Episodic surges in titanium dioxide engineered particle concentrations in surface waters following rainfall events

Quantifying and characterizing engineered particles in environmental systems is key for assessing their risk but remains challenging and requires the distinction between natural and engineered particles. The objective of this study was to characterize and quantify the concentrations of titanium dioxide engineered particles in the Broad River, Columbia, South Carolina, United States during and following rainfall events. The elemental ratio distributions of Ti/Nb, Ti/Fe, and Ti/Al, determined on a single particle basis using inductively coupled plasma-time of flight-mass spectrometry (SP-ICP-TOF-MS), were similar between samples during the different rainfall events, indicating that naturally occurring particles had the same elemental ratios and origin. Therefore, the changes in the Ti/Nb ratios in the bulk water samples were attributed to the introduction of titanium dioxide engineered particles into the Broad River with urban runoff during and following rainfall events. The total concentrations of Ti, Fe, Al, Nb, Ce, and La in the Broad River followed the same trend of rise and fall as the discharge/runoff. The elemental ratios of Ti/Nb were higher (e.g., 330 to 565) than the average crustal values (e.g., 320) and the natural background elemental ratios in surface waters in Columbia, SC (e.g., 266.4 ± 8.9), suggesting contamination with titanium dioxide engineered particles. The concentration of titanium dioxide engineered particles were estimated by mass balance calculations using total titanium concentrations and increases in Ti/Nb ratios above the natural background ratios. The concentrations of titanium dioxide engineered particles in the Broad River varied between 20 and 140 μg TiO₂ L^-1 following rainfall events. The source of titanium dioxide was attributed to urban runoff due to the absence of sewage contamination as indicated by the low size of the gadolinium anomaly. The findings of this study demonstrate that urban runoff is a major source of titanium dioxide engineered particles to urban rivers, which results in episodic high concentrations of titanium dioxide engineered particles, which may pose environmental risks during and following rainfall events. This study also highlights the importance of determining the temporal variations in engineered particle concentrations in surface waters for a more comprehensive risk assessment of engineered particles.