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New Potentials in the Extraction of Trace Metal Using Natural Deep Eutectic Solvents (NADES) Natalia Osowska 1 & Lena Ruzik 1 Received: 8 October 2018 / Accepted: 26 December 2018 # The Author(s) 2019

Abstract The aim of the study was to concentrate on developing new solvents for extraction of selected metal complexes from young barley. Estimation of the amount of elements in compound, not only their total concentration, is very important because only a part from total content of metal is absorbed by human organism. At the beginning, the total amount of elements in young barley was established as 16.69 ± 0.22 μg g−1 (RSD 1.36%) for copper, 156.29 ± 0.82 μg g−1 (RSD 0.52%) for manganese, 155.35 ± 1.29 μg g−1 (RSD 0.83%) for zinc, 9.10 ± 0.21 μg g−1 (RSD 2.36%) for molybdenum, and 0.35 ± 0.01 μg g−1 (RSD 1.63%) for cobalt. The LOD of analyzed elements were as follows (μg L−1): Mn 0.59, Co 0.05, Cu 0.33, Zn 1.2, and Mo 0.12. The LOQ of studied metals were as follows (μg L−1): Mn 1.9, Co 0.18, Cu 1.1, Zn 4.0, and Mo 1.4. After that, the most suitable solvents were identified. The determination of total and extractable amount of metals in young barley was carried out by standalone inductively coupled plasma mass spectrometry (ICP-MS). In addition, a complementary analysis of extracted metal complexes was performed using size exclusion chromatography coupled with inductively coupled plasma mass spectrometry (SEC-ICP-MS) method. It was confirmed that the natural deep eutectic solvents (NADES) are able to extract different metal and metal species in comparison with commonly used solvents. The study indicated that extraction by using the NADES has been successfully applied for determination of metals and metal complexes in young barley. Keywords Ionic liquids . NADES . Young barley . ICP-MS

Introduction Deep eutectic solvents (DES) are new class of solvents obtained by mixing solid compounds that are not necessarily salts, such as choline chloride and sugars. Mixing these compounds helps obtaining a eutectic mixture with a melting point much lower than the individual components (Dai et al. 2013b). Over the past two decades, the scientific community has paid much more attention to ionic liquids (ILs) to find a replacement for organic solvents. Ionic liquids are molten salts, liquid at room temperature, whose enormous potential arises from particular characteristics of these liquids, namely, their physicochemical properties (viscosity, density, hydrophilicity, and solubility), which can be tuned by the combination of different cations and anions (Paiva et al. 2014). However, in recent years, * Lena Ruzik [email protected] 1

Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

research studies in solvents have provided an alternative to ILs—the deep eutectic solvents (DES). They may also have an ionic character and consist a mixture of organic compounds with a melting point significantly lower than the individual component (Paiva et al. 2014; Smith et al. 2014). Recently, researcher