This paper discusses the need for critically evaluating regional-scale (∼200-2,000 km) three-dimensional numerical photochemical air quality modeling systems to establish a model's credibility in simulating the spatio-temporal features embedded in the observations. Because of limitations of currently used approaches for evaluating regional air quality models, a framework for model evaluation is introduced here for determining the suitability of a modeling system for a given application, distinguishing the performance between different models through confidence-testing of model results, guiding model development, and analyzing the impacts of regulatory policy options. The framework identifies operational, diagnostic, dynamic, and probabilistic types of model evaluation. Operational evaluation techniques include statistical and graphical analyses aimed at determining whether model estimates are in agreement with the observations in an overall sense. Diagnostic evaluation focuses on process-oriented analyses to determine whether the individual processes and components of the model system are working correctly, both independently and in combination. Dynamic evaluation assesses the ability of the air quality model to simulate changes in air quality stemming from changes in source emissions and/or meteorology, the principal forces that drive the air quality model. Probabilistic evaluation attempts to assess the confidence that can be placed in model predictions using techniques such as ensemble modeling and Bayesian model averaging. The advantages of these types of model evaluation approaches are discussed in this paper.

Formaldehyde (HCHO) is the most important carcinogen in outdoor air among the 187 hazardous air pollutants (HAPs) identified by the U.S. Environmental Protection Agency (EPA), not including ozone and particulate matter. However, surface observations of HCHO are sparse and the EPA monitoring network could be prone to positive interferences. Here we use 2005-2016 summertime HCHO column data from the OMI satellite instrument, validated with high-quality aircraft data and oversampled on a 5 × 5 km grid, to map surface air HCHO concentrations across the contiguous U.S. OMI-derived summertime HCHO values are converted to annual averages using the GEOS-Chem chemical transport model. Results are in good agreement with high-quality summertime observations from urban sites (-2% bias, r = 0.95) but a factor of 1.9 lower than annual means from the EPA network. We thus estimate that up to 6600-12 500 people in the U.S. will develop cancer over their lifetimes by exposure to outdoor HCHO. The main HCHO source in the U.S. is atmospheric oxidation of biogenic isoprene, but the corresponding HCHO yield decreases as the concentration of nitrogen oxides (NO ≡ NO + NO) decreases. A GEOS-Chem sensitivity simulation indicates that HCHO levels would decrease by 20-30% in the absence of U.S. anthropogenic NO emissions. Thus, NO emission controls to improve ozone air quality have a significant cobenefit in reducing HCHO-related cancer risks.

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

Formaldehyde (HCHO) is an important air pollutant from both an atmospheric chemistry and human health standpoint. This study uses an instrumented photochemical Air Quality Model, CMAQ-DDM, to identify the sensitivity of HCHO concentrations across the United States (U.S.) to major source types and hydrocarbon speciation. In July, biogenic sources of hydrocarbons contribute the most (92% of total hydrocarbon sensitivity), split between isoprene and other alkenes. Among anthropogenic sources, mobile sources of hydrocarbons and nitrogen oxides (NO ) dominate. In January, HCHO is more sensitive to anthropogenic hydrocarbons than biogenic sources, especially mobile sources and residential wood combustion (36% of national hydrocarbon sensitivity). While ozone (O) is three times more sensitive to NO than hydrocarbons across most areas of the U.S., HCHO is six times more sensitive to hydrocarbons than NO, largely due to sensitivity to biogenic precursors and the importance of low-NO chemistry. In winter, both HCHO and O show negative sensitivity to NO (increases with the removal of NO), although O increases are larger. Relative sensitivities do not change substantially across different regions of the country.