Shannon L. Capps

Epoxide Pathways Improve Model Predictions of Isoprene Markers and Reveal Key Role of Acidity in Aerosol Formation

Isoprene significantly contributes to organic aerosol in the southeastern United States where biogenic hydrocarbons mix with anthropogenic emissions. In this work, the Community Multiscale Air Quality model is updated to predict isoprene aerosol from epoxides produced under both high- and low-NOx conditions. The new aqueous aerosol pathways allow for explicit predictions of two key isoprene-derived species, 2-methyltetrols and 2-methylglyceric acid, that are more consistent with observations than estimates based on semivolatile partitioning. The new mechanism represents a significant source of organic carbon in the lower 2 km of the atmosphere and captures the abundance of 2-methyltetrols relative to organosulfates during the simulation period. For the parametrization considered here, a 25% reduction in SOx emissions effectively reduces isoprene aerosol, while a similar reduction in NOx leads to small increases in isoprene aerosol.

Source attribution of particulate matter pollution over North China with the adjoint method

We quantify the source contributions to surface PM2.5 (fine particulate matter) pollution over North China from January 2013 to 2015 using the GEOS-Chem chemical transport model and its adjoint with improved model horizontal resolution (1/4° × 5/16°) and aqueous-phase chemistry for sulfate production. The adjoint method attributes the PM2.5 pollution to emissions from different source sectors and chemical species at the model resolution. Wintertime surface PM2.5 over Beijing is contributed by emissions of organic carbon (27% of the total source contribution), anthropogenic fine dust (27%), and SO2 (14%), which are mainly from residential and industrial sources, followed by NH3 (13%) primarily from agricultural activities. About half of the Beijing pollution originates from sources outside of the city municipality. Adjoint analyses for other cities in North China all show significant regional pollution transport, supporting a joint regional control policy for effectively mitigating the PM2.5 air pollution.

Decreasing Aerosol Water Is Consistent with OC Trends in the Southeast U.S.

Water is a ubiquitous and abundant component of atmospheric aerosols. It influences light scattering, the hydrological cycle, atmospheric chemistry, and secondary particulate matter (PM) formation. Despite the critical importance of aerosol liquid water, mass concentrations are not well-known. Using speciated ion and meteorological data from the Southeastern Aerosol Research and Characterization network, we employ the thermodynamic model ISORROPIAv2.1 to estimate water mass concentrations and evaluate trends from 2001 to 2012 in urban and rural locations. The purpose of this study is to better understand the historical trends of aerosol liquid water in the southeast U.S. in the context of improved air quality and recently noted reductions in particulate organic carbon (OC). Aerosol water mass concentrations decrease by ∼79% from 2001 to 2012 in the region. Decreases are more prominent in rural than in urban areas. Fractional contribution of water to PM also decreases during the same time period, and this is consistent with recently noted improvements in visibility. These findings agree with the hypotheses that aerosol liquid water facilitates formation of biogenic secondary organic aerosol (SOA) and that biogenically derived SOA is modulated in the presence of anthropogenic perturbations.

Sources and Impacts of Atmospheric NH3: Current Understanding and Frontiers for Modeling, Measurements, and Remote Sensing in North America

Ammonia (NH3) contributes to widespread adverse health impacts, affects the climate forcing of ambient aerosols, and is a significant component of reactive nitrogen, deposition of which threatens many sensitive ecosystems. Historically, the scarcity of in situ measurements and the complexity of gas-to-aerosol NH3 partitioning have contributed to large uncertainties in our knowledge of its sources and distributions. However, recent progress in measurements and modeling has afforded new opportunities for improving our understanding of NH3 and the role it plays in these important environmental issues. In the past few years, passive measurements of NH3 have been added to monitoring networks throughout the USA, now in place at more than 60 stations, while mobile measurements aboard aircrafts and vehicles have provide detailed observations during several recent field campaigns. In addition, new remote sensing observations from multiple satellite instruments have begun to provide vast amounts of NH3 observations throughout the globe. These sources of information have collectively driven new air quality modeling capabilities, by revealing deficiencies in current air quality models and spurring development of mechanistic enhancements to models’ physical representation of the diurnal variability and bidirectional nature of NH3 fluxes. In turn, these advanced models require further observational constraints, as existing NH3 measurements are still limited in spatiotemporal coverage. We thus evaluate the potential value of a new geostationary remote sensing instrument (GCIRI) for providing constraints on NH3 fluxes through multiple Observing System Simulation Experiments (OSSEs).

Differences Between Magnitudes and Health Impacts of BC Emissions Across the United States Using 12 km Scale Seasonal Source Apportionment

Recent assessments have analyzed the health impacts of PM2.5 from emissions from different locations and sectors using simplified or reduced-form air quality models. Here we present an alternative approach using the adjoint of the Community Multiscale Air Quality (CMAQ) model, which provides source-receptor relationships at highly resolved sectoral, spatial, and temporal scales. While damage resulting from anthropogenic emissions of BC is strongly correlated with population and premature death, we found little correlation between damage and emission magnitude, suggesting that controls on the largest emissions may not be the most efficient means of reducing damage resulting from anthropogenic BC emissions. Rather, the best proxy for locations with damaging BC emissions is locations where premature deaths occur. Onroad diesel and nonroad vehicle emissions are the largest contributors to premature deaths attributed to exposure to BC, while onroad gasoline emissions cause the highest deaths per amount emitted. Emissions in fall and winter contribute to more premature deaths (and more per amount emitted) than emissions in spring and summer. Overall, these results show the value of the high-resolution source attribution for determining the locations, seasons, and sectors for which BC emission controls have the most effective health benefits.

Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US

Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2× sulfate, RN/2S ≈ 0.8 to 0.9) with approximately 70% of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in μgm−3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid–liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic–organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C≥0.6) compounds including several isoprene-derived tracers as well as levoglu-cosan but decrease particle-phase partitioning for low O: C, monoterpene-derived species.

Premature deaths attributed to source-specific BC emissions in six urban US regions

Recent studies have shown that exposure to particulate black carbon (BC) has significant adverse health effects and may be more detrimental to human health than exposure to PM2.5 as a whole. Mobile source BC emission controls, mostly on diesel-burning vehicles, have successfully decreased mobile source BC emissions to less than half of what they were 30 years ago. Quantification of the benefits of previous emissions controls conveys the value of these regulatory actions and provides a method by which future control alternatives could be evaluated. In this study we use the adjoint of the Community Multiscale Air Quality (CMAQ) model to estimate highly-resolved spatial distributions of benefits related to emission reductions for six urban regions within the continental US. Emissions from outside each of the six chosen regions account for between 7% and 27% of the premature deaths attributed to exposure to BC within the region. While we estimate that nonroad mobile and onroad diesel emissions account for the largest number of premature deaths attributable to exposure to BC, onroad gasoline is shown to have more than double the benefit per unit emission relative to that of nonroad mobile and onroad diesel. Within the region encompassing New York City and Philadelphia, reductions in emissions from large industrial combustion sources that are not classified as EGUs (i.e., non-EGU) are estimated to have up to triple the benefits per unit emission relative to reductions to onroad diesel sectors, and provide similar benefits per unit emission to that of onroad gasoline emissions in the region. While onroad mobile emissions have been decreasing in the past 30 years and a majority of vehicle emission controls that regulate PM focus on diesel emissions, our analysis shows the most efficient target for stricter controls is actually onroad gasoline emissions.

Quantifying sensitivities of ice crystal number and sources of ice crystal number variability in CAM 5.1 using the adjoint of a physically based cirrus formation parameterization

We present the adjoint of a cirrus formation parameterization that computes the sensitivity of ice crystal number concentration to updraft velocity, aerosol, and ice deposition coefficient. The adjoint is driven by simulations from the National Center for Atmospheric Research Community Atmosphere Model version 5.1 CAM 5.1 to understand the sensitivity of formed ice crystal number concentration to 13 variables and quantify which contribute to its variability. Sensitivities of formed ice crystal number concentration to updraft velocity, sulfate number, and is sufficient but sulfate number concentration is low, indicating a sulfate-limited regime. Outside of the tropics, competition between homogeneous and heterogeneous nucleation may shift annually averaged sensitivities to higher magnitudes, when infrequent strong updrafts shift crystal production away from purely heterogeneous nucleation. Outside the tropics, updraft velocity is responsible for approximately 52.70% of the ice crystal number variability. In the tropics, sulfate number concentration and updraft jointly control variability in formed crystal number concentration. Insoluble aerosol species play a secondary, but still important, role in influencing the variability in crystal concentrations, with coarse-mode dust being the largest contributor at nearly 50% in certain regions. On a global scale, more than 95% of the temporal variability in crystal number concentration can be described by temperature, updraft velocity, sulfate number, and coarse-mode dust number concentration.

Estimating potential productivity cobenefits for crops and trees from reduced ozone with U.S. coal power plant carbon standards

A standard for carbon dioxide emissions from power plants in the United States, known as the Clean Power Plan, has been finalized by the Environmental Protection Agency. Decreases in carbon dioxide emissions from fossil fuel combustion have the potential cobenefit of reductions in emissions of oxides of nitrogen, which contribute to the formation of ground-level ozone. Emissions of ozone precursors may result in elevated ozone concentrations nearby or downwind. Chronic exposure of sensitive vegetation to tropospheric ozone reduces its potential productivity. To evaluate the cobenefits of the Clean Power Plan to sensitive vegetation, we estimate ozone concentrations in the continental U.S. in 2020 with a chemical transport model in accordance with reference and alternative Clean Power Plan policy scenarios, which represent a range of possible approaches to reducing carbon dioxide emissions from power plants. The reductions in biomass, or the potential productivity losses, due to the exposure of 4 crops and 11 tree species to ozone are as large as 1.9% and 32%, respectively, in the reference scenario. The least stringent policy scenario reduces these losses by less than 3% for any given species; however, the scenarios consistent with policies resulting in more rigorous nitrogen oxide reductions produce potential productivity losses lower than the reference scenario by as much as 16% and 13% for individual crops or tree species, respectively. This analysis affords the opportunity to consider public welfare cobenefits of a regulation that is designed to reduce carbon dioxide emissions from power plants.

Assessing near-field and downwind impacts of reactivity-based substitutions.

Abstract Three-dimensional chemical transport modeling of six different solvent substitution test scenarios was used to investigate possible transport effects of using volatile organic compound (VOC) reactivity scales for air quality management purposes with a particular focus on the northeastern United States. The primary issues analyzed are whether uses of reactivity-based substitutions adversely affect ozone concentrations downwind of the area in which they are applied and which reactivity scales appear most appropriate for areas where ozone transport between multiple cities is significant. VOC substitution scenarios were designed to assess biases in ozone metrics associated with substituting relatively highly reactive VOCs (as defined by the Maximum Incremental Reactivity [MIR] scale) associated with solvent use with less reactive VOCs that might be considered as possible substitutes. Aiming to balance industrially realistic and scientifically relevant constraints, the set of solvent emissions to be substituted included toluene, isomers of xylene, 2-butoxyethanol by the surrogate, and lower reactivity compounds 2-methylheptane and n-butyl acetate. For a 14-day episode in August 2002, seven scenarios were modeled including base-case emissions, removal of the selected higher reactivity solvent compounds, and substitution tests using the equivalent mass or equivalent reactivity-adjusted emissions based on the MIR and Maximum Ozone Incremental Reactivity (MOIR) reactivity scales. Results show that downwind increases in ozone concentrations are noticeable for the MIR-based substitution test scenarios although sensitivities demonstrate that these could be used to complement oxides of nitrogen (NOx) controls. However, using the MOIR-scaled substitution test scenario led to results that were less biased, and the population-weighted metric showed little bias compared with the base case. Temporally and spatially extensive decreases are evident with the solvent mass substitution and the selected emissions removal test scenarios, supporting the conclusion that reactivity-based control can be used to regionally reduce ozone.