Abstract
Sanitary sewer overflows (SSOs) are a common problem across the United States. An estimated 23,000-75,000 SSOs occurred annually in 2004 discharging between 11 and 38 billion liters of untreated wastewater to receiving waters. SSOs release many contaminants, including engineered nanomaterials (ENMs), to receiving water bodies. Measuring ENM concentrations in environmental samples remains a key challenge in environmental nanotechnology and requires the distinction between natural and engineered particles. This distinction between natural and engineered particles is often hampered by the similarities in the intrinsic properties of natural and engineered particles such as particle size, composition, density, surface chemistry, and by the limitations of the available nanometrology tools. To overcome these challenges, we applied a multi-method approach to measure the concentrations and properties of TiO2 engineered particles (e.g., ENMs and pigments) including 1) multi-element single particle-inductively coupled plasma-mass spectrometry (ME-SP-ICP-MS) to identify elemental associations and to determine elemental ratios in natural particles, 2) total elemental concentrations and ratios calculated from total metal concentrations measured following total sample digestion to estimate engineered particle concentrations, and 3) transmission electron microscopy (TEM) to characterize engineered particle size and morphology. ME-SP-ICP-MS analysis revealed that natural TiO2 particles are often associated with at least one of the following elements Al, Fe, Ce, Si, La, Zr, Nb, Pb, Ba, Th, Ta, W and U, and that elemental ratios of Ti to these elements is typical of riverine particulates and the average crustal ratios, except for Pb likely due to anthropogenic Pb contamination. High TiO2 engineered particle concentrations up to 100 μg L-1 were found in SSOs-impacted surface waters. TEM analysis demonstrated the presence of regular-shape TiO2 particles in SSOs-impacted surface waters. This study provides a comprehensive approach for measuring TiO2 engineered particle concentrations in surface waters. The quantitative data produced in this work can be used as input for modeling studies and pave the road toward routine monitoring of ENMs in environmental systems, validation of ENM fate models, and more accurate ENM exposure and risk assessment.