Integrated Modeling of U.S. Agricultural Soil Emissions of Reactive Nitrogen and Associated Impacts on Air Pollution, Health, and Climate.

Agricultural soils are leading sources of reactive nitrogen (Nr) species including nitrogen oxides (NOx), ammonia (NH3), and nitrous oxide (N2O). The propensity of NOx and NH3 to generate ozone and fine particulate matter and associated impacts on health are highly variable, whereas the climate impacts of long-lived N2O are independent of emission timing and location. However, these impacts have rarely been compared on a spatially resolved monetized basis. In this study, we update the nitrogen scheme in an agroecosystem model to simulate the Nr emissions from fertilized soils across the contiguous United States. We then apply a reduced-form air pollution health effect model to assess air quality impacts from NOx and NH3 and a social cost of N2O to assess the climate impacts. Assuming an $8.2 million value of a statistical life and a $13,100/ton social cost of N2O, the air quality impacts are a factor of ∼7 to 15 times as large as the climate impacts in heavily populated coastal regions, whereas the ratios are closer to 2.5 in sparsely populated regions. Our results show that air pollution, health, and climate should be considered jointly in future assessments of how farming practices affect Nr emissions.

Meteorological based parameters and ozone exceedances in Houston and other cities in Texas.

In the Houston-Galveston-Beaumont (HGB) region considerable scientific effort has been directed at elucidating the relationships among atmospheric circulations and urban mixed-layer ozone concentrations. These studies of the HGB region have provided guidance on the conditions that are used herein to identify specific meteorological parameters that relate with observed exceedances of the National Ambient Air Quality Standard for ozone. These parameters were developed using 15 years of ozone concentrations and localized wind conditions enhanced by incorporating data from a private monitoring network. Using these data, several key parameters were found that described the most common meteorological conditions for an exceedance day in HGB. The most relevant parameters included: the wind direction at midnight, wind speeds from 0 to 6 LST, and the extent of wind direction rotation in a 24-hour period. These parameters, and the meteorological conditions they describe, were also found to occur in an analysis of observational data throughout the state of Texas suggesting large scale forces beyond the influence of a sea breeze. A mixed layer model was developed and shown to illustrate the large-scale synoptic forces found in the observational data. The meteorological parameters, and conditions they describe, could be part of a diagnostic model performance evaluation to assure that accurate predictions of ozone for Texas were not the result of compensating errors.Implications: This study identified meteorological-based parameters that coincided with observed exceedances of the National Ambient Air Quality Standard for ozone across the state of Texas. These parameters can be used in support of regulatory model performance evaluations to assure accuracy in predicting ozone conducive conditions. In Houston, the vast majority of meteorlogical ozone conducive days did not produce an exceedance, suggesting other as yet unidentified conditions that are necessary such as an intermittent emission of precursors.

Predicting secondary organic aerosol phase state and viscosity and its effect on multiphase chemistry in a regional-scale air quality model.

Atmospheric aerosols are a significant public health hazard and have substantial impacts on the climate. Secondary organic aerosols (SOAs) have been shown to phase separate into a highly viscous organic outer layer surrounding an aqueous core. This phase separation can decrease the partitioning of semi-volatile and low-volatile species to the organic phase and alter the extent of acid-catalyzed reactions in the aqueous core. A new algorithm that can determine SOA phase separation based on their glass transition temperature (T g), oxygen to carbon (O : C) ratio and organic mass to sulfate ratio, and meteorological conditions was implemented into the Community Multiscale Air Quality Modeling (CMAQ) system version 5.2.1 and was used to simulate the conditions in the continental United States for the summer of 2013. SOA formed at the ground/surface level was predicted to be phase separated with core-shell morphology, i.e., aqueous inorganic core surrounded by organic coating 65.4 % of the time during the 2013 Southern Oxidant and Aerosol Study (SOAS) on average in the isoprene-rich southeastern United States. Our estimate is in proximity to the previously reported ~ 70 % in literature. The phase states of organic coatings switched between semi-solid and liquid states, depending on the environmental conditions. The semi-solid shell occurring with lower aerosol liquid water content (western United States and at higher altitudes) has a viscosity that was predicted to be 102-1012 Pa s, which resulted in organic mass being decreased due to diffusion limitation. Organic aerosol was primarily liquid where aerosol liquid water was dominant (eastern United States and at the surface), with a viscosity < 102 Pa s. Phase separation while in a liquid phase state, i.e., liquid-liquid phase separation (LLPS), also reduces reactive uptake rates relative to homogeneous internally mixed liquid morphology but was lower than aerosols with a thick viscous organic shell. The sensitivity cases performed with different phase-separation parameterization and dissolution rate of isoprene epoxydiol (IEPOX) into the particle phase in CMAQ can have varying impact on fine particulate matter (PM2.5) organic mass, in terms of bias and error compared to field data collected during the 2013 SOAS. This highlights the need to better constrain the parameters that govern phase state and morphology of SOA, as well as expand mechanistic representation of multiphase chemistry for non-IEPOX SOA formation in models aided by novel experimental insights.

α-Pinene-Derived Organic Coatings on Acidic Sulfate Aerosol Impacts Secondary Organic Aerosol Formation from Isoprene in a Box Model.

Fine particulate matter (PM2.5) is known to have an adverse impact on public health and is an important climate forcer. Secondary organic aerosol (SOA) contributes up to 80% of PM2.5 worldwide and multiphase reactions are an important pathway to form SOA. Aerosol-phase state is thought to influence the reactive uptake of gas-phase precursors to aerosol particles by altering diffusion rates within particles. Current air quality models do not include the impact of diffusion-limiting organic coatings on SOA formation. This work examines how α-pinene-derived organic coatings change the predicted formation of SOA from the acid-catalyzed multiphase reactions of isoprene epoxydiols (IEPOX). A box model, with inputs provided from field measurements taken at the Look Rock (LRK) site in Great Smokey Mountains National Park during the 2013 Southern Oxidant and Aerosol Study (SOAS), was modified to incorporate the latest laboratory-based kinetic data accounting for organic coating influences. Including an organic coating influence reduced the modeled reactive uptake when relative humidity was in the 55-80% range, with predicted IEPOX-derived SOA being reduced by up to 33%. Only sensitivity cases with a large increase in Henry's Law values of an order of magnitude or more or in particle reaction rates resulted in the large statistically significant differences form base model performance. These results suggest an organic coating layer could have an impact on IEPOX-derived SOA formation and warrant consideration in regional and global scale models.

Valuing the Air Quality Effects of Biochar Reductions on Soil NO Emissions.

While it is clear that biochar can alter soil N2O emissions, data on NO impacts are scarce. Reports range from 0 to 67% soil NO emission reductions postbiochar amendment. We use regional air quality and health cost models to assess how these soil NO reductions could influence U.S. air quality and health costs. We find that at 67% soil NO reduction, widespread application of biochar to fertilized agricultural soils could reduce O3 by up to 2.4 ppb and PM2.5 by up to 0.15 µg/m3 in some regions. Modeled biochar-mediated health benefits are up to $4.3 million/county in 2011, with impacts focused in the Midwest and Southwest. These potential air quality and health cobenefits of biochar use highlight the need for an improved understanding of biochar's impacts on soil NO emissions. The benefits reported here should be included with estimates of other biochar benefits, such as crop yield increase, soil water management, and N2O reductions.