurement repeatability was similar in both SDME-LIBS (13-20% RSD) and LIBS (16-20% RSD) methodologies, mainly limited by the LIBS experimental setup used in this work for LIBS analysis of liquid samples. The SDME-LIBS analysis of the certified reference material led to recovery values in the range of 96% to 112%.