Photoactive Titanium Dioxide Films with Embedded Gold Nanoparticles for Quantitative Determination of Mercury Traces in Humic Matter-Containing Freshwaters

Mercury detection in humic matter-containing natural waters is often associated with environmental harmful substances for sample preparation. Herein we report an approach based on photoactive titanium dioxide films with embedded gold nanoparticles (AuNP@TiO2 dipstick) for chemical-free sample preparation and mercury preconcentration. For this purpose, AuNPs are immobilized onto a silicon wafer and further covered with a thin photoactive titanium dioxide layer. The AuNPs allow the preconcentration of Hg traces via amalgamation, while TiO2 acts as a protective layer and, at the same time, as a photocatalyst for UV-C radiation-based sample pretreatment. Humic matter, often present in natural waters, forms stabile complexes with Hg and so hinders its preconcentration prior to detection, causing a minor recovery. This problem is solved here by irradiation during Hg preconcentration onto the photoactive dipstick, resulting in a limit of detection as low as 0.137 ng L−1 using atomic fluorescence spectrometry (AFS). A 5 min preconcentration step is sufficient to obtain successful recovery of Hg traces from waters with up to 10 mg L−1 DOC. The feasibility of the approach was demonstrated by the determination of Hg traces in Danube river water. The results show no significant differences in comparison with standard cold vapor-atomic fluorescence spectrometry (CV-AFS) measurements of the same sample. Hence, this new AuNP@TiO2 dipstick provides a single-step sample preparation and preconcentration approach that combines sustainability with high analytical sensitivity and accuracy.

Clay-Humic Substance Composites for Removal of Pharmaceuticals from Water

Humic substances are the main component of soil organic matter and they actively interact with substances in soils, including pollutants. Humic acid-clay mineral composite materials can be considered as prospective and low-cost sorbents for contaminant removal. The aim of this study is to develop clay mineral and humic acid composite materials and to characterise their possible applications. For this research, montmorillonite, kaolinite and bentonite were saturated with three types of humic substances: technical humic acid from lignite, humic substances extracted from raised bog peat (Latvia) and technical K humate from lignite. Obtained sorbents were characterized using FTIR. The sorption was characterised according to the chosen clay mineral and humic acid type and concentration. Comparing the influence of clay minerals and humic substances on humic matter sorption, it has been found that the sorbed amount of humic substances depend on chosen humic substances and/or clay mineral. Obtained sorbents were used for sorption of chlorpromazine. Results indicate that the most perspective sorbents for chlorpromazine removal are bentonite and bentonite modified with humic acid. However, montmorillonite-humic composites also can be used for removal of chlorpromazine from water.