P. Vasileva

Chitosan film loaded with silver nanoparticles—sorbent for solid phase extraction of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II)

The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters.

Solid phase extraction and diffusive gradients in thin films techniques for determination of total and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) in Black Sea water

Total dissolved and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) were determined at six locations of the Bourgas Gulf of the Bulgarian Black Sea coast. Solid phase extraction procedure based on monodisperse, submicrometer silica spheres modified with 3-aminopropyltrimethoxysilane followed by the electrothermal atomic absorption spectrometry (ETAAS) was developed and applied to quantify the total dissolved metal concentrations in sea water. Quantitative sorption of Cd, Cu, Ni and Pb was achieved in the pH range 7.5–8, for 30 min, adsorbed elements were easily eluted with 2 mL 2 mol L−1 HNO3. Since the optimal pH for quantitative sorption coincides with typical pH of Black Sea water (7.9–8.2), on-site pre-concentration of the analytes without any additional treatment was possible. Detection limits achieved for total dissolved metal quantification were: Cd 0.002 µg L−1, Cu 0.005 µg L−1, Ni 0.03 µg L−1, Pb 0.02 µg L−1 and relative standard deviations varied from 5–13% for all studied elements (for typical Cd, Cu, Ni and Pb concentrations in Black Sea water). Open pore diffusive gradients in thin films (DGT) technique was employed for in-situ sampling and pre-concentration of the sea water and in combination with ETAAS was used to determine the proportion of dynamic (mobile and kinetically labile) species of Cd(II), Cu(II), Ni(II) and Pb(II) in the sea water. Obtained results showed strong complexation for Cu and Pb with sea water dissolved organic matter. The ratios between DGT-labile and total dissolved concentrations found for Cu(II) and Pb(II) were in the range 0.2–0.4. For Cd and Ni, these ratios varied from 0.6 to 0.8, suggesting higher degree of free and kinetically labile species of these metals in sea water.

Nanomaterials for elemental speciation

Various types of nanomaterials such as magnetic nanoparticles, carbon nanostructures, metal oxides, noble metal nanoparticles, and ion imprinted polymers have been incorporated in new innovative approaches for speciation analysis. Small size, high surface to volume ratio, and high chemical reactivity are the properties which make them ideal sorbents for selective separation of chemical species. Nanostructures based on different modifications of the nanoparticles and combinations between them additionally increased the nano-strategies employed for on-line or off-line determination of particular chemical species of elements. The presented review is focused on the use of nanomaterials for speciation analysis, analytical procedures developed and their application for analysis of environmental, food and biological samples. Critical view points on the current limitations and their future perspective are presented.

Application of Starch-Stabilized Silver Nanoparticles as a Colorimetric Sensor for Mercury(II) in 0.005 mol/L Nitric Acid

A sensitive and selective Hg2+ optical sensor has been developed based on the redox interaction of Hg2+ with starch-coated silver nanoparticles (AgNPs) in the presence of 0.005 mol L−1 HNO3. The relative intensity of the localized surface plasmon absorption band of AgNPs at 406 nm is linearly dependent on the concentration of Hg2+ with positive slope for the concentration range 0–12.5 μg L−1 and negative slope for the concentration range 25–500 μg L−1. Experiments performed demonstrated that metal ions (Na+, K+, Mg2+, Ca2+, Pb2+, Cu2+, Zn2+, Cd2+, Fe3+, Co2+, and Ni2+) do not interfere under the same conditions, due to the absence of oxidative activity of these ions, which guarantees the high selectivity of the proposed optical sensor towards Hg2+. The limits of detection and quantification were found to be 0.9 µg L−1 and 2.7 µg L−1, respectively, and relative standard deviations varied in the range 9–12% for Hg content from 0.9 to 12.5 μg L−1 and 5–9% for Hg levels from 25 to 500 μg L−1. The method was validated by analysis of CRM Estuarine Water BCR505. A possible mechanism of interaction between AgNPs and Hg2+ for both concentration ranges was proposed on the basis of UV-Vis, TEM, and SAED analyses.