Dispersive micro solid-phase extraction (DµSPE) with graphene oxide as adsorbent for sensitive elemental analysis of aqueous samples by laser induced breakdown spectroscopy (LIBS)

In this work, the combination of dispersive micro solid-phase extraction (DµSPE) with laser-induced breakdown spectroscopy (LIBS) was evaluated for simultaneous preconcentration and detection of Zn, Cd, Mn, Ni, Cr and Pb in aqueous samples. Two adsorbent materials were tested in the microextraction step, namely graphene oxide and activated carbon. In both cases, the microextraction process consisted in the dispersion of a small quantity of adsorbent in the sample solution containing the analytes. However, while the use of activated carbon required a previous chelation of the metals, this step was avoided with the use of graphene oxide. After extraction, the analytes retained in the adsorbents were analysed by LIBS. Several experimental factors affecting the extraction of the metals (adsorbent amount, pH and extraction time) were optimized by means of the traditional univariate approach. Under optimum microextraction conditions, the analytical features of the proposed DµSPE-LIBS methods were assessed, leading to limits of detection below 100 µg kg−1 and 50 µg kg−1 with the use of activated carbon and graphene oxide, respectively, as adsorbents in the DµSPE process. Trueness evaluation of the most sensitive procedure was carried out by spike and recovery experiments in a real sample of tap water, leading to recovery values in the range 98–110%. This work was supported by the Spanish Ministry of Economy and Competitiveness, (Spain) (Project no. CTQ2016-79991-R and fellowship number BES-2012-058759 (FPI-MICINN)); the Regional Government of Valencia (Spain) (Project no. PROMETEO/2013/038); and the University of Alicante, (Spain) (Grant no. UAUSTI16-04).