Ambient air observations of hazardous air pollutant (HAPs), also known as air toxics, derived from routine monitoring networks operated by states, local agencies, and tribes (SLTs), are analyzed to characterize national concentrations and risk across the nation for a representative subset of the 187 designated HAPs. Observations from the National Air Toxics Trend Sites (NATTS) network of 27 stations located in most major urban areas of the contiguous United States have provided a consistent record of HAPs that have been identified as posing the greatest risk since 2003 and have also captured similar concentration patterns of nearly 300 sites operated by SLTs. Relatively high concentration volatile organic compounds (VOCs) such as benzene, formaldehyde, and toluene exhibit the highest annual average concentration levels, typically ranging from 1 to 5 µg/m 3 . Halogenated (except for methylene chloride) and semivolatile organic compounds (SVOCs) and metals exhibit concentrations typically 2-3 orders of magnitude lower. Formaldehyde is the highest national risk driver based on estimated cancer risk and, nationally, has not exhibited significant changes in concentration, likely associated with the large pool of natural isoprene and formaldehyde emissions. Benzene, toluene, ethylbenzene, and 1,3-butadiene are ubiquitous VOC HAPs with large mobile source contributions that continue to exhibit declining concentrations over the last decade. Common chlorinated organic compounds such as ethylene dichloride and methylene chloride exhibit increasing concentrations. The variety of physical and chemical attributes and measurement technologies across 187 HAPs result in a broad range of method detection limits (MDLs) and cancer risk thresholds that challenge confidence in risk results for low concentration HAPs with MDLs near or greater than risk thresholds. From a national monitoring network perspective, the ability of the HAPs observational database to characterize the multiple pollutant and spatial scale patterns influencing exposure is severely limited and positioned to benefit by leveraging a variety of emerging measurement technologies.Implications: Ambient air toxics observation networks have limited ability to characterize the broad suite of hazardous air pollutants (HAPs) that affect exposures across multiple spatial scales. While our networks are best suited to capture major urban-scale signals of ubiquitous volatile organic compound HAPs, incorporation of sensing technologies that address regional and local-scale exposures should be pursued to address major gaps in spatial resolution. Caution should be exercised in interpreting HAPs observations based on data proximity to minimum detection limit and risk thresholds.PAPER HISTORY