A novel approach for determining total titanium from titanium dioxide nanoparticles suspended in water and biosolids by digestion with ammonium persulfate

Titanium dioxide (i.e. TiO2) in nano-form is a constituent of many nanomaterials that are used in sunscreens, cosmetics, industrial products and in biomedical applications. Quantification of TiO2 nanoparticles in various matrixes is a topic of great interest for researchers studying the potential health and environmental impacts of nanoparticles. However, analysis of TiO2 as Ti4+ is difficult because current digestion techniques require use of strong acids that may be a health and safety risk in the laboratory. To overcome this problem, we developed a new method to digest TiO2 nanoparticles using ammonium persulfate as a fusing reagent. The digestion technique requires short times to completion and optimally requires only 1 g of fusing reagent. The fusion method showed >95% recovery of Ti4+ from 6 μg mL−1 aqueous suspensions prepared from 10 μg mL−1 suspension of different forms of TiO2, including anatase, rutile and mixed nanosized crystals, and amorphous particles. These recoveries were greater than open hot-plate digestion with a tri-acid solution and comparable to microwave digestion with a tri-acid solution. Cations and anions commonly found in natural waters showed no significant interferences when added to samples in amounts of 10 ng to 110 mg, which is a much broader range of these ions than expected in environmental samples. Using ICP-MS for analysis, the method detection limit (MDL) was determined to be 0.06 ng mL−1, and the limit of quantification (LOQ) was 0.20 ng mL−1. Analysis of samples of untreated and treated wastewater and biosolids collected from wastewater treatment plants yielded concentrations of TiO2 of 1.8 and 1.6 ng mL−1 for the wastewater samples, respectively, and 317.4 ng mg−1 dry weights for the biosolids. The reactions between persulfate ions and TiO2 were evaluated using stoichiometric methods and FTIR and XRD analysis. A formula for the fusing reaction is proposed that involves the formation of sulfate radicals.

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► Formation of radical sulfate during the fusion process.
► Acquiring better results than mix acid including hydrofluoric acid.
► Faster process than microwave and hot plate methods of digestion.
► Applicable to both inorganic and organic samples.