Ultratrace determination of metal ions using graphene oxide/carbon nanotubes loaded cellulose membranes and total-reflection X-ray fluorescence spectrometry: A green chemistry approach

In this paper, the determination of ultratrace heavy metal ions was developed by combining a preconcentration method using graphene oxide/carbon nanotubes membranes (GO/CNTs) and total-reflection X-ray fluorescence spectrometry (TXRF). Due to the excellent adsorptive properties of the GO, the foregoing membranes are suitable for effective simultaneous sorption of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) from aqueous solutions. In this method, the aqueous solution is passed through the GO/CNTs membrane. The analytes are eluted from the GO and afterward transferred onto a siliconized quartz reflector for further TXRF analysis using W and Mo target X-ray tubes. The maximum recoveries for all the elements were obtained at pH 5; thus it was chosen for all further experiments. The face centered central composite design was performed to study the influence of the flow-rate and volume of the solution on the recovery of the determined metal ions. Recovery values higher than 96% for all studied metals allow performing efficient preconcentration with an enrichment factor of 133, achieving the limits of detection (LODs) in the range of 0.08–0.21 ng mL−1 for W target X-ray tube with a measurement time of 2000 s, and much lower LODs for Mo target X-ray tube: 0.001–0.002 ng mL−1 with the exception for Cd (0.11 ng mL−1) with a very short measurement time of 600 s. Certified reference materials of spring water and seawater were examined to verify the reliability of the method. The evaluated procedure does not require toxic reagents or organic solvents, thus minimizes the portion of the sample for TXRF measurement, and stands in good accordance with green analytical chemistry basic principles.The project was supported by the National Science Centre (Poland) by the Grants No. 2018/31/B/ST4/00041 and No. 2015/17/B/ST4/03870. This work was also supported by the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S). Marcin Musielak thanks the Program for new interdisciplinary elements of education at the doctoral level for a field of chemistry project (POWR.03.02.00-00-I010/17) for the support.Peer reviewe