In this paper the combination of dispersive micro solid-phase extraction (DMSPE), using multiwalled carbon nanotubes (MWCNTs) as solid sorbents, with total-reflection X-ray fluorescence spectrometry (TXRF) is proposed for preconcentration and determination of lead and cadmium ions in water samples. The proposed sample preparation is quite simple and economic. After the sorption processes of the metals on the MWCNTs, the aqueous sample is separated by centrifugation and the metal loaded MWCNTs are suspended using a small volume of an internal standard solution and analyzed directly by TXRF. Parameters affecting the extraction process (complexing agent, pH of the aqueous sample, amount of MWCNTs) and TXRF analysis (volume of the deposited suspension on the reflector, drying mode, and instrumental parameters) have been carefully evaluated to test the real capability of the developed methodology for the determination of Cd and Pb at trace levels. For both elements the linear range is observed up to 50 ng mL⁻¹. Under optimized conditions detection limits are 1.0 ng mL⁻¹ and 2.1 ng mL⁻¹ for Cd(II) and Pb(II) ions, respectively. Both of the examined elements can be determined with quantitative recoveries (ca. 100%) and with an adequate precision (RSD = 6.0% and 10.5% for Cd(II) and Pb(II), respectively). Our results give insight into the possibilities of the combination of DMSPE and TXRF for trace metal determination in different types of environmental waters (sea, river and waste water).

A novel and selective sorbent for micro-solid phase extraction was synthesized by chemical functionalization of graphene oxide with glycine. The structure of this nanomaterial, referred to as GO-Gly, was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. GO-Gly was used for preconcentration of chromium, zinc, and copper ions from water samples prior to their determination by energy dispersive X-ray fluorescence spectrometry (EDXRF). The proposed procedure is based on dispersion of micro amounts of GO-Gly in aqueous samples. After adsorption of metal ions on its surface, samples were filtered under vacuum and then membrane filters were directly submitted to energy dispersive X-ray fluorescence spectrometric measurements. In order to obtain optimal preconcentration conditions, some parameters affecting sorption process, such as pH, amount of GO-Gly, sorption times, and sample volume, were examined. Under optimal conditions the calibration curves were linear in a 1–150 ng mL⁻¹ range with recoveries higher than 97%. The obtained detection limits for Cr(III), Zn(II), and Cu(II) determinations are 0.15, 0.07, and 0.08 ng mL⁻¹, respectively. A relative standard deviation of the proposed procedure (at a 10 ng mL⁻¹ level for n = 10) is lower than 2.3%. The proposed method was successfully applied for determination of Cr(III), Zn(II), and Cu(II) ions in water samples.